WO2019132356A1 - Grain-oriented electrical steel sheet and manufacturing method therefor - Google Patents

Grain-oriented electrical steel sheet and manufacturing method therefor Download PDF

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Publication number
WO2019132356A1
WO2019132356A1 PCT/KR2018/016033 KR2018016033W WO2019132356A1 WO 2019132356 A1 WO2019132356 A1 WO 2019132356A1 KR 2018016033 W KR2018016033 W KR 2018016033W WO 2019132356 A1 WO2019132356 A1 WO 2019132356A1
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Prior art keywords
steel sheet
annealing
hot
temperature
weight
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PCT/KR2018/016033
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French (fr)
Korean (ko)
Inventor
고현석
한민수
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주식회사 포스코
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Publication of WO2019132356A1 publication Critical patent/WO2019132356A1/en

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    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/76—Adjusting the composition of the atmosphere
    • 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
    • C21D8/1255—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 with diffusion of elements, e.g. decarburising, nitriding
    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/34—Embedding in a powder mixture, i.e. pack cementation
    • C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
    • C23C10/44—Siliconising
    • C23C10/46—Siliconising of ferrous surfaces
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel

Definitions

  • the present invention relates to a grain-oriented electrical steel sheet in which Si is diffused into a substrate having a specific aggregate structure to further improve iron loss and a method for producing the same.
  • the grain-oriented electrical steel sheet is a soft magnetic material having excellent magnetic properties in the rolling direction, consisting of crystal grains having a Goss orientation in which the crystal orientation of the steel sheet is ⁇ 110 ⁇ ⁇ 001 >.
  • the oriented electrical steel sheet is rolled to a final thickness through hot rolling, hot rolling annealing, hot rolling, and then subjected to high temperature annealing for primary recrystallization annealing and secondary recrystallization.
  • the degree of integration of the Goss orientation to be secondary recrystallized becomes higher as the temperature increase rate is slower, and the magnetism is excellent.
  • the rate of temperature rise during high-temperature annealing of a grain-oriented electrical steel sheet is not more than 15 ° C per hour, and not only takes 2 to 3 days to raise the temperature, but also requires energy annealing more than 40 hours.
  • the current high-temperature annealing process is performed in a batch-type annealing in a coil state, the following difficulties arise in the process.
  • a method for manufacturing a directional electrical steel sheet and a directional electrical steel sheet produced by the method are provided. Specifically, it is intended to provide a grain-oriented electrical steel sheet in which iron is diffused into a substrate having a specific aggregate structure, and a method for producing the same.
  • a method of manufacturing a grain-oriented electrical steel sheet according to an embodiment of the present invention includes: And other inevitably incorporated impurities; Heating the slab; Hot rolling the slab to produce a hot-rolled steel sheet; Hot-rolled sheet annealing the hot-rolled steel sheet; A first cold rolling step of hot-rolled steel sheets annealed; Decarburizing and annealing the first rolled steel sheet; Secondarily cold-rolling the steel sheet after decarburization annealing; Final annealing the steel sheet after completion of the second cold rolling; Coating a composition including a muscle-powder on a steel sheet after final annealing to form a coating layer; And annealing the steel sheet on which the coating layer is formed to form a diffusion layer in the steel sheet.
  • a decarburization process may be included in the step of annealing the hot-rolled sheet.
  • the annealing step of the hot-rolled sheet is performed at 850 To 1000 ° C and dew point temperature to 70 ° (:).
  • the step of decarburizing and annealing the primary rolled steel sheet is performed at a temperature of 8501: 701: can be annealed.
  • the step of decarburization annealing the primary cold-rolled steel sheet and the step of secondary cold-rolling the steel sheet after the decarburization annealing can be repeated twice or more.
  • the final annealing step is 850 To 1000 A first step of annealing at a temperature and a dew point temperature of 70 or less and a second step of annealing in an atmosphere of 10001: to 12001: atmospheric temperature and 3 ⁇ 450% by volume or more.
  • the method may further comprise the step of pickling with an aqueous acid solution of 5 to 50 wt% at a temperature of 50 to 1001: for 20 to 100 seconds.
  • the composition may optionally contain. 2019/132356 1 »(: 1 ⁇ 1 ⁇ 2018/016033
  • the muscle-powder may comprise 20 to 80% by weight.
  • the annealing temperature may be 1100 to 1200 ° (:), and the annealing time may be 3 hours or more.
  • the step of forming the primary cold rolled layer or the coating layer may be performed continuously.
  • the grain-oriented electrical steel sheet according to one embodiment of the present invention includes: 2.0% to 8.0%, 0: 0.002% (not including 0%) by weight, and the balance 6 and other inevitably incorporated impurities (A) the diameter of the circumscribed circle and the diameter of the inscribed circle relative to the plane perpendicular to the thickness direction of the steel sheet, and 2) the non-illusion 2/1) 1) is 0.5 Or more of the total gaseous crystal grains, and the substrate includes a diffusion layer formed from the surface of the substrate to the inside of the substrate.
  • the coating layer may comprise 20 to 80% by weight and 6 to 20 to 60% by weight.
  • the coating layer may contain 60 to 200 parts by weight of 1 < 0 > O to 100 parts by weight of the total amount of the muscles.
  • the thickness of the coating layer may be 0.5 to 3.0 ⁇ .
  • the diffusion layer may contain 4.0 to 8.0% by weight.
  • the thickness of the diffusion layer may be from 30 to 150 <
  • the base material may have a grain size of 20 to 500; and a ratio of crystal grains of 80% or more.
  • a grain-oriented electrical steel sheet can be produced only by a short time of annealing. Unlike the conventional method for producing a grain-oriented electrical steel sheet, a step of winding a cold-rolled steel sheet is not required.
  • a method of manufacturing a grain-oriented electrical steel sheet according to an embodiment of the present invention can provide a grain-oriented electrical steel sheet that does not use a grain growth inhibitor. 2019/132356 1 »(: 1 ⁇ 1 ⁇ 2018/016033
  • the steep annealing may be omitted.
  • the grain-oriented electrical steel sheet according to an embodiment of the present invention is easy to diffuse because of its unique aggregate structure characteristic, and can diffuse a large amount of iron into the base material, thereby further improving iron loss.
  • FIG. 1 is a schematic cross-sectional view of a directional electric steel sheet according to an embodiment of the present invention.
  • FIG. 3 is a photograph showing a crystal grain distribution with respect to a plane perpendicular to the thickness direction of the substrate in Comparative Production Example.
  • first, second, and third terms are used to describe various portions, components, regions, layers, and / or sections, but are not limited thereto. These terms are only used to distinguish any moiety, element, region, layer or section from another moiety, moiety, region, layer or section. Thus, a first portion, component, region, layer or section described below may be referred to as a second portion, component, region, layer or section without departing from the scope of the invention.
  • % means weight%, and incision is 0.0001 wt%.
  • goss means crystal grains having an orientation whose crystal orientation is within 15 degrees from ⁇ 110 ⁇ ⁇ 001 >.
  • the term further includes an additional element, which means that an additional amount of the additional element is substituted for the remaining iron.
  • a method of manufacturing a grain-oriented electrical steel sheet includes: a step of forming a slab including: 1.0% to 4.0%, 0: 0.1% to 0.4% by weight, and the balance comprising muscle and other inevitably incorporated impurities; ; Heating the slab; Hot rolling the slab to produce a hot-rolled steel sheet; Hot-rolled sheet annealing the hot-rolled steel sheet; A first cold rolling step of hot-rolled steel sheets annealed; Decarburizing and annealing the primary cold-rolled steel sheet; Secondarily cold-rolling the steel sheet after decarburization annealing; Final annealing the steel sheet after completion of the secondary rolling; On the finished steel sheet after final annealing Coating a composition comprising a powder to form a coating layer; And annealing the steel sheet on which the coating layer is formed to form a diffusion layer in the steel sheet.
  • a method of manufacturing a grain-oriented electrical steel sheet according to an embodiment of the present invention comprises firstly, 81: 1.0 to 4.0%, 0: 0.1 to 0.4% by weight and the balance of 6 and other inevitably incorporated impurities .
  • the content of the slab and the grain in the grain oriented electrical steel sheet after the final annealing step may be 1.0 to 4.0% by weight. More specifically, the content may be from 1.5 to 3.5% by weight.
  • the base material of the finally produced directional steel sheet can contain a larger amount of the base material in the slab. Specifically, 2.0 to 8.0% by weight can be contained in the base material of the finally produced directional electrical steel sheet.
  • the content in the base material means the content in the entire base material including the diffusion layer to be described later, and the average content in the whole base material .
  • Carbon (C) is used for intermediate decarburization annealing and final decarburization annealing.
  • the content of (: in the slab may be 0.1 to 0.4 wt%. More specifically, the content of (: in the slab may be 0.15 to 0.3% by weight.
  • the amount of carbon in the final directional electric steel sheet after the final annealing step in which decarburization is completed may be 0.0020 wt% or less.
  • the slab heating temperature may be 11001: to 13501: higher than the normal reheat temperature.
  • the hot-rolled structure is coarsened and adversely affects magnetism.
  • the hot-rolled structure is not coarsened even when the slab reheating temperature is high, It is advantageous.
  • the heated slab is hot-rolled to produce a hot-rolled steel sheet.
  • annealing of the hot-rolled sheet may include a decarburization process. Specifically, annealing of the hot-rolled sheet was performed at 850 To 1000 Temperature and dew point To 70 deg. (:). After the annealing described above, 2019/132356 1 »(: 1 ⁇ 1 ⁇ 2018/016033
  • hot rolled steel sheet decarburization annealing is performed, pickling is carried out, and primary rolling is performed to produce cold rolled steel sheets.
  • the cold-rolled steel sheet is decarburized and annealed.
  • the decarburization annealing step can be performed in a region where austenite single phase region or a composite phase of ferrite and austenite exist.
  • 850 To 10001 temperature and dew point
  • the amount of decarburization at the time of decarburization annealing may be 0.0300% to 0.0600%.
