WO2018177007A1 - 一种耐消除应力退火的激光刻痕取向硅钢及其制造方法。 - Google Patents

一种耐消除应力退火的激光刻痕取向硅钢及其制造方法。 Download PDF

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WO2018177007A1
WO2018177007A1 PCT/CN2018/074023 CN2018074023W WO2018177007A1 WO 2018177007 A1 WO2018177007 A1 WO 2018177007A1 CN 2018074023 W CN2018074023 W CN 2018074023W WO 2018177007 A1 WO2018177007 A1 WO 2018177007A1
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laser
silicon steel
annealing
oriented silicon
groove
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PCT/CN2018/074023
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English (en)
French (fr)
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赵自鹏
李国保
杨勇杰
吴美洪
马长松
吉亚明
凌晨
谢伟勇
郭建国
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宝山钢铁股份有限公司
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Priority to US16/492,800 priority Critical patent/US11355275B2/en
Priority to RU2019129983A priority patent/RU2721255C1/ru
Priority to KR1020197029635A priority patent/KR102316204B1/ko
Priority to BR112019019990-0A priority patent/BR112019019990B1/pt
Priority to CA3055234A priority patent/CA3055234C/en
Priority to EP18774249.9A priority patent/EP3604565A4/en
Priority to JP2019548294A priority patent/JP6884875B2/ja
Priority to MX2019010751A priority patent/MX2019010751A/es
Publication of WO2018177007A1 publication Critical patent/WO2018177007A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F27/00—Details of transformers or inductances, in general
    • H01F27/24—Magnetic cores
    • H01F27/245—Magnetic cores made from sheets, e.g. grain-oriented
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/362—Laser etching
    • B23K26/364—Laser etching for making a groove or trench, e.g. for scribing a break initiation groove
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
    • C21D8/1222—Hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
    • C21D8/1233—Cold rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1244—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest
    • C21D8/1266—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest between cold rolling steps
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
    • C21D8/1283—Application of a separating or insulating coating
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1294—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a localized treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/06—Etching of iron or steel

Definitions

  • the present invention relates to oriented silicon steel and a method of manufacturing the same, and more particularly to a laser score-oriented silicon steel resistant to stress relief annealing and a method of manufacturing the same.
  • the transformer is a basic component in the power transmission system, and its loss accounts for about 40% of the loss in the power transmission system.
  • the iron core prepared by laminating or winding the oriented silicon steel accounts for about 20% of the total loss in the working state. Core loss is often referred to as iron loss. It can be seen that reducing the iron loss of oriented silicon steel is of great significance to the national economy and environmental protection.
  • Oriented silicon steel is a ferromagnetic material, which is named after its internal grain ⁇ 110 ⁇ 001> orientation is basically the same as that of the steel plate. Since the oriented silicon steel has the best magnetic permeability in the ⁇ 110 ⁇ 001> direction, it is widely used in the manufacture of transformers for power transmission.
  • the magnetic permeability of oriented silicon steel is generally characterized by B8, that is, the magnetic flux density of silicon steel plate under the excitation magnetic field of 800A/m, the unit is T; the iron loss is generally characterized by P17/50, that is, in the silicon steel plate under the alternating excitation field of 50Hz The ineffective electric energy consumed by magnetization when the magnetic flux density reaches 1.7T, the unit is W/kg. Under normal circumstances, B8 and P17/50 characterize the basic performance of oriented silicon steel under the working condition of the transformer.
  • the basic manufacturing process for oriented silicon steel is as follows.
  • a steel material having a certain silicon content is subjected to iron making, steel making, continuous casting, and then subjected to a hot rolling process, and then subjected to two cold rollings with or with intermediate annealing to roll the steel to a target thickness, and then subjected to decarburization annealing to form a primary recrystallized steel sheet having an oxide film on the surface; then a MgO-based release agent is applied to the surface of the steel sheet, and a high temperature annealing of 20 Hr or more is performed to form an oriented silicon steel sheet having a secondary recrystallized structure, which is then subjected to hot drawing and flattening. Annealing, and applying a coating coating and baking process to form a finished oriented silicon steel.
  • the oriented silicon steel sheet has the characteristics of high magnetic inductance and low iron loss, and is particularly suitable for the manufacture of a transformer core.
  • the oriented silicon steel loss is composed of three parts: hysteresis loss, eddy current loss and abnormal eddy current loss.
  • Hysteresis loss is the energy loss caused by magnetic hysteresis caused by inclusions, crystal defects, internal stress and other factors in the magnetization and demagnetization process, causing the magnetic induction to lag behind the magnetic field strength change; eddy current loss It is the energy loss caused by the eddy current caused by the change of the magnetic flux during the magnetization process, which is related to the electrical conductivity and thickness of the silicon steel plate.
  • the abnormal eddy current loss is the energy loss caused by the difference of the magnetic domain structure when the silicon steel plate is magnetized. Affected by the width of the magnetic domain.
  • the magnetic domain structure inside the grain of the oriented silicon steel is formed by the combination of spontaneous magnetization and demagnetizing field, and the magnetic moments of the atoms in the single magnetic domain are arranged in the same direction, so that the macroscopic crystals exhibit ferromagnetism.
  • the magnetic domains of oriented silicon steel are mainly 180° magnetic domains arranged in antiparallel under the condition of no external magnetic field, and the single magnetic domain width can usually reach several tens of micrometers or even several millimeters. A transition layer of tens to hundreds of atomic layers exists between adjacent magnetic domains, which is called a magnetic domain wall.
  • the magnetic moment is driven by the external field, and the magnetic domain wall migration causes the adjacent magnetic domains to be mutually annexed, thereby realizing the magnetic conductive function.
  • Refining the magnetic domain that is, reducing the magnetic domain width, can effectively reduce the abnormal eddy current loss, is an important method to reduce the iron loss of the silicon steel plate, and is also one of the main directions for the advancement of the oriented silicon steel technology.
  • the technique of performing nicking on the surface of oriented silicon steel to refine the magnetic domain and reduce the iron loss can be divided into two categories according to the effect of the nicking: one is the stress-free annealing nick, and the laser beam, the plasma beam, and the electron beam.
  • the method further forms a linear thermal stress region at a certain interval on the surface, so that sub-magnetic domains appear around the region, thereby reducing the magnetic domain width of 180°, thereby achieving the purpose of reducing iron loss.
  • the magnetic domain refining effect of such a method disappears after the stress relief annealing disappears with the thermal stress at the nick, and the iron loss returns to the original level, so it can only be used for the manufacture of laminated core transformers without stress relief annealing;
  • One type is resistant to stress-relieving annealing.
  • the current reported technical means are mechanical, electrochemical corrosion, laser beam, etc.
  • the basic technical solution is to form a linear strain zone on the surface of oriented silicon steel to redistribute its internal energy and reduce it.
  • the 180° magnetic domain width reduces the iron loss.
  • the oriented silicon steel produced by such a method does not recover after the stress relief annealing, so it can be applied to the manufacture of a wound core transformer requiring stress relief annealing.
  • the wound core transformer makes full use of the superiority of the oriented silicon steel to the magnetic properties, and has obvious advantages in terms of loss and noise, so it is favored by downstream users.
  • Resistant stress-relieving annealed oriented silicon steel is particularly suitable for the manufacture of this type of transformer and is the direction of technological advancement.
  • U.S. Patent No. 4,707,720 uses a mechanical pressure method to form a micro-strain region on the surface of the silicon steel. After the stress relief annealing, small grains are formed under the strained region, and the orientation of the small crystal grains is different from the orientation of the substrate, thereby producing a magnetic domain refining effect.
  • U.S. Patent No. 7,066,780 uses a method of electrolytic etching to form a heat-resistant scoring effect. Firstly, the oriented silicon steel plate with the bottom layer is processed by a laser, and the bottom layer is peeled off to expose the metal substrate to the region, and then immersed in the electrolyte to form an electrode pair between the silicon steel plate and the platinum electrode, and the electrode potential is positively and negatively controlled by alternately controlling. Varying, electrolytically etching the substrate causes the region to form a linear groove that is nearly rectangular.
  • U.S. Patent No. 7,045,025 utilizes a laser beam to locally heat the surface of a silicon steel sheet before or after hot drawing flat annealing to form a remelting zone, which melts and solidifies the coating material and a part of the metal matrix to form a remelting zone. Controlling the width and depth of the remelting zone reduces the iron loss of the silicon steel sheet.
  • Chinese patent CN102941413A adopts multiple laser engraving methods to achieve precise control of groove depth and width, which reduces the iron loss of silicon steel sheet by more than 8%.
  • U.S. Patent No. 6,130,139,932 forms a groove having a certain depth on the surface of silicon steel by controlling the energy density of the laser beam. The equiaxed crystal region is formed at the groove to reduce the size of the secondary recrystallized grain and the magnetic domain is refined.
  • Oriented silicon steel heat-resistant scoring technology is to form a series of grooves or strains on the surface of the steel plate by a certain means, so that the magnetic domains are refined and the iron loss is reduced. Since the presence of the groove or strain does not change due to annealing, the iron loss reduction effect does not disappear during the stress relief annealing process, and thus is particularly suitable for the manufacture of a wound core transformer.