  • the annealing may be carried out at a temperature of 1000 to 1200 It can be further annealed at a temperature of 0 ° C and a dew point temperature of 01 ° C or below.
  • the grain size on the surface of the electric steel sheet grows to a great extent, but the crystal grains inside the electric steel sheet remain as a fine structure.
  • the size of the surface ferrite grains after this decarburization annealing is 150? To 250%.
  • the steel sheet having undergone decarburization annealing is subjected to secondary cold rolling. It is known that it is effective to carry out hot rolling at a high pressure lowering rate which is close to 90% in the manufacturing process of a conventional high magnetic flux density directional electric steel sheet. This is because only the primary recrystallized grains 33 grain form an environment favorable for grain growth.
  • the method of manufacturing a grain-oriented electrical steel sheet according to an embodiment of the present invention internally diffuses 0 033 grain in a surface layer caused by decarburization annealing and cold rolling without using abnormal grain growth of 0 083 orientation grain, 033 is advantageously formed so as to distribute the number of crystal grain orientation. Therefore, cold rolling is carried out at a reduction ratio of 50% to 70% A number of texture structures can be formed in the surface layer. More specifically
  • the step of decarburizing and annealing the cold-rolled steel sheet and the step of cold-rolling the steel sheet after the decarburization annealing can be repeated two or more times. By repeating this process two or more times, a large number of 0 033 texture structures can be formed in the surface layer portion 2019/132356 1 »(: 1 ⁇ 1 ⁇ 2018/016033
  • final annealing can be performed successively after cold rolling.
  • the final annealing is performed at 850 To 1000
  • the atmosphere of the second step may be 3 ⁇ 4 90 vol% or more.
  • the cold-rolled sheet before final annealing is in a state in which decarburization annealing proceeds so that the amount of carbon black remaining in the slab is 40 wt% to 60 wt% of the minimum amount of carbon in the slab. Therefore, at the first stage of the final annealing, the carbon grains are removed and the crystal grains formed in the surface layer are diffused into the inside. In the first step, decarburization can be performed so that the amount of carbon in the steel sheet is 0.01 wt% or less.
  • grain size of crystal grains can be within 1Tm, unlike the case where grains are grown by conventional abnormal grain growth, A plurality of goth grain grains having a small grain size may be present.
  • the pickling step may use an aqueous acid solution of 5 to 50% by weight.
  • an aqueous solution containing inorganic acid such as hydrochloric acid, nitric acid or sulfuric acid can be used as the acid aqueous solution. If the concentration of the aqueous acid solution is too low, proper pickling may not be achieved. In addition, when the concentration of the acid aqueous solution is too large, the surface roughness of the steel sheet becomes too high, which may adversely affect magnetism.
  • the pickling step can be carried out at a temperature of from 50 to 100 < 1 > If the temperature is too low, pickling may not be done properly. If the temperature is too high, re-oxidation may occur.
  • the pickling step can be pickled for 20 to 100 seconds. If the time is too short, the removal of the oxide layer may not be sufficiently performed. If the time is too long, the magnetism may be deteriorated due to the non-uniformity of the acid pickling ability between the crystal grains and the crystal grains. More specifically, the pickling step may be pickled for 25 to 50 seconds.
  • composition containing the powder is coated to form a coating layer.
  • the powder may be in the form of a slurry containing a solvent.
  • the solvent is not particularly limited, but may include water or an alcohol.
  • It can be manufactured by high-temperature firing in a possible firing furnace.
  • the final annealing process operated in the conventional batch mode can be operated as a continuous annealing process, and the step of forming the diffusion layer from the first cold pressing step can be continuously performed. 2019/132356 1 »(: 1 ⁇ 1 ⁇ 2018/016033
  • the steel sheet on which the coating layer is formed is annealed to form a diffusion layer in the steel sheet.
  • the annealing process can be carried out at a temperature of 1100 to 1200 ° C.
  • the annealing time may be 3 hours or more. If the annealing temperature is too low or the annealing time is too short, smooth diffusion may not occur.
  • a directional electrical steel sheet 100 according to an embodiment of the present invention includes a substrate 10 and a coating layer 20 formed on the surface of the substrate 10.
  • the substrate 10 includes a diffusion layer 11 formed from the surface of the substrate 10 to the inside of the substrate 10.
  • the substrate comprises: 2.0% to 8.0%, 0: 0.002% or less (does not include 0%) and the balance includes muscle and other inevitably incorporated impurities.
  • the element content and the reason for the base material have been described in detail with respect to the above-described production method of the grain-oriented electrical steel sheet, and therefore, a repetitive description thereof will be omitted.
  • the carbon content in the substrate may be 0.002 wt% or less, unlike the carbon content in the slab, since it includes decarburization in the manufacturing process.
  • the content of the slurry may be 2.0 to 8.0 wt%, unlike the content in the slab.
  • the circumscribed circle means the smallest circle among the virtual circles surrounding the outside of the crystal grains
  • the inscribed circle means the largest circle of the virtual circles included in the crystal grains.
  • the size of the crystal grains of the base material according to an embodiment of the present invention may be 80% or more of the total crystal grains in the range of 20m to 500m.
  • the substrate 10 according to the embodiment of the present invention has a crystal grain size of
  • Base 10 can contain a diffusion layer 11 formed into the substrate from the surface of the substrate (10) diffused in one embodiment of the invention.
  • (: 11) is, the base material 10 in the diffusion layer forming step prior to Means a portion where the content after the diffusion layer formation step is larger than the content of the base material 10 in the diffusion layer forming step.
  • the content of the diffusion layer 11 may be 4.0 to 8.0 wt%, the remainder including 6 and other inevitably incorporated impurities.
  • the content of the diffusion layer 11 may be 1.0 to 5.0% by weight higher than the content of the substrate.
  • the content in the diffusion layer 11 may form a concentration gradient in the thickness direction. In an embodiment of the present invention, the content in the diffusion layer 11 means an average content of the whole.
  • the thickness of the diffusion layer 11 may be 30 to 150 [mu] m. As described above, due to the unique texture of the substrate 10, the thickness of the diffusion layer 11 is increased.
  • the coating layer 20 may be formed to a thickness of 0.5 to 3.0. If the thickness of the coating layer 20 is too thin, it may not be possible to supply enough ⁇ for diffusion. If the thickness of the coating layer 20 is too large, there is a limit to the diffusion, and there may arise a problem that the bonding force between the substrate 10 and the coating layer 20 is weakened.
  • the coating layer 20 to 80 wt% of? And 20 to 60 wt% of 6 may be contained. If the coating composition comprises 10 and the sum of 6 2019/132356 1 »(: 1 ⁇ 1 ⁇ 2018/016033
  • the steel sheet serves as a binder so that the six grains adhere well to the steel sheet.
  • the slabs containing 3.22% and 0: 0.245% by weight and consisting of the residual roots and unavoidable impurities were heated at a temperature of 1250 and then hot rolled to a thickness of 1.6111111, followed by annealing at a temperature of 870 ° (: dew point temperature of 60 [ After annealing for 120 seconds, annealing was carried out for 30 seconds at an annealing temperature of 1100 ° C in a mixed gas atmosphere of hydrogen and nitrogen at a dew point of 0 ° (or less). After the hot-rolled sheet was annealed, it was pickled, followeded by cold rolling at a reduction ratio.
  • the cold-rolled steel sheet was subjected to decarburization annealing at an annealing temperature of 870 ° C (dew point temperature: 60 ° C) for 60 seconds, followed by hydrogen annealing at a dew point temperature of 0 ° (1 or less in a hydrogen and nitrogen mixed gas atmosphere, Annealed for 50 seconds, cooled, pickled, and then cold-rolled at a reduction ratio of 60%.
  • decarburization annealing is performed in a mixed gas atmosphere of hydrogen and nitrogen (dew point temperature 60 ° 0) for 60 seconds at a temperature of 900 ° (:
  • Heat treatment was performed in a 100% 3 ⁇ 4 atmosphere for 3 minutes.
  • the cold-rolled steel sheet was subjected to decarburization annealing at a temperature of 870 ° C. (dew point temperature: 60 °) for 60 seconds, hydrogen and dew point temperature (0.) , Cooled, pickled, and secondarily cold rolled at a reduction ratio of 60%.
  • the final thickness was 288 mm.
  • annealing was performed for 60 seconds in a mixed gas atmosphere of hydrogen and nitrogen at a temperature of 900 DEG C (dew point temperature: 60 DEG C for 60 seconds, followed by annealing for 3 minutes in a 100:
  • the carbon content of the final steel plate was 30 ?? 01 .
  • Table 1 is a table showing the relative sizes of the inscribed circle and the circumscribed circle of the Fe- 33 crystal grains in the production example shown in Fig.
  • the ratio 2/1) 1) of all 0 083 grains is 0.5 or more.
  • the slabs containing 3.18%, 0: 0.055%, and 0.1% by weight of the residual roots and unavoidable impurities were heated at a temperature of 1150 °
  • Hot-rolling to 2.2 TM thickness followed by performing hot-rolled steel sheet annealing of the conventional grain-oriented electrical steel sheet and subjected to pickling after the cooling, which was then cold-rolled to 288 / ⁇ 1 thickness.
  • simultaneous decarburization annealing was performed for 3 minutes at an annealing temperature of 850 DEG C in a mixed atmosphere of hydrogen, nitrogen gas and ammonia at a dew point temperature of 60 DEG. Thereafter, the temperature was increased to 15 degrees / degree and then annealed at a high temperature of 1200 degrees (:) for 20 hours.
  • Table 2 is a table showing the relative sizes of the inscribed circle and the circumscribed circle of the grain-oriented electrical steel sheet shown in Fig. 3 and showing the vias 2/1) 1).
  • the substrate prepared in the comparative example is a crystal having a long elliptical structure, so that the value of defects / values is smaller than that described in the embodiment of the present invention.
  • Preparation and comparison of the final annealed sheet to a grain-oriented electrical steel sheet base material produced in Production Example was 80 ° (: using a solution of 25 ⁇ 1 ⁇ concentration from subjected to a pickling process for 20 seconds.