  • the heat-resistant scoring technology realized by electrochemical method has complicated process, a certain degree of chemical pollution, and the formed groove shape and depth controllability are poor, and it is difficult to obtain an oriented silicon steel sheet with stable and uniform magnetic properties; mechanical pressure is adopted.
  • the technical solution for forming the groove has extremely high requirements on the toothed roller, and the high hardness of the magnesium silicate under the surface of the oriented silicon steel leads to rapid wear of the toothed roller and high manufacturing cost in a large batch; the groove is formed by laser multiple scanning, and the positioning accuracy is repeated.
  • Oriented silicon steel is named for its inner crystal grains having substantially the same direction, and is an electrical steel sheet having a certain silicon content and having an easy magnetization direction substantially the same as the rolling direction of the manufacturing process.
  • There is a 180° magnetic domain inside the steel plate which is the same or opposite to the direction of easy magnetization of the crystal grain.
  • the magnetic pole in the steel plate moves rapidly through the magnetic domain wall between adjacent magnetic domains, so that it has a good guide. Magnetic properties, the resulting transformer has high magnetic permeability and low iron loss.
  • Constantly reducing the iron loss of silicon steel material is the development direction of silicon steel technology.
  • the metallurgical method is used to control the secondary recrystallization structure and improve the orientation degree to reduce the iron loss. It is possible to make the grain easy magnetization direction coincide with the rolling direction of the steel sheet, that is, to reduce the grain orientation deviation angle; and second, to reduce the iron loss by reducing the magnetic domain width, that is, to refine the magnetic domain. Refining the magnetic domains can reduce the abnormal eddy current loss of the oriented silicon steel.
  • a solution such as the one disclosed in U.S. Patent No. 7,442,260 B2, U.S. Patent No.
  • 5,241,151 A, etc. applies a micro-linear thermal stress region perpendicular to the rolling direction on the surface of the finished oriented silicon steel by means of laser or electron beam, etc., and the stress is perpendicular to the rolling direction in the vicinity thereof.
  • ° Magnetic domain which reduces the magnetic domain width of 180°, thus reducing the iron loss of oriented silicon steel. This kind of product has been widely used in the manufacture of various laminated core transformers.
  • a stress-relieving annealing refinement magnetic domain technique that is, a groove having a certain shape is formed on the surface of the silicon steel sheet by chemical etching or mechanical pressure.
  • the presence of a free magnetic pole at the groove causes the material energy to redistribute, the magnetic domain width decreases, and the iron loss decreases. Since the groove does not change during the stress relief annealing process, the oriented silicon steel sheet produced by this type of technology can be applied to the manufacture of a wound core transformer, collectively referred to as a heat resistant nicking technique.
  • the heat-resistant nicking techniques currently available for commercial use are chemical etching and mechanical scoring.
  • the chemical etching method is a chemical reaction, so the groove uniformity and the process controllability are poor, and the environment is polluted; the technical solution of forming the strain zone by mechanical pressure is due to the high hardness of the silicon steel material.
  • the size of the groove is small, which requires high hardness and processing precision of the mechanical device.
  • U.S. Patent No. 7,045,025 uses a laser processing method to form a hot melt zone. Due to the high melting point of the metal and high thermal conductivity, the edge of the groove will form a crater-like protrusion formed by the melting of the metal, and a metal gasification will be formed in the vicinity to form a cooling and recondensing.
  • the object of the present invention is to provide a laser-scratch-oriented silicon steel sheet which is resistant to stress relief annealing and a manufacturing method thereof, which has low manufacturing cost, and the finished scoring effect does not disappear during the stress relief annealing process, and is particularly suitable for a wound core transformer. Manufacturing.
  • a laser-scratch-oriented silicon steel resistant to stress-relieving annealing adopts laser scoring to form parallel linear grooves on one or both sides of oriented silicon steel, and the linear grooves are perpendicular or at an angle to the rolling direction of the steel plate
  • the maximum height of the edge of the linear groove is not more than 5 ⁇ m
  • the maximum height of the spatter in the unmarked area between adjacent linear grooves is not more than 5 ⁇ m
  • the proportion of the area occupied by the spatter in the vicinity of the linear groove is not more than 5%.
  • the height of the spatter in the non-notch region between the linear grooves is not more than 2 ⁇ m, and the proportion of the area occupied by the spatter in the vicinity of the linear groove is not more than 2.5%.
  • the bottom center line of said linear notch line roughness R a of not more than 2.1 ⁇ m.
  • the bottom center line of said linear notch line roughness R a of not more than 0.52 ⁇ m.
  • the linear groove shape is approximately triangular, trapezoidal, semi-circular or elliptical.
  • the linear groove has an angle of 0-30° with the rolling direction of the steel sheet.
  • the linear groove has a width of 5 to 300 ⁇ m, a groove depth of 5 to 60 ⁇ m, and a spacing between adjacent linear grooves of 1 to 10 mm.
  • the invention relates to a method for manufacturing stress-relieving annealing laser-marked oriented silicon steel according to the present invention, which comprises smelting, continuous casting, hot rolling, primary cold rolling with intermediate annealing, decarburization annealing, high temperature annealing, and hot stretching.
  • Flattening and coating an insulating coating to form a finished oriented silicon steel characterized in that it further comprises a laser scoring step, which is performed before or after the decarburization annealing, or before or after the hot drawing flattening annealing;
  • the nicks include:
  • the film-forming substance of the protective film is a metal oxide powder, and water having a weight percentage of between 0.3% and 5.5%.
  • the protective film has a thickness of between 1.0 ⁇ m and 13.0 ⁇ m.
  • the metal oxide powder is water-insoluble, and is a single powder or a combination of several powders, and the particles having a particle diameter of ⁇ 500 ⁇ m in the powder account for ⁇ 10% by volume.
  • the metal oxide powder is one or a combination of an alkaline earth metal oxide, Al 2 O 3 , ZnO or ZrO.
  • the laser generating pump source type used in the laser scoring step is one or a combination of a CO 2 laser, a solid laser, and a fiber laser, and the laser is continuous or pulsed.
  • the power density I of the laser in the laser scoring step is not less than 1.0 ⁇ 10 6 W/cm 2
  • the average energy density e 0 is between 0.8 J/mm 2 and 8.0 J/mm 2
  • the average The ratio a of the energy density to the thickness of the protective film is between 0.6 and 7.0.
  • the method for manufacturing the laser-marked oriented silicon steel resistant to stress relief annealing comprises smelting, continuous casting, hot rolling, primary cold rolling with intermediate annealing, decarburization annealing, coating on the surface of the steel sheet.
  • MgO release agent, temperature annealing, hot-drawn flat annealing and coating of an insulating coating to form a finished oriented silicon steel characterized in that after the decarburization annealing, laser scoring is performed, and a series of steel sheets are rolled on the surface of the oriented silicon steel.
  • the invention studies in detail the heat diffusion in the process of laser grooving under different surface states of the silicon steel sheet, and the method of preventing the hot melt and the spatter from adhering to the deposit near the groove, and creatively proposes coating the protective film and the laser on the surface of the oriented silicon steel.
  • the method of manufacturing the heat-resistant score-oriented silicon steel by engraving and then brushing can form a stable and controllable groove by one laser scanning, refine the magnetic domain to reduce iron loss, and does not cause significant degradation of the lamination coefficient, and the iron loss thereof The drop effect does not disappear after stress relief annealing.
  • the inventors observed under a high-speed camera microscope that the edge of the groove is caused by the heat transfer in the process of laser grooving, and the metal in the vicinity of the groove is vaporized by plasma or plasma. The body is rapidly cooled under purging conditions and condensed on the surface of the silicon steel sheet to form.
  • the inventors found a solution to control the edge projection of the groove by applying a laser scribe on the protective film.
  • Figure 2 illustrates the effect of the grooved edge projection on the lamination factor and the scope of the present invention.
  • the edge protrusion height exceeds 5 ⁇ m, the lamination coefficient drops below 95%, which cannot meet the requirements of the transformer core manufacturing process. Therefore, it is necessary to control the height of the groove edge protrusion within 5 ⁇ m.
  • Figure 3 illustrates the range of spatter height, area ratio and lamination factor between adjacent grooves required by the present invention.
  • the lamination coefficient of the oriented silicon steel sheet can be maintained at 95% or more.
  • the silicon steel sheet lamination coefficient will remain above 96%, which is a preferred range of the present invention.
  • the edge protrusion height and the spatter height of the present invention all refer to the maximum height, and Non-average height.
  • the roughness R a of the centerline of the bottom of the groove has an important influence on the uniformity of magnetic properties of the finished silicon steel sheet.
  • the reason for this phenomenon is that the uneven bottom of the groove causes a difference in the magnetic permeability at different positions.
  • the shallower part of the groove has higher magnetic permeability, while the deeper part has more magnetic flux leakage, resulting in lower magnetic permeability, and the magnetic permeability is uneven, resulting in disordered energy field distribution inside the material. ° Sub-domain, iron loss can not be improved.
  • Figure 4 illustrates the rule that the standard deviation of the iron loss P17/50 between silicon steel sheets increases with the increase of Ra .
  • R a exceeds 2.1 ⁇ m
  • the P17/50 standard deviation between silicon steel sheets increases rapidly, exceeding 0.034 W/kg, which greatly increases the uncertainty of the performance of the transformer. Therefore, the center line roughness of the groove bottom is controlled at Within 2.1 ⁇ m.
  • R a is less than 0.52 ⁇ m
  • P17 / 50 dips below 0.013W / kg, good uniformity
  • the present invention is a preferred range.
  • the above-mentioned groove edge protrusion, spatter and the bottom unevenness of the groove are inevitable phenomena due to the inevitable heat fusion or diffusion phenomenon when the laser evaporation ablation material forms the groove.
  • the inventors can effectively control the edge protrusion and the splash deposit of the groove until it completely disappears, the groove is uniform, and the iron loss is remarkably lowered.
  • the method for introducing a protective film before laser scoring of the invention can sufficiently reduce the heat diffusion generated during the laser grooving process, and, for the unavoidable splash material, since it only condenses on the surface of the coating, in the subsequent brushing process As the film is cleaned, it is cleaned up, thus minimizing the formation of surface spatter.
  • the effect of the protective film applied and scored is as shown in FIG. 7, and the finally obtained oriented silicon steel sheet groove after the subsequent brushing is as shown in FIG.
  • the groove has a high flatness, and there is no slag or spatter formed by thermal diffusion in the vicinity, and can be used for the manufacture of a wound core transformer.
  • the protective film material In order to effectively reduce the thermal diffusion during the engraving process, the protective film material needs to have excellent thermal conductivity properties and has a good absorption effect on the laser to fully improve the ablation efficiency of the laser engraving process.
  • the inventors have determined in detail the relevant parameters of the protective film to fully function, including the main components of the protective film, the moisture content, and the particle size distribution of the protective film.
  • the moisture in the protective film has a direct influence on the projections on the edge of the groove. This is because during the laser ablation process, the vaporization and volatilization of the moisture in the protective film can remove heat, provide a directional channel for heat conduction, reduce or even eliminate the diffusion of heat to the edge of the base groove when the groove is formed, and reduce the hot melt layer at the edge. Small, so a uniform and controllable grooved morphology can be formed. However, the presence of excess moisture causes high temperature oxidation of the substrate during ablation, deteriorating magnetic properties, and film thickness is not easily controlled during roll coating or spraying operations.
  • the inventors have determined that the moisture content of not less than 0.3% by weight is favorable for the heat to diffuse through the protective film to form a controllable groove; the weight percentage does not exceed 5.5%, and the high temperature caused by the laser scoring can be effectively controlled. Oxidation.
  • the moisture in the protective film described by the present inventors may exist in the state of free water or crystal water, and when the moisture exists in one form, the weight percentage is the percentage of the weight of the moisture; When both free water and crystal water are present in the protective film, the weight percentage refers to the total weight percentage of the two moistures.
  • the protective film used in the present invention before the scoring is formed by water-soluble metal oxide powder by roll coating or spray coating.
  • the proportion of the particle diameter ⁇ 500 ⁇ m should not exceed 10%. This is because particles of different sizes have different scattering effects on the laser, which directly affects the ablation efficiency of the laser groove.
  • the proportion of particles with a diameter of ⁇ 500 ⁇ m exceeds 10%, the scattering effect of the protective film on the laser is obvious, the laser ablation efficiency is low, and the grooved edge protrusion caused by the thermal melting phenomenon may occur. Therefore, the particle size of the protective film material required by the present invention is such that the proportion of the particles having a diameter of ⁇ 500 ⁇ m cannot exceed 10%.
  • the protective film used in the invention before the laser scoring is that the metal oxide powder is dispersed into water and formed into a slurry by high-speed stirring, coated on the surface of the steel strip by roller coating or spraying, and dried at a temperature of 200 ° C or higher. .
  • the inventors have determined through trial and error that the water-insoluble metal oxide has high dispersibility after high-speed stirring in water, can effectively adhere to the surface of the silicon steel, and carries a certain amount of free water or crystal water, which is beneficial to the outward diffusion of heat during laser scoring. Thereby, a notch groove having a good shape is formed.
  • the water-insoluble metal oxide is preferably an alkaline earth metal oxide, Al 2 O 3 , ZnO or ZrO.
  • the laser power density I used in the present invention must be higher than 1.0 ⁇ 10 6 W/cm 2 .
  • the definition of the laser power density I is as follows:
  • P is the laser output power and S is the spot area containing more than 96% of the beam energy.
  • Figure 5 illustrates the laser power density I and the iron loss improvement rate and lamination coefficient after scoring in the present invention.
  • a power density I of 1.0 ⁇ 10 6 W/cm 2 the iron loss improvement rate and the lamination coefficient both jumped. This is because when the power density I is less than 1.0 ⁇ 10 6 W/cm 2 , the surface absorbance of laser light during laser engraving is very low, most of the laser energy is reflected, and the surface heated region does not reach the vaporization temperature, and the groove is formed. Mainly by melting, a melt is formed at the edge of the score, and finally a side protrusion is formed.
  • the edge protrusion is formed by re-melting and condensing the protective film and the base material, and the subsequent brushing cannot be eliminated.
  • the power density I is equal to or exceeds 1.0 ⁇ 10 6 W/cm 2
  • the laser ablation is mainly gasification, the light absorption rate is greatly improved, and the groove efficiency is remarkably improved.
  • the gasification material is brought out of the notch area by the action of the purge gas and the dust collection system, and a small amount of residual material falls near the groove, and is cleaned together with the protective film in the subsequent brushing process, and finally the groove type is controllable.
  • the groove. Therefore, the laser power density required by the present invention ranges from greater than or equal to 1.0 x 10 6 W/cm 2 .
  • the inventors additionally studied the correlation between the incident laser energy and the magnetic properties of the final product in detail, and found that the two are closely related.
  • the laser energy density e 0 represents the total energy of the laser received per unit area, and its definition is:
  • D y represents the length of the spot along the scanning direction and V s is the laser scanning speed.
  • the laser energy density is too low, less than 0.8J/mm 2 , and the laser ablation stripping material is few, which is not enough to form the effect of refining the magnetic domain; the laser energy density is too high, higher than 8.0J/mm 2 , it will bring Excessive laser energy, on the one hand, the depth of the groove formed is too large to reduce the magnetic sensation, on the other hand, the controllability of the groove is deteriorated, the bottom is not flat, and the edge is prone to melt-formed protrusion.
  • Fig. 6 is an example of a 0.23 mm oriented silicon steel illustrating the beneficial effects of the scope of the present invention.
  • the indentation groove can refine the magnetic domain and reduce the iron loss, the magnetic permeability at the groove is very low, which has a certain damage effect on B8.
  • the inventors have studied in detail the relationship between the groove size and the iron loss and magnetic induction of the silicon steel sheet, and found that in order to reduce the iron loss of the silicon steel sheet and ensure that the B8 is not significantly lowered, the groove size and the spacing need to satisfy the predetermined conditions.
  • the groove width is less than 20 ⁇ m, the scoring is difficult to achieve.
  • the coupling energy between the free magnetic poles on both sides of the groove increases, compensating for the system energy change caused by the magnetic flux leakage, and the magnetic domain cannot be effectively refined.
  • the groove rolling direction exceeds 300 ⁇ m, the groove pitch is too large, the magnetic induction is significantly reduced; the groove depth formed on the substrate is less than 5 ⁇ m, the magnetic domain refining effect is small, and the silicon steel sheet loss is not reduced; The groove depth is greater than 50 ⁇ m, a large number of free magnetic poles lead to more exposed magnetic flux, and the iron loss is not much decreased, but the magnetic induction is obviously reduced.
  • the kerf spacing and the transverse angle of the score line to the steel sheet also significantly affect the iron loss performance and the magnetic induction performance.
  • the adjacent groove is too small, less than 1mm, the groove is too dense, and the magnetic induction is obviously reduced. If the spacing between adjacent grooves is too large, more than 10mm, the refinement magnetic domain cannot be formed in an effective range, and the iron loss can not be improved; the angle between the groove line and the rolling direction of the steel plate is greater than 30°, and the magnetic domain refining effect is weakened.
  • the iron loss improvement rate is very low.
  • the groove conditions suitable for the magnetic domain refinement of the silicon steel sheet to reduce the iron loss without significantly reducing the magnetic induction are: the groove width is between 5 and 300 ⁇ m, the groove depth is between 5 and 60 ⁇ m, and the adjacent groove is The spacing is between 1-10mm.
  • the invention adopts a protective film to realize a method of heat-resistant laser scoring, which is formed by one-scan, and the formed groove exhibits one of an approximately triangular shape, a trapezoidal shape, a semi-circular shape and an elliptical shape in the cross-sectional direction of the steel plate or a deformation thereof, and
  • the scoring lines are arranged in parallel along the steel sheet, all of which fall within the scope of protection of the present invention, and the groove size formed is equivalent to the protection range described in the present invention.