  • the pickled steel plate had a content of 33.5% by weight
  • the powders of the system were mixed with a mixture of calcined powder and ethyl alcohol, and the coated powder was annealed at 1100 to 1200 ° C for 5 hours to form a coating layer having a thickness of 1.7 ⁇ ⁇ .
  • Table 3 shows the contents of the entire substrate, the content of the diffusion layer, and the thickness of the diffusion layer with respect to the annealing time.
  • the grain size is less than 1/100 of that of a conventional grain-oriented electrical steel sheet, and the ratio of the diameter of the circumscribed circle 1) and the diameter of the inscribed circle 2/1)
  • the diffusion is uniformly and well caused, and the iron loss is excellent as well as the content.
  • the slabs containing 2.0% by weight, 0.20% by weight, and the remainder of the slabs and inevitable impurities were heated at a temperature of 1250 DEG C, followed by hot rolling to a thickness of 1.6 DEG C, followed by annealing at a temperature of 870 DEG C: After annealing at a dew point temperature of 60 ° C for 120 seconds, hot rolled sheet annealing was carried out under hydrogen and a dew point temperature of 0 ° C (hydrogen and nitrogen gas mixture atmosphere at an annealing temperature of 1100 ° and 30 seconds, By cold rolling.
  • the hot-rolled sheet was subjected to decarburization annealing at a temperature of 870 ° (dew point: 60 °) for 60 seconds, followed by hydrogen and dew point temperature 0 ° 0 , Cooled, pickled, and then cold-rolled at a reduction ratio of 60%.
  • decarburization annealing was performed at a temperature of 900 ° C. for 60 seconds in a mixed gas atmosphere of hydrogen and nitrogen (dew point temperature: 60 °), and then 1050 °
  • Annealing was performed for 3 minutes in a 100% atmosphere.
  • the final annealed plate was subjected to a pickling process for 20 seconds using a 1% aqueous solution of 80% (: 25% strength).
  • a 1% aqueous solution of 80% (: 25% strength).
  • 33.5% by weight of the powder was mixed with steel (0: 101) at 0,

Abstract

A method for manufacturing a grain-oriented electrical steel sheet according to one embodiment of the present invention comprises the steps of: preparing a slab comprising, by weight %, 1.0% to 4.0% of Si, 0.1% to 0.4% of C, and the balance of Fe and impurities inevitably incorporated thereto; heating the slab; hot-rolling the slab to afford a hot-rolled steel sheet; hot-band annealing the hot-rolled steel sheet; primarily cold rolling the hot-band annealed, hot-rolled steel sheet; decarbonization annealing the primarily cold-rolled steel sheet; secondarily cold rolling the steel sheet that has been decarbonization annealed; conducting final annealing on the steel sheet that has undergone the secondarily cold rolling; applying a composition Fe-Si powder to the steel sheet that has undergone the final annealing, to form an Si coating layer; and annealing the Si coating layer-formed steel sheet to form an Si diffusion layer inside the steel sheet.

Description

【명세서】  【Specification】
【발명의 명칭】  Title of the Invention
방향성 전기강판및 이의 제조방법  Directional electrical steel sheet and manufacturing method thereof
【기술분야】  TECHNICAL FIELD
방향성 전기강판(GRAIN ORIENTED ELECTRICAL STEEL SHEET) 및 이의 제조방법 (METHOD FOR MANUFACTURING THE SAME)에 관한것이다. 구체적으로, 특유의 집합조직을갖는기재에 Si를확산시켜, 철손이 더욱향상된 방향성 전기강판및 이의 제조방법에 관한것이다.  (GRAIN ORIENTED ELECTRICAL STEEL SHEET), and METHOD FOR MANUFACTURING THE SAME. More specifically, the present invention relates to a grain-oriented electrical steel sheet in which Si is diffused into a substrate having a specific aggregate structure to further improve iron loss and a method for producing the same.
【발명의 배경이 되는기술】  TECHNICAL BACKGROUND OF THE INVENTION
방향성 전기강판은강판의 결정방위가 {110}<001>인 일명 고스 (Goss) 방위를갖는결정립들로이루어진 압연방향의 자기적 특성이 뛰어난연자성 재료이다.  The grain-oriented electrical steel sheet is a soft magnetic material having excellent magnetic properties in the rolling direction, consisting of crystal grains having a Goss orientation in which the crystal orientation of the steel sheet is {110} < 001 >.
이러한 방향성 전기강판은슬라브 가열 후 열간 압연， 열연판소둔, 넁간압연을통하여 최종두께로압연된다음, 1차재결정 소둔과 2차재결정 형성을위하여 고온소둔을거쳐 제조된다.  The oriented electrical steel sheet is rolled to a final thickness through hot rolling, hot rolling annealing, hot rolling, and then subjected to high temperature annealing for primary recrystallization annealing and secondary recrystallization.
이때， 고온소둔시에는승온율이 느릴수록 2차재결정되는 Goss방위의 집적도가 높아져 자성이 우수한 것으로 알려져 있다. 통상 방향성 전기강판의 고온소둔중승온율은시간당 15°C 이하로써 승온으로만 2내지 3일이 소요될 뿐만 아니라 40시간 이상의 순화소둔이 필요하므로 에너지 소모가 심한 공정이라고 할 수 있다. 또한 현재의 최종 고온소둔 공정은 코일 상태에서 배치 (Batch)형태의 소둔을실시하기 때문에 공정상의 다음과 같은어려움이 발생하게 된다. 첫째， 코일상태에서의 열처리로 인한코일의 외권부와내권부온도 편차가발생하여 각부분에서 동일한 열처리 패턴을 적용할수 없어 외권부와내권부의 자성편차가발생한다. 둘째, 탈탄소둔 후 MgO를표면에 코팅하고 고온소둔중 Base coating을 형성하는과정에서 다양한표면결함이 발생하기 때문에 실수율을떨어뜨리게된다. 셋째， 탈탄 소둔이 끝난탈탄판을코일형태로 감은후고온소둔후 다시 평탄화소둔을 거쳐 절연코팅을 하기 때문에 생산공정이 3단계로 나누어지게 됨으로써 실수율이 떨어지는문제점이 발생한다.  At this time, it is known that, at a high temperature annealing, the degree of integration of the Goss orientation to be secondary recrystallized becomes higher as the temperature increase rate is slower, and the magnetism is excellent. Usually, the rate of temperature rise during high-temperature annealing of a grain-oriented electrical steel sheet is not more than 15 ° C per hour, and not only takes 2 to 3 days to raise the temperature, but also requires energy annealing more than 40 hours. In addition, since the current high-temperature annealing process is performed in a batch-type annealing in a coil state, the following difficulties arise in the process. First, due to the heat treatment in the coil state, there occurs a temperature deviation between the outer and inner parts of the coil, so that the same heat treatment pattern can not be applied to each part, resulting in magnetism deviation between the outer part and the inner part. Second, since the MgO is coated on the surface after decarburization annealing and various surface defects are formed in the process of forming the base coating during the high temperature annealing, the rate of water drop is decreased. Third, since the decarburized annealed annealed decarburized plate is wound in a coil form, then annealed at high temperature, and then subjected to planarization annealing, the insulating coating is performed. Thus, the production process is divided into three stages, thereby causing a problem of a low yield rate.
【발명의 내용】 2019/132356 1»（：1^1{2018/016033 DISCLOSURE OF THE INVENTION 2019/132356 1 »(: 1 ^ 1 {2018/016033
【해결하고자하는과제】 [Problem to be solved]
본 발명의 일 실시예에서는 방향성 전기강판의 제조방법 및 이에 의하여 제조된 방향성 전기강판을 제공하고자 한다. 구체적으로, 특유의 집합조직을 갖는 기재에 를 확산시켜， 철손이 더욱 향상된 방향성 전기강판및 이의 제조방법을제공하고자한다.  In one embodiment of the present invention, a method for manufacturing a directional electrical steel sheet and a directional electrical steel sheet produced by the method are provided. Specifically, it is intended to provide a grain-oriented electrical steel sheet in which iron is diffused into a substrate having a specific aggregate structure, and a method for producing the same.
【과제의 해결수단】  MEANS FOR SOLVING THE PROBLEMS
본발명의 일실시예에 의한방향성 전기강판의 제조방법은，중량%로,
Figure imgf000004_0001
및 기타 불가피하게 혼입되는 불순물을 포함하는 슬라브를 제조하는 단계; 슬라브를 가열하는 단계; 슬라브를 열간 압연하여 열연 강판을 제조하는 단계; 열연 강판을 열연판소둔하는단계; 열연판소둔된 열연강판을 1차냉간압연하는단계; 1차 넁간 압연된 강판을 탈탄 소둔하는 단계; 탈탄 소둔이 완료된 강판을 2차 냉간 압연하는 단계; 2차 냉간 압연이 완료된 강판을 최종 소둔하는 단계; 최종소둔이 완료된 강판에 근- 분말포함하는조성물을코팅하여 코팅층을 형성하는단계; 및 ^ 코팅층이 형성된 강판을소둔하여 강판 내부에 확산층을형성하는단계를포함한다. A method of manufacturing a grain-oriented electrical steel sheet according to an embodiment of the present invention includes:
Figure imgf000004_0001
And other inevitably incorporated impurities; Heating the slab; Hot rolling the slab to produce a hot-rolled steel sheet; Hot-rolled sheet annealing the hot-rolled steel sheet; A first cold rolling step of hot-rolled steel sheets annealed; Decarburizing and annealing the first rolled steel sheet; Secondarily cold-rolling the steel sheet after decarburization annealing; Final annealing the steel sheet after completion of the second cold rolling; Coating a composition including a muscle-powder on a steel sheet after final annealing to form a coating layer; And annealing the steel sheet on which the coating layer is formed to form a diffusion layer in the steel sheet.
열연판소둔하는단계에서 탈탄과정을포함할수있다.  And a decarburization process may be included in the step of annealing the hot-rolled sheet.
열연판 소둔하는 단계는 850
Figure imgf000004_0002
내지 1000 온도 및 이슬점 온도 내지 70°（：에서 소둔할수있다. The annealing step of the hot-rolled sheet is performed at 850
Figure imgf000004_0002
To 1000 ° C and dew point temperature to 70 ° (:).
1차 넁간 압연된 강판을 탈탄 소둔하는 단계는 8501： 내지 1000 온도및 이슬점
Figure imgf000004_0003
701：에서 소둔할수있다. The step of decarburizing and annealing the primary rolled steel sheet is performed at a temperature of 8501:
Figure imgf000004_0003
701: can be annealed.
1차냉간 압연된 강판을 탈탄소둔하는 단계 및 탈탄소둔이 완료된 강판을 2차냉간압연하는단계는 2회 이상반복할수있다.  The step of decarburization annealing the primary cold-rolled steel sheet and the step of secondary cold-rolling the steel sheet after the decarburization annealing can be repeated twice or more.
최종 소둔하는 단계는 850
Figure imgf000004_0005
내지 1000
Figure imgf000004_0004
온도 및 이슬점 온도 70方이하에서 소둔하는제 1단계 및 10001： 내지 12001：온도및 ¾ 50부피% 이상의 분위기에서 소둔하는제 2단계를포함할수있다. The final annealing step is 850
Figure imgf000004_0005
To 1000
Figure imgf000004_0004
A first step of annealing at a temperature and a dew point temperature of 70 or less and a second step of annealing in an atmosphere of 10001: to 12001: atmospheric temperature and ¾50% by volume or more.
최종소둔하는단계 이후， 5내지 50중량%의 산수용액을이용하여， 50내지 1001： 온도에서 20초 내지 100초동안산세하는단계를더 포함할 수있다.  After the final annealing step, the method may further comprise the step of pickling with an aqueous acid solution of 5 to 50 wt% at a temperature of 50 to 1001: for 20 to 100 seconds.
코팅층을형성하는단계에서， 조성물은 的를더 포함할수있다. 2019/132356 1»（：1^1{2018/016033 In the step of forming the coating layer, the composition may optionally contain. 2019/132356 1 »(: 1 ^ 1 {2018/016033
코팅층을 형성하는 단계에서, 근- 분말은 ^를 20 내지 80 중량% 포함할수있다. In the step of forming the coating layer, the muscle-powder may comprise 20 to 80% by weight.
^ 확산층을형성하는단계에서, 소둔온도는 1100내지 1200°（：이고, 소둔시간은 3시간이상일수있다.  In the step of forming the diffusion layer, the annealing temperature may be 1100 to 1200 ° (:), and the annealing time may be 3 hours or more.
1차냉간압연하는답계 내지 코팅층을형성하는단계는연속하여 이루어질수있다.  The step of forming the primary cold rolled layer or the coating layer may be performed continuously.
본 발명의 일 실시예에 의한 방향성 전기강판은， 중량%로， : 2.0% 내지 8.0%, 0：0.002% 이하（0%를 포함하지 않는다） 및 잔부는 6 및 기타 불가피하게 혼입되는불순물을포함하는 기재 및 기재의 표면 상에 형성된 코팅층을포함하고, 기재는강판의 두께 방향과수직하는 면에 대하여, 외접원의 지름（아）과 내접원의 지름 2）외 비幻2/1）1）가 0.5이상인 고스 결정립이 전체 고스 결정립 중 95 면적% 이상 포함하고， 기재는 기재의 표면에서부터 기재의 내부방향으로형성된 확산층을포함한다. The grain-oriented electrical steel sheet according to one embodiment of the present invention includes: 2.0% to 8.0%, 0: 0.002% (not including 0%) by weight, and the balance 6 and other inevitably incorporated impurities (A) the diameter of the circumscribed circle and the diameter of the inscribed circle relative to the plane perpendicular to the thickness direction of the steel sheet, and 2) the non-illusion 2/1) 1) is 0.5 Or more of the total gaseous crystal grains, and the substrate includes a diffusion layer formed from the surface of the substrate to the inside of the substrate.
코팅층은 를 20내지 80중량%및 6를 20내지 60중량%포함할 수있다. The coating layer may comprise 20 to 80% by weight and 6 to 20 to 60% by weight.
^코팅층은 및 근의 합량 100중량부에 대하여， 1\他0를 60내지 200 중량부더 포함할수있다. 코팅층의 두께는 0.5내지 3.0_일수있다.  The coating layer may contain 60 to 200 parts by weight of 1 &lt; 0 &gt; O to 100 parts by weight of the total amount of the muscles. The thickness of the coating layer may be 0.5 to 3.0 ~.
확산층은 를 4.0내지 8.0중량%포함할수있다.  The diffusion layer may contain 4.0 to 8.0% by weight.
확산층의 두께는 30내지 150_일수있다.  The thickness of the diffusion layer may be from 30 to 150 &lt;
기재는결정립 크기가 20 내지 500；■인 결정립의 비율이 80%이상일 수있다.  The base material may have a grain size of 20 to 500; and a ratio of crystal grains of 80% or more.
【발명의 효과】  【Effects of the Invention】
본 발명의 일 실시예에 의하면， 최종 소둔시 코일 상태에서 배치犯 此）형태의 소둔을 실시하지 않고 연속적인 소둔을 실시할수 있는 방향성 전기강판의 제조방법을제공할수있다.  According to an embodiment of the present invention, it is possible to provide a method of manufacturing a grain-oriented electrical steel sheet in which continuous annealing can be performed without annealing in the form of a coil in the coil state at the final annealing.
또한, 단시간의 소둔만으로도방향성 전기강판을생산할수있다. 또한, 종래의 방향성 전기강판의 제조 방법과 달리 냉연강판을 권취하는공정이 필요없다.  In addition, a grain-oriented electrical steel sheet can be produced only by a short time of annealing. Unlike the conventional method for producing a grain-oriented electrical steel sheet, a step of winding a cold-rolled steel sheet is not required.
또한， 본 발명의 일 실시예에 의한 방향성 전기강판의 제조방법은, 결정립성장억제제를사용하지 않는방향성 전기강판을제공할수있다. 2019/132356 1»（：1^1{2018/016033 In addition, a method of manufacturing a grain-oriented electrical steel sheet according to an embodiment of the present invention can provide a grain-oriented electrical steel sheet that does not use a grain growth inhibitor. 2019/132356 1 »(: 1 ^ 1 {2018/016033
또한， 본 발명의 일 실시예에 의한 방향성 전기강판의 제조방법은， 침질소둔을생략할수있다. Further, in the method of manufacturing a grain-oriented electrical steel sheet according to an embodiment of the present invention, the steep annealing may be omitted.
또한， 본 발명의 일 실시예에 의한 방향성 전기강판은， 특유의 집합조직 특성으로인하여, 의 확산이 용이하며, 기재내부로다량의 ^를 확산시켜 , 철손을더욱향상시킬수있다.  In addition, the grain-oriented electrical steel sheet according to an embodiment of the present invention is easy to diffuse because of its unique aggregate structure characteristic, and can diffuse a large amount of iron into the base material, thereby further improving iron loss.
【도면의 간단한설명】  BRIEF DESCRIPTION OF THE DRAWINGS
도 1 은 본 발명의 일 실시예에 의한 방향성 전기강판의 개략적인 단면을나타낸다.  1 is a schematic cross-sectional view of a directional electric steel sheet according to an embodiment of the present invention.
도 2는 제조예에서 기재의 두께 방향과 수직하는 면에 대한
Figure imgf000006_0001
분포를 £650분석을통하여 나타낸사진이다. 2 is a graph showing the relationship between the thickness
Figure imgf000006_0001
The distribution is shown by £ 650 analysis.
도 3은 비교제조예에서 기재의 두께 방향과 수직하는 면에 대한 결정립 분포를표시한사진이다.  3 is a photograph showing a crystal grain distribution with respect to a plane perpendicular to the thickness direction of the substrate in Comparative Production Example.
【발명을실시하기 위한구체적인내용】  DETAILED DESCRIPTION OF THE INVENTION
제 1， 제 2및제 3등의 용어들은다양한부분， 성분， 영역， 층및/또는 섹션들을 설명하기 위해 사용되나 이들에 한정되지 않는다. 이들 용어들은 어느부분， 성분， 영역, 층또는 섹션을 다른부분， 성분， 영역, 층또는 섹션과구별하기 위해서만사용된다. 따라서 , 이하에서 서술하는제 1부분， 성분， 영역, 층또는 섹션은본 발명의 범위를 벗어나지 않는범위 내에서 제 2부분， 성분， 영역， 층또는섹션으로언급될수있다.  Terms such as first, second, and third terms are used to describe various portions, components, regions, layers, and / or sections, but are not limited thereto. These terms are only used to distinguish any moiety, element, region, layer or section from another moiety, moiety, region, layer or section. Thus, a first portion, component, region, layer or section described below may be referred to as a second portion, component, region, layer or section without departing from the scope of the invention.
여기서 사용되는 전문 용어는 단지 특정 실시예를 언급하기 위한 것이며， 본 발명을 한정하는 것을의도하지 않는다. 여기서 사용되는단수 형태들은 문구들이 이와 명백히 반대의 의미를 나타내지 않는 한 복수 형태들도 포함한다. 명세서에서 사용되는 "포함하는”의 의미는 특정 특성， 영역,정수，단계，동작，요소및/또는성분을구체화하며，다른특성,영역， 정수， 단계， 동작， 요소 및/또는 성분의 존재나 부가를 제외시키는 것은 아니다.  The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. The singular forms as used herein include plural forms as long as the phrases do not expressly express the opposite meaning thereto. Means that a particular feature, region, integer, step, operation, element and / or component is specified and that the presence or absence of other features, regions, integers, steps, operations, elements, and / It does not exclude addition.