  • FIG. 1 is a macroscopic view showing the formation of a scored linear groove on the surface of an oriented silicon steel by laser scoring of the present invention
  • Figure 3 is a graphical representation of the range of surface area ratios and maximum heights of spatters required by the present invention
  • Figure 5 is a range of laser power density required by the present invention.
  • Figure 6 is a graphical representation of the range of ratios of laser energy density to film thickness required by the present invention.
  • Figure 7 is a surface topography of a laser scoring after the protective film of the present invention.
  • Fig. 8 is a view showing the scoring morphology of the protective film after cleaning in the present invention.
  • the laser-scratch-oriented silicon steel 10 with stress relief annealing forms a parallel linear groove 20 on one or both sides of the oriented silicon steel by laser scoring, and the linear groove and the steel plate
  • the rolling direction is perpendicular or at an angle; the maximum height of the edge of the linear groove is not more than 5 ⁇ m, and the maximum height of the spatter in the non-notched area between adjacent linear grooves is not more than 5 ⁇ m, and the area near the linear groove is splashed.
  • the proportion of the area occupied by the object does not exceed 5%.
  • the bottom center line of said linear notch line roughness R a of not more than 2.1 ⁇ m.
  • the linear groove shape is approximately triangular, trapezoidal, semi-circular or elliptical.
  • the linear groove has an angle of 0-30° with the rolling direction of the steel sheet.
  • the linear groove has a width of 5 to 300 ⁇ m, a groove depth of 5 to 60 ⁇ m, and a spacing between adjacent linear grooves of 1 to 30 mm.
  • the oriented silicon steel is subjected to iron-making, steel-making, continuous casting and hot-rolling processes, and then cold-rolled to a final thickness of 0.23 mm. After decarburization annealing, a surface oxide layer is formed and then the surface is coated with MgO release agent.
  • the unreacted residual MgO was washed away, and then a protective film was formed on the surface by roll coating and drying, and then a YAG laser was used to carry along the steel sheet to perform equidistant linear groove scribing, laser
  • the output power is 2000W
  • the average pulse width is 800ns
  • the focus of the laser on the surface of the steel plate is elliptical
  • the short axis is 0.016mm
  • the long axis is 0.5mm
  • the scanning speed is 50m/s
  • the calculated laser power density is 3.2 ⁇ 10 7 W/cm 2 .
  • the laser energy density is 3.2 J/mm 2 ; the formed score line is perpendicular to the rolling direction of the steel plate, and the distance between the adjacent score lines is 4 mm; then the brushing process is performed to remove the surface protective film and the scatter residue residue. Finally, an insulating coating is applied to the surface thereof and finally annealed to form a finished silicon steel sheet.
  • the magnetic properties were measured by the method of GB/T 3655-2008 measuring the magnetic properties of electrical steel sheets (bands with Epstein squares), using the density, resistivity and electrical properties of GB/T 19289-2003 electrical steel sheets (belts).
  • the measurement method of the lamination coefficient "measures the lamination coefficient, and the measurement results of the examples and the comparative examples are shown in Table 1.
  • Examples 1-10 have better iron loss, magnetic induction and lamination coefficient properties, and the magnetic properties or lamination coefficients of Comparative Examples 1-10 are relatively poor within the scope of the present invention. .
  • Embodiment 2 Influence of center line roughness R a on magnetic performance fluctuation
  • the oriented silicon steel is subjected to iron making, steel making, continuous casting, hot rolling, and then cold rolled to roll the steel sheet to a final thickness of 0.225 mm.
  • a surface oxide layer is formed and a MgO release agent is coated on the surface.
  • annealing at 1200 ° C for 20 hours the unreacted residual MgO was washed away; then a ZnO protective film was formed on the surface by roll coating and dried to a film thickness of 2.5 ⁇ m; then a continuous CO 2 laser was used to roll along the steel sheet.
  • the formed score line is perpendicular to the rolling direction of the steel plate, and the distance between the adjacent score lines is 4.5 mm; then the brushing process is performed to remove the surface protective film and the scatter residue Finally, an insulating coating is applied to the surface thereof and finally annealed to form a finished silicon steel sheet.
  • the magnetic properties were measured by the SST 60 mm ⁇ 300 mm method, and the measurement results of the examples and comparative examples are shown in Table 2.
  • the oriented silicon steel is subjected to iron making, steel making, continuous casting and hot rolling, and then cold rolled to a final thickness of 0.255 mm.
  • the Al 2 O 3 protective film is applied on the surface by spraying, and the Al 2 O 3 particles in the protective film are protected.
  • ⁇ 500 ⁇ m particles account for about 5%; then use the YAG laser with a pulse width of 300 nanoseconds for linear micro-groove scoring, by adjusting the focus spot size, scanning speed, control laser scoring energy, the formed groove Approximate triangle, the angle between the grooved line and the steel plate is 8°, and the distance along the rolling direction is 4mm; then the surface protective film is removed by brushing, after decarburization annealing, the surface oxide layer is formed and the surface is coated with MgO release agent.
  • the coil After the coil is rolled into a steel coil, it is kept under high temperature annealing conditions of 1250 ° C for 20 hours, and finally the residual MgO is washed away, and an insulating coating is applied on the surface thereof and finally annealed to form a finished silicon steel sheet.
  • the magnetic properties were measured by the method of GB/T 3655-2008 measuring the magnetic properties of electrical steel sheets (bands with Epstein squares), using the density, resistivity and electrical properties of GB/T 19289-2003 electrical steel sheets (belts).
  • the measurement method of the lamination coefficient "measures the lamination coefficient, and the measurement results of the examples and the comparative examples are shown in Table 3.
  • the oriented silicon steel is subjected to iron making, steel making, continuous casting and hot rolling, and then cold rolled to a final thickness of 0.195 mm. After decarburization annealing, a surface oxide layer is formed and then the surface is coated with MgO release agent.
  • the control is about 9.5 ⁇ m, and then the YAG laser is used to carry out the equal-space linear groove engraving along the steel plate.
  • the laser output power is 2000W
  • the average width of the single pulse is 800ns
  • the laser spot is focused on the surface of the steel plate with an elliptical shape and a short axis of 0.016.
  • Mm, long axis 0.5mm, scanning speed 50m/s, calculated laser power density is 3.2 ⁇ 10 7 W/cm 2
  • laser energy density is 3.2J/mm 2
  • the score line formed is perpendicular to the rolling direction of the steel plate. The distance between the adjacent score lines is 4 mm; the high temperature annealing is maintained at 1250 ° C for 20 hours, the unreacted residual MgO is washed away, and finally the surface is coated with an insulating coating and finally annealed to form a finished silicon steel sheet.
  • the magnetic properties were measured by the method of GB/T 3655-2008 measuring the magnetic properties of electrical steel sheets (bands with Epstein squares), using the density, resistivity and electrical properties of GB/T 19289-2003 electrical steel sheets (belts).
  • the measurement method of the lamination factor "measures the lamination coefficient, and the measurement results of the examples and the comparative examples are shown in Table 4.
  • the film thickness of the magnesium oxide release agent is controlled to reach the range of energy density and film thickness ratio required by the present invention, so that the magnesium oxide has the functions of a release agent and a protective film, and the residual oxidation is performed after high temperature annealing. Magnesium is washed away with splashing substances.
  • the laser process parameters in the scope of the present invention can obtain a silicon steel sheet with magnetic domain refinement and reduced iron loss, and the laser process or the iron loss or lamination exceeding the scope of the present invention. The coefficient is low.
  • the present invention forms a linear groove on the surface of the steel sheet by means of a protective film covering and a laser scanning. Due to the absorption characteristics of the protective film on the laser, the shape of the formed groove is fully controlled, the iron loss of the obtained silicon steel sheet is significantly reduced, and the lamination coefficient is not significantly deteriorated, and is particularly suitable for the wound core.
  • the manufacture of transformers. The invention has simple process, high production efficiency, high application value and use prospect.

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Abstract

一种耐消除应力退火的激光刻痕取向硅钢板及其制造方法，采用激光刻痕方式在取向硅钢（10）的单面或双面刻痕形成平行线状刻槽（20），该线状刻槽（20）与钢板轧制方向垂直或成一角度；线状刻槽（20）边缘凸起最大高度不超过5μm，相邻线状刻槽（20）之间的无刻痕区域飞溅物最大高度不超过5μm，且线状刻槽（20）附近区域飞溅物所占面积比例不超过5％。其制造成本低，成品刻痕效果在消除应力退火过程中不消失，适用于卷绕铁芯变压器的制造。

Description

一种耐消除应力退火的激光刻痕取向硅钢及其制造方法。 技术领域
本发明涉及取向硅钢及其制造方法，特别涉及一种耐消除应力退火的激光刻痕取向硅钢及其制造方法。
背景技术
近年来，全球能源环境问题日益突出，节能降耗需求在世界范围内不断增长，各国普遍提高了相应设备的能耗标准，降低各类设备对能源的无功消耗。目前，变压器作为电力传输系统中的基本组成部件，其损耗约占电力传送系统中损耗的40％左右。其中，由取向硅钢层叠或卷绕而制成的铁芯，在工作状态下的无功损耗约占总损耗的20％左右。铁芯损耗通常简称为铁损。可见，降低取向硅钢的铁损对国民经济和环境保护具有重大意义。
取向硅钢是一种铁磁材料，以其内部晶粒{110}<001>位向与钢板轧向排列基本一致而得名。由于取向硅钢{110}<001>方向的导磁性最好，因此其被广泛应用于电力传输中变压器的制造。取向硅钢的导磁性一般用B8表征，即在800A/m的激励磁场下硅钢板的磁通密度，单位为T；铁损一般用P17/50表征，即在50Hz的交流励磁场下硅钢板中磁通密度达到1.7T时磁化所消耗的无效电能，单位为W/kg通常情况下，B8和P17/50表征了取向硅钢在变压器工作状态下的基本性能。
取向硅钢的基本制造流程如下。
具有一定硅含量的钢材经过炼铁、炼钢、连铸，而后经过热轧工序，再经过一次或含中间退火的两次冷轧，将钢材轧至目标厚度，之后再经过脱碳退火，形成表面具有氧化膜的初次再结晶钢板；而后在钢板表面涂覆以MgO为主的隔离剂，进行20Hr以上的高温退火，形成具有二次再结晶组织的取向硅钢板，然后再经过热拉伸平整退火，并施以涂层涂覆及烘烤工艺，制成成品取向硅钢。该取向硅钢板具有高磁感、低铁损特点，特别 适用于变压器铁芯的制造。
取向硅钢铁损由磁滞损耗、涡流损耗和反常涡流损耗三部分组成。磁滞损耗是磁化和反磁化过程中，由于材料中夹杂物、晶体缺陷、内应力等因素阻碍磁畴壁运动，造成磁感应强度落后于磁场强度变化的磁滞现象而引起的能量损耗；涡流损耗是磁化过程中磁通改变感生出局部电动势而引起涡电流所造成的能量损耗，与硅钢板的电导率和厚度有关；反常涡流损耗是硅钢板磁化时磁畴结构不同而引起的能量损耗，主要受磁畴宽度影响。
取向硅钢晶粒内部的磁畴结构是自发磁化和退磁场共同作用形成，单一磁畴内部原子磁矩排列方向相同，从而使宏观晶体显示出铁磁性质。取向硅钢的磁畴在无外界磁场条件下主要为反向平行排列的180°磁畴，单一磁畴宽度通常可以达到几十微米甚至数毫米。相邻磁畴间存在着几十到数百个原子层的过渡层，称为磁畴壁。磁化过程中，外场驱动下磁矩转动，磁畴壁迁移使相邻磁畴相互吞并，从而实现导磁功能。细化磁畴，即减小磁畴宽度，可有效降低反常涡流损耗，是降低硅钢板铁损的重要方法，也是取向硅钢技术进步的主要方向之一。
在取向硅钢表面实施刻痕使磁畴细化而降低铁损的技术，根据刻痕的效果可分为两大类：一类是不耐消除应力退火刻痕，通过激光、等离子束、电子束等方式在表面以一定间距形成线状热应力区，使该区域周围出现亚磁畴，从而减小180°磁畴宽度，达到降低铁损的目的。此类方法的磁畴细化效果经过消除应力退火后随刻痕处热应力消除而消失，铁损回复到原来水平，因此只能用于不经消除应力退火的叠片铁芯变压器制造；另一类是耐消除应力退火刻痕，目前报道的技术手段有机械、电化学腐蚀、激光束等，其基本技术方案是在取向硅钢表面形成线状应变区，使其内部能量重新分配，减小180°磁畴宽度，从而降低铁损，此类方法制造的取向硅钢经过消除应力退火后铁损不发生回复，因此能够应用于需消除应力退火的卷绕铁芯变压器的制造。卷绕铁芯变压器充分利用了取向硅钢轧向磁性能的优异性，在损耗和噪音方面均有明显优势，因此受到下游用户的青睐。耐消除应力退火取向硅钢特别适用于该类型变压器制造，是技术进步的方向。
美国专利US4770720采用机械压力方式在硅钢表面形成微应变区，经过消除应力退火后应变区下方形成小晶粒，由于小晶粒的位向与基板位向不同，从而产生磁畴细化效果。
美国专利US7063780利用电解腐蚀的方法形成耐热刻痕效果。首先利用激光对带底层的取向硅钢板进行线状加工，剥离底层使该区域裸露出金属基体，再在电解液中浸泡，使硅钢板和铂电极形成电极对，通过交替控制电极电位正负的变化，电解腐蚀基板使该区域形成接近矩形的线状刻槽。
美国专利US7045025利用激光束在热拉伸平整退火前或后的硅钢板表面进行线状局部加热，形成重熔区，将涂层物质和部分金属基体熔化后再冷却、固化形成重熔区，通过控制重熔区的宽度和深度使硅钢板铁损降低。
中国专利CN102941413A采用多次激光刻槽的方式，实现刻槽深度和宽度的精确控制，使硅钢片铁损下降8％以上。美国专利US20130139932通过控制激光光束能量密度在硅钢表面形成具有一定深度的刻槽，刻槽处形成等轴晶区使二次再结晶晶粒尺寸减小，磁畴得以细化。
取向硅钢耐热刻痕技术是通过一定手段在钢板表面形成一系列刻槽或应变，使磁畴得以细化，铁损降低。由于刻槽或应变的存在不会因退火而发生改变，铁损降低效果不会在消除应力退火过程消失，因此特别适用于卷绕铁芯变压器的制造。
如何高效、低成本的生产耐消除应力退火取向硅钢是钢铁制造企业面临的共同难题，其关键难点在于刻痕刻槽的微观特性和宏观批量制造的不可兼得性。
以往通过电化学方式实现的耐热刻痕技术，工序复杂，存在一定程度化学污染，且形成的刻槽形状、深度可控性较差，不易获得磁性能稳定均匀的取向硅钢片；采用机械压力形成刻槽的技术方案对齿辊要求极高，且取向硅钢表面硅酸镁底层硬度高导致齿辊磨损很快，大批量制造成本高；采用激光多次扫描的方式形成刻槽，重复定位精度要求高，流水线生产面临困难；采用激光热熔融方式形成刻槽或重熔区的方式，易在刻槽边缘及其附近产生火山口状凸起和飞溅物，硅钢片叠片系数下降，且制成变压器 在服役过程中有片间导通的风险。
取向硅钢因其内部晶粒具有大致相同方向而得名，是具有一定硅含量，且其易磁化方向与制造工序轧制方向大致相同的电工钢板。在钢板内部存在着与晶粒易磁化方向相同或反向的180°磁畴，在交流磁化过程中钢板内磁极通过相邻磁畴间的磁畴壁移动而实现快速转动，因此具有良好的导磁性能，所制成变压器导磁效率高，铁损低。
不断降低硅钢材料铁损是硅钢技术的发展方向，现如今公认有两种技术路线降低硅钢片铁损：其一，通过冶金学方法控制二次再结晶组织、提高取向度来降低铁损，尽可能使晶粒易磁化方向与钢板轧向相一致，即减小晶粒取向偏离角；其二，通过减小磁畴宽度的方式来降低铁损，即细化磁畴。细化磁畴可使取向硅钢反常涡流损耗降低。诸如美国专利 US7442260B2、US5241151A等公开的方案，通过激光或电子束等方式在成品取向硅钢表面施加与轧向大致相垂直的微型线状热应力区，应力在其附近区域产生垂直于轧向的90°磁畴，使180°磁畴宽度减小，从而降低取向硅钢的铁损，该类产品已广泛应用于各类叠片铁芯变压器的制造。
随着节能环保的需求越来越高，卷绕铁芯变压器正逐渐受到市场青睐。由于卷绕铁芯的硅钢板是沿钢板轧向卷制而成，充分利用了取向硅钢轧向上磁性能的优异性，因此相比叠片铁芯具有低损耗、低噪音、无剪切废料等优点，特别适用于中小型节能型变压器的制造。但由于铁芯在卷制过程中产生内应力，硅钢板铁损性能劣化，因此铁芯必须要经过消除应力退火。消除应力退火的工艺通常为在保护气氛中经过800℃或以上、不低于2hr的保温，此时材料内部位错完全回复，内应力完全消除，硅钢片磁性能达到最佳状态。采用以往激光或电子束产生线状应力区细化磁畴的取向硅钢板，在经过消除应力退火后细化磁畴效果随应力消失而消失，因此不能用于卷绕铁芯变压器的制造。
为了上述使细化磁畴效果能够在消除应力退火后保持，人们开发了耐消除应力退火细化磁畴技术，即采用化学侵蚀、机械压力等方式在硅钢板表面形成具有一定形状的刻槽，刻槽处产生自由磁极的存在使材料能量重新分配，磁畴宽度减小，铁损降低。由于刻槽在消除应力退火过程中不发生变化，因此采用该类技术生产的取向硅钢板可以应用于卷绕铁芯变压器 的制造，统称为耐热刻痕技术。
目前得到商业化应用的耐热刻痕技术分别为化学侵蚀法和机械刻痕法。采用化学侵蚀方法由于其生产过程属于化学反应，因此刻槽均匀性和过程可控性均较差，并且对环境有一定污染；采用机械压力形成应变区的技术方案，由于硅钢材料硬度很高而刻槽尺寸细小，对机械装置硬度和加工精度要求很高。美国专利US7045025采用激光加工形成热熔融区的方案，由于金属熔点高、导热率高，刻槽边缘会形成因为金属熔化形成的火山口状凸起，附近会产生金属气化后冷却重凝形成的附着性堆积物，降低硅钢片的叠片系数，同时也会增大在制成变压器服役过程中的片间导通风险；中国专利CN102941413A使用多次激光刻痕克服飞溅物导致叠片系数下降的难题，但反复刻痕效率低，重复定位难度大，难以实现工业化流水线的批量生产。