어느부분이 다른부분의 "위에” 또는 11상에" 있다고언급하는경우, 이는 바로 다른 부분의 위에 또는 상에 있을 수 있거나 그 사이에 다른 부분이 수반될수 있다. 대조적으로어느부분이 다른부분의 "바로위에" 있다고언급하는경우, 그사이에 다른부분이 개재되지 않는다. 2019/132356 1»（：1^1{2018/016033 When any portion of this "mentioned that the 11 or the" on top "of other parts, which can be can be directly on or above the other part, or accompanied by different parts therebetween. In contrast, when referring to a part being "directly above" another part, no other part is interposed therebetween. 2019/132356 1 »(: 1 ^ 1 {2018/016033
다르게 정의하지는 않았지만， 여기에 사용되는 기술용어 및 과학용어를포함하는모든용어들은본발명이 속하는기술분야에서 통상의 지식을가진자가일반적으로 이해하는의미와동일한의미를가진다. 보통 사용되는 사전에 정의된 용어들은 관련기술문헌과 현재 개시된 내용에 부합하는 의미를 가지는 것으로 추가 해석되고, 정의되지 않는 한 이상적이거나매우공식적인의미로해석되지 않는다. Unless otherwise defined, all terms including technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Commonly used predefined terms are further interpreted as having a meaning consistent with the relevant technical literature and the present disclosure, and are not to be construed as ideal or very formal meanings unless defined otherwise.
또한， 특별히 언급하지 않는 한 %는 중량%를 의미하며， 切 은 0.0001중량%이다.또한고스（卵 결정립이란결정방위가 {110}<001>로부터 15도이내의 방위를갖는결정립을의미한다.  Unless otherwise specified,% means weight%, and incision is 0.0001 wt%. In addition, goss means crystal grains having an orientation whose crystal orientation is within 15 degrees from {110} < 001 >.
본발명의 일실시예에서 추가원소를더 포함하는것의 의미는추가 원소의 추가량만큼잔부인철 을대체하여 포함하는것을의미한다. 이하， 본 발명의 실시예에 대하여 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는실시예에한정되지 않는다.  In an embodiment of the present invention, the term further includes an additional element, which means that an additional amount of the additional element is substituted for the remaining iron. Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
본발명의 일실시예에 의한방향성 전기강판의 제조방법은，중량%로， ^ : 1.0% 내지 4.0%, 0：0.1% 내지 0.4% 및 잔부는 근 및 기타 불가피하게 혼입되는 불순물을 포함하는 슬라브를 제조하는 단계; 슬라브를 가열하는 단계; 슬라브를 열간 압연하여 열연 강판을 제조하는 단계; 열연 강판을 열연판소둔하는단계; 열연판소둔된열연강판을 1차냉간압연하는단계 ; 1차 냉간 압연된 강판을 탈탄 소둔하는 단계; 탈탄 소둔이 완료된 강판을 2차 냉간 압연하는 단계; 2차 넁간 압연이 완료된 강판을 최종 소둔하는 단계; 최종소둔이 완료된 강판에
Figure imgf000007_0001
분말포함하는조성물을코팅하여 코팅층을 형성하는단계; 및 코팅층이 형성된 강판을소둔하여 강판 내부에 확산층을형성하는단계를포함한다. A method of manufacturing a grain-oriented electrical steel sheet according to an embodiment of the present invention includes: a step of forming a slab including: 1.0% to 4.0%, 0: 0.1% to 0.4% by weight, and the balance comprising muscle and other inevitably incorporated impurities; ; Heating the slab; Hot rolling the slab to produce a hot-rolled steel sheet; Hot-rolled sheet annealing the hot-rolled steel sheet; A first cold rolling step of hot-rolled steel sheets annealed; Decarburizing and annealing the primary cold-rolled steel sheet; Secondarily cold-rolling the steel sheet after decarburization annealing; Final annealing the steel sheet after completion of the secondary rolling; On the finished steel sheet after final annealing
Figure imgf000007_0001
Coating a composition comprising a powder to form a coating layer; And annealing the steel sheet on which the coating layer is formed to form a diffusion layer in the steel sheet.
본 발명의 일 실시예에 따른 방향성 전기강판의 제조방법은， 먼저, 중량%로, 81： 1.0% 내지 4.0%, 0：0.1% 내지 0.4% 및 잔부는 6 및 기타 불가피하게혼입되는불순물을포함하는슬라브를제조한다. A method of manufacturing a grain-oriented electrical steel sheet according to an embodiment of the present invention comprises firstly, 81: 1.0 to 4.0%, 0: 0.1 to 0.4% by weight and the balance of 6 and other inevitably incorporated impurities .
조성을한정한이유는하기와같다.  The reason for limiting the composition is as follows.
실리콘（ ）는 전기강판의 자기이방성을 낮추고 비저항을 증가시켜 2019/132356 1»（：1^1{2018/016033 Silicon () lowers the magnetic anisotropy of the electrical steel sheet and increases the resistivity 2019/132356 1 »(: 1 ^ 1 {2018/016033
철손을 개선한다. 함량이 1.0 중량% 미만인 경우에는 철손이 열위하게 되며 , 4.0중량%초과인경우취성이 증가한다.따라서 ,슬라브및 최종소둔 단계 이후 방향성 전기강판에서의 의 함량은 1.0 내지 4.0중량% 일 수 있다. 더욱구체적으로 의 함량은 1.5내지 3.5중량%일수있다. Improve core loss. If the content is less than 1.0% by weight, the iron loss is inferior and when it exceeds 4.0% by weight, the brittleness increases. Therefore, the content of the slab and the grain in the grain oriented electrical steel sheet after the final annealing step may be 1.0 to 4.0% by weight. More specifically, the content may be from 1.5 to 3.5% by weight.
본 발명의 일 실시예에서 강판의 표면에 코팅층을 형성한 후, 소둔하여, 를기재내부로 층을확산시키기 때문에, 최종제조된방향성 전기강판의 기재 내에는 가 슬라브 내의 보다 다량 함유할 수 있다. 구체적으로최종제조된방향성 전기강판의 기재 내에는 가 2.0내지 8.0 중량% 포함될 수 있다. 더욱 구체적으로 최종 제조된 방향성 전기강판의 기재내에는 가 3.0내지 7.0중량%포함될수있다.기재내의 함량이란 후술할 확산층을포함하는전체 기재 내에서의 함량을의미하며， 전체 기재내에서의 평균함량을의미한다.  In one embodiment of the present invention, since a coating layer is formed on the surface of a steel sheet and then the steel sheet is annealed to diffuse the layer into the base material, the base material of the finally produced directional steel sheet can contain a larger amount of the base material in the slab. Specifically, 2.0 to 8.0% by weight can be contained in the base material of the finally produced directional electrical steel sheet. The content in the base material means the content in the entire base material including the diffusion layer to be described later, and the average content in the whole base material .
탄소（ 는 중간 탈탄소둔 및 최종 탈탄소둔중에 표증부의
Figure imgf000008_0001
결정립이 중심부로 확산하기 위하여 중심부의 가 표층부로 빠져 나오는 과정이 필요하기 때문에 슬라브 중（:의 함량은 0.1 내지 0.4중량% 일 수 있다. 더욱 구체적으로 슬라브 중（：의 함량은 0.15내지 0.3중량% 일 수 있다. 또한， 탈탄이 완료된 최종 소둔 단계 이후 최종 방향성 전기강판에서의 탄소량은 0.0020중량%이하일수있다. Carbon (C) is used for intermediate decarburization annealing and final decarburization annealing.
Figure imgf000008_0001
In order to diffuse the crystal grains to the center portion, a process of coming out to the surface layer of the center portion is required, so the content of (: in the slab may be 0.1 to 0.4 wt%. More specifically, the content of (: in the slab may be 0.15 to 0.3% by weight. Further, the amount of carbon in the final directional electric steel sheet after the final annealing step in which decarburization is completed may be 0.0020 wt% or less.
다음으로, 제조된 슬라브를 가열 한다. 슬라브 가열 온도는 통상의 재가열온도보다높은 11001： 내지 13501：일수있다.  Next, the produced slab is heated. The slab heating temperature may be 11001: to 13501: higher than the normal reheat temperature.
슬라브 가열시 온도가 높을 경우 열연 조직이 조대화되어 자성에 악영향을 미치게 되는문제점이 있다. 그러나본발명의 일 실시예에 의한 방향성 전기강판의 제조 방법은 탄소의 함량이 종래보다 많아 슬라브 재가열온도가높더라도열연조직이 조대화되지 않으며 ,통상의 경우보다 높은온도에서 재가열함으로써 , 열간압연시 유리하다.  When the slab is heated at a high temperature, there is a problem that the hot-rolled structure is coarsened and adversely affects magnetism. However, in the method of manufacturing a grain-oriented electrical steel sheet according to an embodiment of the present invention, the hot-rolled structure is not coarsened even when the slab reheating temperature is high, It is advantageous.
다음으로 가열이 완료된 슬라브를 열간 압연하여 열연 강판을 제조한다.  Next, the heated slab is hot-rolled to produce a hot-rolled steel sheet.
다음으로 열연 강판을 열연판 소둔한다. 이때 열연판 소둔은 탈탄 과정을포함할수 있다. 구체적으로열연판소둔은 850
Figure imgf000008_0002
내지 1000
Figure imgf000008_0003
온도 및 이슬점
Figure imgf000008_0004
내지 70°（：에서 소둔할 수 있다. 전술한 소둔 이후, 2019/132356 1»（：1^1{2018/016033 Next, the hot-rolled steel sheet is subjected to hot-rolled sheet annealing. At this time, annealing of the hot-rolled sheet may include a decarburization process. Specifically, annealing of the hot-rolled sheet was performed at 850
Figure imgf000008_0002
To 1000
Figure imgf000008_0003
Temperature and dew point
Figure imgf000008_0004
To 70 deg. (:). After the annealing described above, 2019/132356 1 »(: 1 ^ 1 {2018/016033
1000 내지 12001：의 온도 및 이슬점 온도 01： 이하에서 추가 소둔할 수 있다. 1000 to 12001: and dew point temperature 01: or less.
다음으로 열연판 탈탄 소둔을 실시한 후 산세를 하고 1차 넁간 압연을실시하여 냉연강판을제조한다.  Next, hot rolled steel sheet decarburization annealing is performed, pickling is carried out, and primary rolling is performed to produce cold rolled steel sheets.