发明内容
本发明的目的在于提供一种耐消除应力退火的激光刻痕取向硅钢板及其制造方法，其制造成本低，成品刻痕效果在消除应力退火过程中不消失，特别适用于卷绕铁芯变压器的制造。
为达到上述目的，本发明的技术方案是：
一种耐消除应力退火的激光刻痕取向硅钢，采用激光刻痕方式在取向硅钢的单面或双面刻痕形成平行线状刻槽，该线状刻槽与钢板轧制方向垂直或成一角度；线状刻槽边缘凸起最大高度不超过5μm，相邻线状刻槽之间的无刻痕区域飞溅物最大高度不超过5μm，且线状刻槽附近区域飞溅物所占面积比例不超过5％。
优选的，所述线状刻槽之间的无刻痕区域飞溅物高度不超过2μm，且线状刻槽附近区域飞溅物所占面积比例不超过2.5％。
优选的，所述线状刻槽底部中心线的线粗糙度R a不超过2.1μm。
优选的，所述线状刻槽底部中心线的线粗糙度R a不超过0.52μm。
优选的，所述线状刻槽形状为近似三角形、梯形、半圆形或椭圆形。
优选的，所述线状刻槽与钢板轧制方向成的角度为0-30°之间。
优选的，所述线状刻槽宽度5～300μm，刻槽深度5～60μm，相邻线状 刻槽之间间距1～10mm。
本发明所述的耐消除应力退火的激光刻痕取向硅钢的制造方法，包括冶炼、连铸、热轧、一次或含有中间退火的两次冷轧、脱碳退火、高温退火、经热拉伸平整退火并涂布绝缘涂层形成成品取向硅钢；其特征是，还包括激光刻痕步骤，所述激光刻痕在脱碳退火前、或在热拉伸平整退火前或后实施；所述激光刻痕包括：
1)在取向硅钢表面形成保护膜；
2)激光刻痕，在取向硅钢表面形成一系列与钢板轧制方向垂直或成一角度的线状刻槽；
3)刷洗取向硅钢表面，移除保护膜并烘干。
优选的，所述保护膜的成膜物质为金属氧化物粉末，及重量百分比介于0.3％～5.5％之间的水。
优选的，所述保护膜的厚度在1.0μm～13.0μm之间。
优选的，所述金属氧化物粉末为非水溶性，为单一粉末或几种粉末的组合，粉末中粒径≥500μm的颗粒占比≤10％体积比。
优选的，所述金属氧化物粉末为碱土金属氧化物、Al 2O 3、ZnO或ZrO中的一种或几种组合。
优选的，所述激光刻痕步骤中采用的激光发生泵源类型是CO 2激光器、固体激光器、光纤激光器中的一种或几种组合，激光为连续式或脉冲式。
优选的，所述激光刻痕步骤中激光的功率密度I不低于1.0×10 6W/cm 2，平均能量密度e 0介于0.8J/mm 2～8.0J/mm 2之间，且平均能量密度与保护膜膜厚的比例a介于0.6～7.0之间。
又，本发明所述的耐消除应力退火的激光刻痕取向硅钢的制造方法，包括冶炼、连铸、热轧、一次或含有中间退火的两次冷轧、脱碳退火、在钢板表面涂覆MgO隔离剂、温退火、经热拉伸平整退火并涂布绝缘涂层形成成品取向硅钢；其特征是，所述脱碳退火后实施激光刻痕，在取向硅钢表面形成一系列与钢板轧制方向垂直或成一角度的线状刻槽。
本发明详细研究了硅钢片不同表面状态下激光刻槽过程中的热扩散，及阻止热熔融和飞溅物在刻槽附近附着堆积的方法，创造性地提出了在取 向硅钢表面涂布保护膜、激光刻槽而后刷洗的方式制造耐热刻痕取向硅钢的方法，可以一次激光扫描形成稳定可控的刻槽，细化磁畴降低铁损，且不会造成叠片系数的显著劣化，其铁损下降效果在经过消除应力退火后不消失。本发明人在高速摄像显微镜下观察发现，刻槽边缘凸起是由于激光刻槽过程中的传热导致部分金属熔化堆积所致，而刻槽附近飞溅物则是被蒸发气化的金属或等离子体在吹扫条件下迅速冷却，凝结在硅钢片表面而形成。发明人通过施加保护膜后激光刻痕的方式，找到了控制刻槽边缘凸起的解决方案。图2说明了刻槽边部凸起对叠片系数的影响规律及本发明范围。边缘凸起高度超过5μm时，叠片系数下降至95％以下，不能满足变压器铁芯制造工艺要求，因此需要将刻槽边缘凸起的高度控制在5μm以内。
图3说明了本发明所要求的相邻刻槽之间的飞溅物高度、所占面积比例与叠片系数的范围。相邻刻槽之间形成的飞溅物高度不超过5μm，且单位面积上飞溅物所占比例不超过5.0％时，可使取向硅钢片叠片系数保持在95％以上。特别的，飞溅物高度不超过2μm，单位面积上飞溅物所占比例不超过2.5％时，硅钢片叠片系数将保持在96％以上，为本发明的优选范围。
需要说明的是，为了防止变压器服役过程中片间由于飞溅物或凸起造成的潜在导通或振动噪音增大风险，本发明所述的边缘凸起高度和飞溅物高度均指最大高度，而非平均高度。
此外，刻槽底部中心线的粗糙度R a对成品硅钢片磁性能均匀性有重要影响。刻槽底部中心线的线粗糙度R a越大，片间磁性能波动也越大。造成这种现象的原因是刻槽底部不均匀导致了不同位置导磁效率有差别。刻槽较浅的部位导磁率较高，而较深的部分则存在较多的漏磁导致磁导率较低，且导磁率不均匀导致材料内部能量场分布紊乱，刻槽附近产生大量非180°亚磁畴，铁损反而得不到改善。图4说明了硅钢片间铁损P17/50的标准差随R a的增加而增大的规律。当R a超过2.1μm时，硅钢片间的P17/50标准差增大迅速，超过0.034W/kg，大大增加制成变压器性能的不确定性，因此需将刻槽底部中心线粗糙度控制在2.1μm以内。特别的，当R a低于0.52μm时，P17/50波动低于0.013W/kg，均匀性良好，是本发明的优选范 围。
上述刻槽边部凸起、飞溅物及刻槽底部不平整均是由于激光蒸发烧蚀材料形成刻槽时，由于不可避免的热熔融或扩散现象所导致的必然现象。本发明人通过调整激光能量和保护膜厚度、含水率及颗粒度参数，可实现刻槽边缘凸起和飞溅堆积物的有效控制，直至完全消失，刻槽均匀，铁损显著降低。
本发明在激光刻痕之前引入保护膜的方法，可以充分减少激光刻槽过程中产生的热扩散，并且，对于不可避免的飞溅物质，由于其仅凝结在覆膜表面，在后续刷洗过程中将随着覆膜的清理而一并被清理，因此最大程度上减少了表面飞溅物的形成。其保护膜施加并刻痕后效果如图7所示，经过后续刷洗后的最终获得的取向硅钢片刻槽如图8所示。刻槽平整度高，附近无热扩散形成的熔渣和飞溅物质等，能够用于卷绕铁芯变压器的制造。
为了有效减少刻槽过程中的热扩散，保护膜材料需要有优异的热导率性质，且对激光有良好的吸收作用，以充分提高激光刻槽过程的烧蚀效率。本发明人通过详细研究确定了保护膜充分发挥作用的相关参量，包括保护膜主要成分、水分含量、形成保护膜的颗粒物大小分布。
本发明人的研究表明，保护膜中的水分对于刻槽边缘的凸起物有直接影响。这是由于在激光烧蚀过程中保护膜中水分气化挥发可带走热量，为热传导提供定向通道，减小甚至消除刻槽时热量向基体刻槽边缘的扩散，使边部热熔融层减小，因此可形成均匀可控的刻槽形貌。但过量水分的存在会造成烧蚀过程中基板的高温氧化，劣化磁性能，且辊涂或喷涂作业时膜厚不易控制。本发明人通过反复试验，确定重量百分比不低于0.3％的水分有利于热量通过保护膜向外扩散，形成可控的刻槽；重量百分比不超过5.5％，可以有效控制激光刻痕造成的高温氧化。需说明的是，本发明人所述及的保护膜中水分，可以以自由水或结晶水状态存在，当水分以其中一种形态存在时，重量百分比即该水分的重量所占百分比里；当保护膜中同时存在自由水和结晶水时，重量百分比是指两种水分的重量百分比总计。
本发明在刻痕前所使用的保护膜为非水溶性的金属氧化物粉末经过辊涂或喷涂的方式形成。其中，粒子直径≥500μm的数量所占比例不能超 过10％。这是因为不同大小的粒子对激光有不同的散射效果，从而直接影响激光刻槽的烧蚀效率。直径≥500μm粒子数量占比超过10％时，保护膜对激光的散射效果明显，激光烧蚀效率低，会出现热熔融现象造成的刻槽边部凸起。因此，本发明要求的保护膜物质颗粒度范围为，直径≥500μm的颗粒数量占比不能超过10％。
本发明在激光刻痕前使用的保护膜为金属氧化物粉末分散到水中经过高速搅拌形成浆液、以辊涂或喷涂的方式在钢带表面涂布，并在200℃以上温度环境下烘干形成。本发明人通过反复试验，确定非水溶性的金属氧化物在水中高速搅拌后分散性好，能够有效附着在硅钢表面，并携带一定自由水或结晶水，利于激光刻痕时热量向外扩散，从而形成具有良好形状的刻痕刻槽。特别的，非水溶性金属氧化物以碱土金属氧化物及Al 2O 3、ZnO、ZrO为优选。
此外，本发明中使用的激光功率密度I必须高于1.0×10 6W/cm 2.其中激光功率密度I的定义式如下：
Figure PCTCN2018074023-appb-000001
其中P为激光输出功率，S为包含96％以上光束能量的光斑面积。
图5说明了本发明中激光功率密度I与刻痕后铁损改善率和叠片系数的规律。功率密度I在1.0×10 6W/cm 2处，铁损改善率和叠片系数均发生跳跃性变化。这是因为功率密度I小于1.0×10 6W/cm 2时，激光刻槽时表面对激光的吸收率很低，大部分激光能量被反射，表面受热区域达不到气化温度，刻槽形成以熔融为主，在刻痕边缘形成熔融物，最终形成边部凸起。此时边部凸起是保护膜与基体材料重熔并凝结形成，后续刷洗无法消除。当功率密度I等于或超过1.0×10 6W/cm 2时，激光烧蚀以气化为主，光吸收率大大提高，刻槽效率显著提升。气化物质在吹扫气体和集尘系统的共同作用下被带出刻痕区域，少量残留物质落在刻槽附近，在后续的刷洗过程中连同保护膜被清理掉，最终得到槽型可控的刻槽。因此，本发明要求的激光功率密度范围为大于或等于1.0×10 6W/cm 2.
本发明人另外详细研究了入射激光能量和最终成品磁性能的相关性，结果发现二者密切相关。以激光能量密度e 0表示单位面积上接受的激光总能量，其定义式为：
Figure PCTCN2018074023-appb-000002
其中，D y表示光斑沿扫描方向的长度，V s为激光扫描速度。
激光能量密度过低，低于0.8J/mm 2，激光烧蚀剥离的材料很少，不足以形成细化磁畴的效果；激光能量密度过高，高于8.0J/mm 2，则会带入过多的激光能量，一方面所形成刻槽深度过大降低磁感，另一方面也会使刻槽可控性变差，底部不平，且边部易发生熔融形成的凸起。
进一步，发明人通过反复实验研究发明了激光能量密度和表面覆膜相匹配以使取向硅钢磁性能最佳化的技术方案。具体而言，即通过控制二者比值，达到优化刻槽效果的目的。图6是以0.23mm取向硅钢为例，说明了本发明范围的有益效果。激光能量密度和表面覆膜厚度比值a低于0.6时，P17/50得不到明显改善；a值高于7.0时，P17/50改善率渐小，但磁感B8迅速劣化，这是由于刻槽漏磁和热传导范围扩大共同作用的结果。
同时，虽然刻痕刻槽的存在能够细化磁畴，降低铁损，但刻槽处磁导率很低，对B8有一定损害作用。本发明人详细研究了刻槽尺寸与硅钢片铁损和磁感的关系发现，为使硅钢片铁损降低，同时保证B8不显著降低，刻槽尺寸及间距需满足既定条件。当刻槽宽度低于20μm时，刻痕实现难度大，同时，刻槽两侧自由磁极间的耦合能增大，补偿了漏磁造成的系统能量变化，磁畴不能得到有效细化。当刻槽轧向尺寸超过300μm时，刻槽间距过大，磁感降低显著；刻痕在基体上形成的刻槽深度小于5μm，磁畴细化效果很小，硅钢片损耗得不到降低；刻槽深度大于50μm，大量的自由磁极导致裸露磁通过多，铁损下降不多，但磁感降低明显。
此外，刻痕间距和刻痕线与钢板横向夹角也显著地影响铁损性能和磁感性能。相邻刻槽过小，低于1mm，刻槽过于密集，磁感降低明显。相邻刻槽间距过大，超过10mm，不能在有效的范围内形成细化磁畴，铁损得不到改善；刻槽线与钢板轧制方向夹角大于30°，磁畴细化效果减弱，铁损改善率很低。因此，适合硅钢片磁畴细化降低铁损而不显著降低磁感的刻槽条件为：刻槽宽度介于5-300μm之间，刻槽深度介于5-60μm之间，相邻刻槽间距介于1-10mm之间。
本发明采用保护膜实现耐热激光刻痕的方法，一次扫描成型，所形成 的刻槽在钢板横截面方向上呈现近似三角形、梯形、半圆形、椭圆形中的一种或其变形，及刻痕线沿钢板轧向平行排布，均属于本发明的保护范围，所形成的刻槽尺寸等同于本发明中所述的保护范围。
附图说明
图1为本发明激光刻痕在取向硅钢表面形成刻痕线状刻槽的宏观图示；
图2为本发明要求的刻槽边缘最大凸起高度范围；
图3为本发明所要求的飞溅物所占表面积比例与最大高度的范围图示；
图4为本发明形成刻槽底部中心线粗糙度的要求范围；
图5为本发明要求的激光功率密度的范围；
图6为本发明要求的激光能量密度与覆膜厚度比值的范围图示；
图7为本发明中保护膜后实施激光刻痕的表面形貌；
图8为本发明中保护膜清洗后的刻痕形貌。
具体实施方式
以下对本发明的实施形态及效果举例说明，但发明方案不限于实施例中所述方案。
参见图1，本发明的耐消除应力退火的激光刻痕取向硅钢10，采用激光刻痕方式在取向硅钢的单面或双面刻痕形成平行线状刻槽20，该线状刻槽与钢板轧制方向垂直或成一角度；线状刻槽边缘凸起最大高度不超过5μm，相邻线状刻槽之间的无刻痕区域飞溅物最大高度不超过5μm，且线状刻槽附近区域飞溅物所占面积比例不超过5％。
优选的，所述线状刻槽底部中心线的线粗糙度R a不超过2.1μm。
优选的，所述线状刻槽形状为近似三角形、梯形、半圆形或椭圆形。
优选的，所述线状刻槽与钢板轧制方向成的角度为0-30°之间。
优选的，所述线状刻槽宽度5～300μm，刻槽深度5～60μm，相邻线状刻槽之间间距1～30mm。
实施例一
取向硅钢经过炼铁、炼钢、连铸、热轧工艺，再经过一次冷轧轧至最终厚度0.23mm，经过脱碳退火工艺，形成表面氧化层后再其表面涂覆MgO隔离剂，高温退火1250℃保持20小时，清洗掉未反应残余的MgO，之后在其表面利用采用辊涂法并经过烘干形成保护膜，之后采用YAG激光器沿钢板轧向实施等间距线状刻槽刻痕，激光输出功率为2000W，脉冲平均宽度为800ns，激光在钢板表面聚焦光斑为椭圆形，短轴0.016mm，长轴0.5mm，扫描速度50m/s，计算激光功率密度为3.2×10 7W/cm 2，激光能量密度为3.2J/mm 2；所形成的刻痕线与钢板轧向相垂直，相邻刻痕线间距为4mm；然后实施刷洗工艺将表面保护膜及刻痕飞溅物残渣等祛除，最后在其表面涂覆绝缘涂层并进行最终退火形成成品硅钢片。
采用《GB/T 3655-2008用爱泼斯坦方圈测量电工钢片(带)磁性能的方法》测定磁性能，采用《GB/T 19289-2003电工钢片(带)的密度、电阻率和叠装系数的测量方法》测定叠片系数，实施例和比较例的测定结果见表1。
从表1中可以看出，实施例1-10均有较好的铁损、磁感和叠片系数性能，而不在本发明范围内比较例1-10的磁性能或叠片系数相对较差。
实施例二中心线粗糙度R a对磁性能波动的影响
取向硅钢经过炼铁、炼钢、连铸、热轧工艺，再经过一次冷轧将钢板轧至最终厚度0.225mm，经过脱碳退火工艺，形成表面氧化层后在表面涂覆MgO隔离剂，之后高温退火1200℃保持20小时，清洗掉未反应残余的MgO；之后在其表面利用采用辊涂法并烘干形成ZnO保护膜，膜厚控制在2.5μm；之后采用连续式CO 2激光器沿钢板轧向实施等间距线状刻槽刻痕；所形成的刻痕线与钢板轧向相垂直，相邻刻痕线间距为4.5mm；然后实施刷洗工艺将表面保护膜及刻痕飞溅物残渣等祛除，最后在其表面涂覆绝缘涂层并进行最终退火形成成品硅钢片。
采用SST 60mm×300mm方法测定磁性能，实施例和比较例的测定结果见表2。
从表2的对比可以看出，本发明范围内的激光参数能够实现硅钢片磁 性能的均匀稳定，超出本发明范围的比较例则由于刻槽底部中心线R a过大造成磁性能波动增大。
实施例三
取向硅钢经过炼铁、炼钢、连铸、热轧工艺，再经过一次冷轧轧至最终厚度0.255mm，在其表面采用喷涂方法施加Al 2O 3保护膜，保护膜中Al 2O 3颗粒≥500μm粒子占比为5％左右；之后利用脉冲宽度为300纳秒的YAG激光进行线状微刻槽刻痕，通过调节聚焦光斑大小、扫描速度、控制激光刻痕能量，所形成的刻槽近似三角形，刻槽线与钢板横向夹角为8°，沿轧向间距为4mm；然后经过刷洗将表面保护膜祛除干净，经过脱碳退火，形成表面氧化层后在其表面涂覆MgO隔离剂，卷制成钢卷后在1250℃的高温退火条件下保持20小时，最后清洗掉残余MgO，并在其表面涂覆绝缘涂层并进行最终退火形成成品硅钢片。