다음으로 냉연강판을 탈탄 소둔한다. 이 때, 탈탄 소둔하는 단계는 오스테나이트 단상영역 또는 페라이트 및 오스테나이트의 복합상이 존재하는영역에서 실시할수 있다. 구체적으로 850
Figure imgf000009_0001
내지 10001： 온도및 이슬점
Figure imgf000009_0002
내지 70° (:에서 소둔할수 있다. 또한， 분위기는수소 및 질소의 혼합가스분위기일 수 있다. 또한, 탈탄소둔시 탈탄량은 0.0300 % 내지 0.0600^%일수있다. 전술한소둔이후， 1000내지 1200°(：의 온도및 이슬점 온도 01： 이하에서 추가소둔할수있다. Next, the cold-rolled steel sheet is decarburized and annealed. At this time, the decarburization annealing step can be performed in a region where austenite single phase region or a composite phase of ferrite and austenite exist. Specifically, 850
Figure imgf000009_0001
To 10001: temperature and dew point
Figure imgf000009_0002
The amount of decarburization at the time of decarburization annealing may be 0.0300% to 0.0600%. After the above-described annealing, the annealing may be carried out at a temperature of 1000 to 1200 It can be further annealed at a temperature of 0 ° C and a dew point temperature of 01 ° C or below.
이러한 탈탄 소둔 과정에서 전기강판의 표면의 결정립의 크기는 조대하게 성장 하게 되지만 전기강판의 내부의 결정립은 미세한 조직으로 남게된다. 이러한 탈탄 소둔 이후 표면 페라이트 결정립의 크기는 150 ! 내지 250；■일수있다.  In this decarburization annealing process, the grain size on the surface of the electric steel sheet grows to a great extent, but the crystal grains inside the electric steel sheet remain as a fine structure. The size of the surface ferrite grains after this decarburization annealing is 150? To 250%.
다음으로, 탈탄 소둔이 완료된 강판을 2차 냉간 압연한다. 통상의 고자속밀도 방향성 전기강판의 제조 공정에 있어서 넁간 압연은 90%에 가까운고압하율로 1회실시하는것이 효과적인것으로알려져 있다. 이것이 1차 재결정립 중的33 결정립만이 입자성장하기 유리한 환경을 만들어주기 때문이다. Next, the steel sheet having undergone decarburization annealing is subjected to secondary cold rolling. It is known that it is effective to carry out hot rolling at a high pressure lowering rate which is close to 90% in the manufacturing process of a conventional high magnetic flux density directional electric steel sheet. This is because only the primary recrystallized grains 33 grain form an environment favorable for grain growth.
그러나 본 발명의 일 실시예에 따른 방향성 전기강판의 제조방법은 0083 방위 결정립의 비정상 입자성장을 이용하지 않고 탈탄소둔 및 냉간 압연에 의하여 발생한 표층부의 0033 결정립을 내부 확산시키는 것이므로 표증부에서 0033방위 결정립을다수분포하도록형성하는것이 유리하다. 따라서， 냉간압연시 압하율 50%내지 70%에서 냉간압연을실시하는
Figure imgf000009_0003
집합조직이 표층부에서 다수 형성 될 수 있다. 더욱 구체적으로However, since the method of manufacturing a grain-oriented electrical steel sheet according to an embodiment of the present invention internally diffuses 0 033 grain in a surface layer caused by decarburization annealing and cold rolling without using abnormal grain growth of 0 083 orientation grain, 033 is advantageously formed so as to distribute the number of crystal grain orientation. Therefore, cold rolling is carried out at a reduction ratio of 50% to 70%
Figure imgf000009_0003
A number of texture structures can be formed in the surface layer. More specifically
55%내지 65%일수있다. 55% to 65%.
전술한 냉연강판을 탈탄 소둔하는 단계 및 탈탄 소둔이 완료된 강판을 2차냉간 압연하는 단계는 2회 이상반복하여 실시할수 있다. 2회 이상반복하여 실시함으로써, 0033집합조직이 표층부에서 다수형성 될수 2019/132356 1»（：1^1{2018/016033 The step of decarburizing and annealing the cold-rolled steel sheet and the step of cold-rolling the steel sheet after the decarburization annealing can be repeated two or more times. By repeating this process two or more times, a large number of 0 033 texture structures can be formed in the surface layer portion 2019/132356 1 »(: 1 ^ 1 {2018/016033
있다. have.
다음으로 탈탄 소둔 및 2차 냉간 압연이 완료된 전기강판은 최종 소둔을실시한다.  Next, final annealing is performed on the electric steel sheet after decarburization annealing and secondary cold rolling.
본 발명의 일 실시예에 의한 방향성 전기강판의 제조방법에서는 기존의 배치 0） 此）방식과 달리 냉간 압연에 이어 연속으로 최종 소둔을 실시할수있다.  In the method of manufacturing a grain-oriented electrical steel sheet according to an embodiment of the present invention, unlike the conventional arrangement, final annealing can be performed successively after cold rolling.
본 발명의 일 실시예에 의한 방향성 전기강판의 제조방법에서 최종 소둔은 850
Figure imgf000010_0002
내지 1000
Figure imgf000010_0001
온도및 이슬점 온도 70°（：이하에서 소둔하는제 1 단계 및 10001： 내지 12001： 온도 및 ¾ 50 부피% 이상의 분위기에서 소둔하는 제 2 단계를 포함할 수 있다. 또한 제 2 단계의 분위기는 ¾ 90 부피%이상일수있다. In the method for producing a grain-oriented electrical steel sheet according to an embodiment of the present invention, the final annealing is performed at 850
Figure imgf000010_0002
To 1000
Figure imgf000010_0001
A first step of annealing at a temperature of 70 DEG C or lower and a second step of annealing at a temperature of 10001: to 12001: 50 DEG C and an atmosphere of at least 50 vol%. The atmosphere of the second step may be ¾ 90 vol% or more.
최종 소둔 전 냉연판은 탈탄 소둔이 진행되어 소강 탄소량이 최소 슬라브의 탄소량 대비 40중량%내지 60중량%남아있는상태이다. 따라서 최종 소둔 시 제 1 단계에서는 탄소가 빠져나가면서 표층부에 형성된 결정립이 내부로확산된다. 제 1단계에서는강판중의 탄소량을 0.01중량% 이하가되도록탈탄을실시할수있다.  The cold-rolled sheet before final annealing is in a state in which decarburization annealing proceeds so that the amount of carbon black remaining in the slab is 40 wt% to 60 wt% of the minimum amount of carbon in the slab. Therefore, at the first stage of the final annealing, the carbon grains are removed and the crystal grains formed in the surface layer are diffused into the inside. In the first step, decarburization can be performed so that the amount of carbon in the steel sheet is 0.01 wt% or less.
이 후， 제 2 단계에서는 1 단계에서 확산된 고스 방위를 가진 집합조직이 성장하게 된다. 본발명의 일 실시예에 의한방향성 전기강판의 제조방법에서는 고스 집합조직은 종래의 비정상 입자성장에 의하여 결정립이 성장된경우와달리 결정립의 입경은 1™이내 일수있다.따라서， 종래의 방향성 전기강판에 비하여 결정립의 크기가 작은 고스 결정립이 다수개존재하는집합조직을가질수있다.  Thereafter, in the second step, a texture having a Goss orientation diffused in the first step is grown. In the method of manufacturing a grain-oriented electrical steel sheet according to an embodiment of the present invention, grain size of crystal grains can be within 1Tm, unlike the case where grains are grown by conventional abnormal grain growth, A plurality of goth grain grains having a small grain size may be present.
이렇게 제조된 강판은 강판의 두께 방향과 수직하는 면에 대하여, 외접원의 지름 0）1）과 내접원의 지름（此）의 비어2/1）1）가 0.5이상인 고스 결정립이 전체 고스결정립 중 95면적%이상포함할수 있다. 강판의 결정· 조직에 대해서는후술할방향성 전기강판에 대하여 구체적으로설명한다. 다음으로， 최종소둔이 완료된 강판을산세하는단계를더 포함할수 있다. 산세하는 공정을 통해 강판의 표면에 자연스럽게 형성되는산화층이 제거된다. 산화층을 제거함으로써， 의 확산이 더욱 원활히 이루어질 수 있다. 2019/132356 1»（：1^1{2018/016033 1) of the circumscribed circle and the vias 2/1) 1) of the diameter of the inscribed circle of 0.5 or more are formed on the surface perpendicular to the thickness direction of the steel sheet, %. Regarding the crystal / structure of the steel sheet, a directional electrical steel sheet to be described later will be described in detail. Next, a step of pickling the steel sheet after final annealing may be further included. Through the pickling process, the oxide layer formed naturally on the surface of the steel sheet is removed. By removing the oxide layer, the diffusion of Hf can be made more smoothly. 2019/132356 1 »(: 1 ^ 1 {2018/016033
산세하는단계는 5내지 50중량%의 산수용액을이용할수 있다. 이 때 산 수용액은 염산， 질산 또는 황산 등 무기산을 포함하는 수용액을 사용할 수 있다. 산 수용액의 농도가 너무 작은 경우， 적절한 산세가 이루어지지 않을 수 있다. 또한， 산 수용액의 농도가너무 큰 경우， 강판 표면의 조도가너무높아져， 자성에 악영향을줄수있다. The pickling step may use an aqueous acid solution of 5 to 50% by weight. At this time, an aqueous solution containing inorganic acid such as hydrochloric acid, nitric acid or sulfuric acid can be used as the acid aqueous solution. If the concentration of the aqueous acid solution is too low, proper pickling may not be achieved. In addition, when the concentration of the acid aqueous solution is too large, the surface roughness of the steel sheet becomes too high, which may adversely affect magnetism.
산세하는 단계는 50내지 1001：의 온도에서 수행될 수 있다. 온도가 너무 낮은 경우 산세가 적절히 이루어지지 않는 문제가 발생할 수 있다. 온도가너무높은경우， 재산화의 문제가발생할수있다.  The pickling step can be carried out at a temperature of from 50 to 100 &lt; 1 &gt; If the temperature is too low, pickling may not be done properly. If the temperature is too high, re-oxidation may occur.