采用《GB/T 3655-2008用爱泼斯坦方圈测量电工钢片(带)磁性能的方法》测定磁性能，采用《GB/T 19289-2003电工钢片(带)的密度、电阻率和叠装系数的测量方法》测定叠片系数，实施例和比较例的测定结果见表3。
从表3可以看出，激光能量密度在本发明范围的实施例具有较好的磁性能，而比较例超出本发明范围，磁性能均要差于本发明。
实施例四
取向硅钢经过炼铁、炼钢、连铸、热轧工艺，再经过一次冷轧轧至最终厚度0.195mm，经过脱碳退火工艺，形成表面氧化层后再其表面涂覆MgO隔离剂，膜厚控制在9.5μm左右，之后采用YAG激光器沿钢板轧向实施等间距线状刻槽刻痕，激光输出功率为2000W，单脉冲平均宽度为800ns，激光在钢板表面聚焦光斑为椭圆形，短轴0.016mm，长轴0.5mm，扫描速度50m/s，计算激光功率密度为3.2×10 7W/cm 2，激光能量密度为3.2J/mm 2；所形成的刻痕线与钢板轧向相垂直，相邻刻痕线间距为4mm；高温退火1250℃保持20小时，清洗掉未反应残余的MgO，最后在其表面涂覆绝缘涂层并进行最终退火形成成品硅钢片。
采用《GB/T 3655-2008用爱泼斯坦方圈测量电工钢片(带)磁性能的方法》测定磁性能，采用《GB/T 19289-2003电工钢片(带)的密度、电阻率和叠装系数的测量方法》测定叠片系数，实施例和比较例的测定结果见表4。
本实施例中控制氧化镁隔离剂的膜厚，使其达到本发明所要求的能量密度与膜厚比范围，从而使得氧化镁同时具有隔离剂和保护膜的作用，在高温退火后将残余氧化镁和飞溅物质等一同清洗掉。以上本发明实施例和比较例的比较可以看出，处于本发明范围的激光工艺参数能够得到磁畴细化、铁损降低的硅钢片，超出本发明范围的激光工艺或者铁损高或者叠片系数低。
综上所述，本发明采用保护膜覆盖和激光一次扫描的方式在钢板表面形成线状刻槽。由于保护膜对激光的吸收特性，充分保证了所形成刻槽的形貌可控，使获得的成品硅钢片铁损显著降低，且叠片系数不会发生明显劣化，特别适用于卷绕铁芯变压器的制造。本发明工序简单，生产效率高，具有很高的应用价值和使用前景。
Figure PCTCN2018074023-appb-000003
Figure PCTCN2018074023-appb-000004
Figure PCTCN2018074023-appb-000005
Figure PCTCN2018074023-appb-000006

Claims (15)

  1. 一种耐消除应力退火的激光刻痕取向硅钢，采用激光刻痕方式在取向硅钢的单面或双面刻痕形成平行线状刻槽，该线状刻槽与钢板轧制方向垂直或成一角度；线状刻槽边缘凸起最大高度不超过5μm，相邻线状刻槽之间的无刻痕区域飞溅物最大高度不超过5μm，且线状刻槽附近区域飞溅物所占面积比例不超过5％。
  2. 如权利要求1所述的耐消除应力退火的激光刻痕取向硅钢，其优选范围为，飞溅物高度不超过2μm，单位面积上飞溅物所占比例不超过2.5％。
  3. 如权利要求1或2所述的耐消除应力退火的激光刻痕取向硅钢，其特征是，所述线状刻槽底部中心线的线粗糙度R a不超过2.1μm。
  4. 如权利要求1或2所述的耐消除应力退火的激光刻痕取向硅钢，其特征是，所述线状刻槽底部中心线的线粗糙度Ra不超过0.52μm。
  5. 如权利要求1或2或3或4所述的耐消除应力退火的激光刻痕取向硅钢，其特征是，所述线状刻槽形状为近似三角形、梯形、半圆形或椭圆形。
  6. 如权利要求1或2或3或4或5所述的耐消除应力退火的激光刻痕取向硅钢，其特征是，所述线状刻槽与钢板轧制方向成的角度为0-30°之间。
  7. 如权利要求1或2或3或4或5或6所述的耐消除应力退火的激光刻痕取向硅钢，其特征是，所述线状刻槽宽度5～300μm，刻槽深度5～60μm，相邻线状刻槽之间间距1～10mm。
  8. 如权利要求1～7中任何一项所述的耐消除应力退火的激光刻痕取向硅钢的制造方法，包括冶炼、连铸、热轧、一次或含有中间退火的两次冷轧、含表面涂布MgO隔离剂的脱碳退火、高温退火、经热拉伸平整退火形成成品取向硅钢；其特征是，还包括激光刻痕，所述激光刻痕在脱碳退火前、或在热拉伸平整退火前或后实施；该激光刻痕包括：
    1)在取向硅钢表面形成保护膜；
    2)激光刻痕，在取向硅钢表面形成一系列与钢板轧制方向垂直或成一角度的线状刻槽；
    3)刷洗取向硅钢表面，移除保护膜并烘干。
  9. 如权利要求8所述的耐消除应力退火的激光刻痕取向硅钢的制造方法，其特征是，所述保护膜的成膜物质为金属氧化物粉末，及重量百分比介于0.3％～5.5％之间的水。
  10. 如权利要求8或9所述的耐消除应力退火的激光刻痕取向硅钢的制造方法，其特征是，所述保护膜的厚度在1.0μm～13.0μm之间。
  11. 如权利要求9所述的耐消除应力退火的激光刻痕取向硅钢的制造方法，其特征是，所述金属氧化物粉末为非水溶性，为单一粉末或几种粉末的组合，粉末中粒径≥500μm的颗粒占比≤10％体积比。
  12. 如权利要求8或11所述的耐消除应力退火的激光刻痕取向硅钢的制造方法，其特征是，所述金属氧化物粉末为碱土金属氧化物、Al 2O 3、ZnO或ZrO中的一种或几种组合。
  13. 如权利要求8所述的耐消除应力退火的激光刻痕取向硅钢的制造方法，其特征是，所述激光刻痕步骤中激光的功率密度I不低于1.0×10 6W/cm 2，平均能量密度e 0介于0.8J/mm 2～8.0J/mm 2之间，且平均能量密度与保护膜膜厚的比例a介于0.6～7.0之间。
  14. 如权利要求1～7中任何一项所述的耐消除应力退火的激光刻痕取向硅钢的制造方法，包括冶炼、连铸、热轧、一次或含有中间退火的两次冷轧、脱碳退火、在钢板表面涂覆MgO隔离剂、温退火、经热拉伸平整退火并涂布绝缘涂层形成成品取向硅钢；其特征是，所述脱碳退火后实施激光刻痕，在取向硅钢表面形成一系列与钢板轧制方向垂直或成一角度的线状刻槽。
  15. 如权利要求8或14所述的耐消除应力退火的激光刻痕取向硅钢的制造方法，其特征是，所述激光刻痕步骤中采用的激光发生泵源类型是CO 2激光器、固体激光器、光纤激光器中的一种或几种组合，激光为连续式或脉冲式。
PCT/CN2018/074023 2017-03-27 2018-01-24 一种耐消除应力退火的激光刻痕取向硅钢及其制造方法。 WO2018177007A1 (zh)

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JP2023507438A (ja) * 2019-12-20 2023-02-22 ポスコホールディングス インコーポレーティッド 方向性電磁鋼板およびその磁区微細化方法

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