산세하는단계는 20초내지 100초동안산세할수 있다. 시간이 너무 짧은경우， 산화층의 제거가충분히 이루어지지 않을수 있다. 시간이 너무 긴 경우， 결정립 내부와 결정립경 간의 산세능의 불균일성으로 인하여 오히려 자성이 열악해질수있다. 더욱구체적으로산세하는단계는 25내지 50초간산세할수있다.  The pickling step can be pickled for 20 to 100 seconds. If the time is too short, the removal of the oxide layer may not be sufficiently performed. If the time is too long, the magnetism may be deteriorated due to the non-uniformity of the acid pickling ability between the crystal grains and the crystal grains. More specifically, the pickling step may be pickled for 25 to 50 seconds.
다음으로， 최종 소둔 완료된 강판에
Figure imgf000011_0001
분말 포함하는 조성물을 코팅하여 코팅층을형성한다.Next, on the steel sheet after final annealing
Figure imgf000011_0001
The composition containing the powder is coated to form a coating layer.
Figure imgf000011_0002
분말의 용이한 분산 및 표면 도포를 위해， 용매를 포함하는 슬러리 형태일 수 있다. 용매로는 특별히 한정하지 아니하나, 물또는알코올을포함할수있다.
Figure imgf000011_0006
Figure imgf000011_0002
For easy dispersion and surface application of the powder, it may be in the form of a slurry containing a solvent. The solvent is not particularly limited, but may include water or an alcohol.
Figure imgf000011_0006
가능한소성로에서 고온소성을거쳐 제조할수있다. It can be manufactured by high-temperature firing in a possible firing furnace.
조성물은 분말외에
Figure imgf000011_0003
포함할수 있다. 1«的는 강판내의 확산시에 고온에 의한강판사이의 판붙음현상을방지하는소둔분리제로 작용할 뿐만 아니라 은- 분말이 강판내에 잘 부착이 될 수 있도록 바인더로서의 역할을한다.
Figure imgf000011_0004
첨가시
Figure imgf000011_0005
100중량부에 대하여 60내지 200중량부첨가할수있다. In addition to the powder,
Figure imgf000011_0003
You can include it. 1 &quot; serves not only as an annealing separator for preventing plate adhesion between steel plates due to high temperature at the time of diffusion in the steel sheet, but also serves as a binder so that the silver-powder can adhere well in the steel sheet.
Figure imgf000011_0004
Upon addition
Figure imgf000011_0005
60 to 200 parts by weight may be added per 100 parts by weight of the resin.
전술하였듯이,본발명의 일실시예에서는종래 배치 형태로운영되는 최종소둔공정을연속소둔공정으로운영할수있으며， 1차냉간압안하는 단계내지 확산층을형성하는단계는연속하여 이루어 질수있다. 2019/132356 1»（：1^1{2018/016033 As described above, in one embodiment of the present invention, the final annealing process operated in the conventional batch mode can be operated as a continuous annealing process, and the step of forming the diffusion layer from the first cold pressing step can be continuously performed. 2019/132356 1 »(: 1 ^ 1 {2018/016033
다음으로， 코팅층이 형성된 강판을 소둔하여 강판 내부에 확산층을형성한다. 이 때소둔공정은 1100내지 1200°(：의 온도에서수행할 수있다.소둔시간은 3시간이상일수있다.소둔온도가너무낮거나，소둔 시간이 너무짧은경우， 원활한 ^ 확산이 일어나지 않을수있다. Next, the steel sheet on which the coating layer is formed is annealed to form a diffusion layer in the steel sheet. At this time, the annealing process can be carried out at a temperature of 1100 to 1200 ° C. The annealing time may be 3 hours or more. If the annealing temperature is too low or the annealing time is too short, smooth diffusion may not occur.
도 1에서는 본 발명의 일 실시예에 의한 방향성 전기강판의 단면을 개략적으로 나타낸다. 도 1에 나타나듯이, 본 발명의 일 실시예에 의한 방향성 전기강판 (100)은 기재 (10) 및 기재 (10)의 표면 상에 형성된 코팅층 (20)을 포함한다. 기재 (10)는 기재 (10)의 표면에서부터 기재 (10)의 내부방향으로형성된 확산층 (11)을포함한다.  1 schematically shows a cross section of a directional electrical steel sheet according to an embodiment of the present invention. 1, a directional electrical steel sheet 100 according to an embodiment of the present invention includes a substrate 10 and a coating layer 20 formed on the surface of the substrate 10. The substrate 10 includes a diffusion layer 11 formed from the surface of the substrate 10 to the inside of the substrate 10.
이하에서는각구성별로상세히 설명한다.  Hereinafter, each configuration will be described in detail.
기재는 : 2.0%내지 8.0%, 0：0.002%이하 (0%를포함하지 않는다) 및 잔부는 근 및 기타 불가피하게 혼입되는 불순물을 포함한다. 기재의 원소 함량 및 이유에 대해서는 전술한방향성 전기강판의 제조방법과관련해서 구체적으로설명하였으므로， 중복되는설명은생략한다. 전술하였듯이， 제조 과정에서 탈탄과정을포함하므로，기재내의 탄소함량은슬라브내의 탄소 함량과달리 0.002중량%이하로포함할수있다. 또한, 제조과정에서 가 코팅층 (20)에서부터 확산하므로, 의 함량이 슬라브내의 함량과달리 2.0내지 8.0중량%포함할수있다.  The substrate comprises: 2.0% to 8.0%, 0: 0.002% or less (does not include 0%) and the balance includes muscle and other inevitably incorporated impurities. The element content and the reason for the base material have been described in detail with respect to the above-described production method of the grain-oriented electrical steel sheet, and therefore, a repetitive description thereof will be omitted. As described above, the carbon content in the substrate may be 0.002 wt% or less, unlike the carbon content in the slab, since it includes decarburization in the manufacturing process. In addition, since it diffuses from the coating layer 20 during the manufacturing process, the content of the slurry may be 2.0 to 8.0 wt%, unlike the content in the slab.
기재는 강판의 두께 방향과 수직하는 면에 대하여， 외접원의 지름 (1)1)과 내접원의 지름的2)의 비犯2/1)1)가 0.5이상인 고스 결정립이 전체 고스 결정립 중 95 면적% 이상포함할 수 있다. 여기서， 외접원이란 결정립의 외부를 둘러싸는 가상의 원 중 가장 작은 원을 의미하고, 내접원이란 결정립의 내부에 포함되는 가상의 원 중 가장 큰 원을 의미한다.  1) of the circumscribed circle 1) and the diameter of the inscribed circle 2) relative to the plane perpendicular to the thickness direction of the steel sheet is not less than 95 area% of the entire goss grain, Or more. Here, the circumscribed circle means the smallest circle among the virtual circles surrounding the outside of the crystal grains, and the inscribed circle means the largest circle of the virtual circles included in the crystal grains.
본 발명의 일 실시예에 의한 기재의 조직은， 표면의 고스 결정립이 강판의 내부로 성장하게 되므로 둥근 형태의 결정립이 생성된다. 반면， 기존의 방향성 전기강판은 본 발명의 일 실시예에 의한조직보다 긴 타원 형태의 결정립이 생성된다.  In the structure of the base material according to the embodiment of the present invention, since the goth crystal grains on the surface grow into the inside of the steel sheet, a round grain shape is produced. On the other hand, in the conventional directional electrical steel sheet, grain of elliptical shape longer than the structure according to one embodiment of the present invention is produced.
이처럼 본 발명의 일 실시예에 의한 특유의 기재 조직으로 인하여， 더욱우수한자성을얻을수있다. 2019/132356 1»（：1^1{2018/016033 As described above, due to the unique base structure according to the embodiment of the present invention, more excellent magnetic properties can be obtained. 2019/132356 1 »(: 1 ^ 1 {2018/016033
본 발명의 일 실시예에 의한 기재의 결정립의 크기는 20m 내지 500_인 것이 전체결정립중 80%이상일수있다. The size of the crystal grains of the base material according to an embodiment of the present invention may be 80% or more of the total crystal grains in the range of 20m to 500m.
이처럼 본발명의 일실시예에 의한기재 (10)는결정립의 크기가 통상의  As described above, the substrate 10 according to the embodiment of the present invention has a crystal grain size of
방향성 전기강판에 비하여 1/100 이하로 작은 특유의 미세조직으로 인하여, 압연면 ( 면)에 대해 결정립계가 다수 형성되며， 이러한 다수 결정립계를 통해 ^가 원활히 확산될 수 있다. 따라서， 후술할 확산층 (11)이 두껍게 형성될 뿐만 아니라그분포가 일정하게 되고， 또한， 가 다량 확산될 수 있다. 결과적으로 의 다량 확산을 통해 방향성 전기강판의 철손이 더욱향상된다.  Many grain boundaries are formed on the rolled surface (surface) due to a specific microstructure of less than 1/100 of the grain-oriented electrical steel sheet, and the grain can be smoothly diffused through the plurality of grain boundaries. Therefore, not only the diffusion layer 11 to be described later is formed thick, its distribution is constant, and the diffusion layer 11 can be diffused in a large amount. As a result, the iron loss of the grain oriented electrical steel sheet is further improved by the large amount of diffusion.
기재 (10)는 기재 (10)의 표면으로부터 기재 내부로 형성된 확산층 (11)을포함할수있다.본발명의 일실시예에서 확산층 (：11)이란， 기재 (10)내에서， 확산층형성 단계 이전의 기재 (10)의 함량보다, 확산층 형성 단계 이후， 의 함량이 증가한부분을의미한다. 구체적으로 확산층 (11)의 함량은 4.0내지 8.0중량%가될수있다.이 때 ,잔부는 6 및 및 기타 불가피하게 혼입되는 불순물을 포함한다. 구체적으로 확산층 (11)의 함량은기재의 함량보다 1.0내지 5.0중량%높을수 있다.
Figure imgf000013_0001
내에서 함량은두께 방향으로농도구배를형성할수 있으며 ,본발명의 일실시예에서 ^확산층 (11)내의 함량은전체에 대한 평균함량을의미한다. Base 10 can contain a diffusion layer 11 formed into the substrate from the surface of the substrate (10) diffused in one embodiment of the invention. (: 11) is, the base material 10 in the diffusion layer forming step prior to Means a portion where the content after the diffusion layer formation step is larger than the content of the base material 10 in the diffusion layer forming step. Specifically, the content of the diffusion layer 11 may be 4.0 to 8.0 wt%, the remainder including 6 and other inevitably incorporated impurities. Specifically, the content of the diffusion layer 11 may be 1.0 to 5.0% by weight higher than the content of the substrate.
Figure imgf000013_0001
The content in the diffusion layer 11 may form a concentration gradient in the thickness direction. In an embodiment of the present invention, the content in the diffusion layer 11 means an average content of the whole.
확산층 (11)의 두께는 30 내지 150 _ 로 형성될 수 있다. 전술하였듯이， 기재 (10)의 특유의 집합조직으로 인하여， 확산층 (11)의 두께가두껍게 형성된다.  The thickness of the diffusion layer 11 may be 30 to 150 [mu] m. As described above, due to the unique texture of the substrate 10, the thickness of the diffusion layer 11 is increased.
기재 (10)의 표면상에는 코팅층 (20)이 형성된다. ^ 코팅층 (20)은 0.5내지 3.0 두께로형성될수있다. 코팅층 (20)의 두께가너무얇으면, ^확산을위한충분한 ^를공급하지 못할수있다. 코팅층 (20)의 두께가 너무 두꺼우면， 확산에는 한계가 있으며, 오히려, 기재 (10)와 코팅층 (20)간의 결합력이 약화되는문제가발생할수있다.  On the surface of the substrate 10, a coating layer 20 is formed. The coating layer 20 may be formed to a thickness of 0.5 to 3.0. If the thickness of the coating layer 20 is too thin, it may not be possible to supply enough ^ for diffusion. If the thickness of the coating layer 20 is too large, there is a limit to the diffusion, and there may arise a problem that the bonding force between the substrate 10 and the coating layer 20 is weakened.
코팅층 (20)내에는 ^를 20내지 80중량%및 6를 20내지 60중량% 포함할수 있다. 코팅 조성물이 1 0를더 포함하는 경우, 및 6의 합량 2019/132356 1»（：1^1{2018/016033 In the coating layer 20, 20 to 80 wt% of? And 20 to 60 wt% of 6 may be contained. If the coating composition comprises 10 and the sum of 6 2019/132356 1 »(: 1 ^ 1 {2018/016033
100중량부에 대하여, 1 0를 60내지 200중량부더 포함할수있다. ¾¾0는 강판내의 확산시에 고온에 의한 강판사이의 판 붙음 현상을 방지하는 소둔분리제로 작용할 뿐만 아니라 6 입자가 강판내에 잘 부착이 될 수 있도록바인더로서의 역할을한다. 10 to 60 parts by weight per 100 parts by weight may be included. In addition to functioning as an annealing separator for preventing plate adhesion between the steel plates due to high temperature at the time of diffusion in the steel sheet, the steel sheet serves as a binder so that the six grains adhere well to the steel sheet.
이하, 실시예를통해상세히 설명한다. 단하기의 실시예는본발명을 예시하는것일뿐,본발명의 내용이 하기의 실시예에 의하여 한정되는것은 아니다.  Hereinafter, the embodiment will be described in detail. The following examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
제조예 : 방향성 전기강판기재의 제조  Production Example: Preparation of Oriented Electrical Steel Sheets
중량%로 : 3.22%, 0：0.245% 를 함유하고 잔부 근 및 불가피한 불순물로 이루어진 슬라브를 1250 의 온도에서 가열한 다음 1.6111111두께로 열간압연하고,이어 소둔온도 870° (:，이슬점 온도 60°〔에서 120초간소둔후, 수소，이슬점 온도 0°(：이하수소，질소혼합가스분위기에서 소둔온도 1100^ 및 30초간 소둔을 실시하였다. 열연판 소둔을 마치고 냉각한 후 산세를 실시하고， 60%의 압하율로냉간압연하였다.  The slabs containing 3.22% and 0: 0.245% by weight and consisting of the residual roots and unavoidable impurities were heated at a temperature of 1250 and then hot rolled to a thickness of 1.6111111, followed by annealing at a temperature of 870 ° (: dew point temperature of 60 [ After annealing for 120 seconds, annealing was carried out for 30 seconds at an annealing temperature of 1100 ° C in a mixed gas atmosphere of hydrogen and nitrogen at a dew point of 0 ° (or less). After the hot-rolled sheet was annealed, it was pickled, Followed by cold rolling at a reduction ratio.
냉간압연된판은다시 소둔온도 870° (:，이슬점 온도 60° (:에서 60초간 탈탄소둔후， 수소， 이슬점 온도 0°(1이하수소， 질소혼합가스분위기에서 소둔하고, 소둔온도 1100^ 및 50초간 소둔을 실시하고 냉각한 후 산세를 실시하고， 60%의 압하율로냉간압연하였다.  The cold-rolled steel sheet was subjected to decarburization annealing at an annealing temperature of 870 ° C (dew point temperature: 60 ° C) for 60 seconds, followed by hydrogen annealing at a dew point temperature of 0 ° (1 or less in a hydrogen and nitrogen mixed gas atmosphere, Annealed for 50 seconds, cooled, pickled, and then cold-rolled at a reduction ratio of 60%.
이후 최종 소둔시에는 900° (:의 온도에서 수소， 질소의 습윤 (이슬점 온도 60°0 혼합가스 분위기에서 60초간 탈탄 소둔을 실시한 후 1050° (:의 In the final annealing, decarburization annealing is performed in a mixed gas atmosphere of hydrogen and nitrogen (dew point temperature 60 ° 0) for 60 seconds at a temperature of 900 ° (:
100% ¾분위기에서 3분동안열처리를실시하였다. Heat treatment was performed in a 100% ¾ atmosphere for 3 minutes.
냉간압연된판은다시 소둔온도 870° (:，이슬점 온도 60° (:에서 60초간 소둔 후， 수소， 이슬점 온도 0。 (:이하 수소， 질소 혼합가스 분위기에서 소둔온도 1100^및 50초간탈탄소둔을실사하고냉각한후산세를실시하고， 60%의 압하율로 2차냉간압연하였다. 최종두께는 288,였다.  The cold-rolled steel sheet was subjected to decarburization annealing at a temperature of 870 ° C. (dew point temperature: 60 °) for 60 seconds, hydrogen and dew point temperature (0.) , Cooled, pickled, and secondarily cold rolled at a reduction ratio of 60%. The final thickness was 288 mm.
이후 최종 소둔시에는 900° (:의 온도에서 수소， 질소의 습윤 (이슬점 온도 60°0혼합가스분위기에서 60초간소둔을실시한후 1050° (:의 100% ¾ 분위기에서 3분 동안 소둔을 실시하였다. 최종 강판의 탄소 함량은 30??01 이었다. Thereafter, at final annealing, annealing was performed for 60 seconds in a mixed gas atmosphere of hydrogen and nitrogen at a temperature of 900 DEG C (dew point temperature: 60 DEG C for 60 seconds, followed by annealing for 3 minutes in a 100: The carbon content of the final steel plate was 30 ?? 01 .
압연면에 대한的33결정립 분포를 £630분석을통하여 나타낸사진을 2019/132356 1»(：1^1{2018/016033 The distribution of the grain 33 on the rolled surface is shown by the analysis of £ 630 2019/132356 1 »(: 1 ^ 1 {2018/016033
도 2에 나타내었다. 2.
표 1 은 도 2에 나타난 제조예에서의 能33 결정립의 내접원과 외접원의 상대적인크기를측정하고그비 (敗/아)를나타낸표이다. Table 1 is a table showing the relative sizes of the inscribed circle and the circumscribed circle of the Fe- 33 crystal grains in the production example shown in Fig.
【표 11  [Table 11
Figure imgf000015_0001
Figure imgf000015_0001
표 1에서 나타나듯이, 모든 0083결정립의 비的2/1)1)가 0.5이상임을 확인할수있다. As shown in Table 1, it can be confirmed that the ratio 2/1) 1) of all 0 083 grains is 0.5 or more.
비교제조예 : 방향성 전기강판기재의 제조 2019/132356 1»(：1^1{2018/016033 Comparative Production Example: Preparation of Oriented Electrical Steel Sheets 2019/132356 1 »(: 1 ^ 1 {2018/016033
중량%로 : 3.18%, 0：0.055%, 0.1% 를 함유하고 잔부 근 및 불가피한 불순물로 이루어진 슬라브를 1150°（:의 온도에서 가열한 다음The slabs containing 3.18%, 0: 0.055%, and 0.1% by weight of the residual roots and unavoidable impurities were heated at a temperature of 1150 °
2.2™두께로열간압연하고， 이어 통상의 방향성 전기강판의 열연판소둔을 실시하고냉각한후산세를실시하고, 288/^1두께로냉간압연하였다. Hot-rolling to 2.2 ™ thickness, followed by performing hot-rolled steel sheet annealing of the conventional grain-oriented electrical steel sheet and subjected to pickling after the cooling, which was then cold-rolled to 288 / ^ 1 thickness.
이후， 이슬점 온도 60°〔 수소, 질소 혼합가스 및 암모니아 혼합 분위기에서 소둔온도 850°0 에서 3분간 동시탈탄질화 소둔을 실시하였다. 이후승온율 15도/느로승은한후 1200 °（：에서 20시간을유지하는고온소둔을 실시하였다.  Then, simultaneous decarburization annealing was performed for 3 minutes at an annealing temperature of 850 DEG C in a mixed atmosphere of hydrogen, nitrogen gas and ammonia at a dew point temperature of 60 DEG. Thereafter, the temperature was increased to 15 degrees / degree and then annealed at a high temperature of 1200 degrees (:) for 20 hours.
2차재결정의 조직사진을도 3에 나타내었다.  A photograph of the structure of the secondary recrystallization is shown in Fig.
표 2 는 도 3에 나타난 방향성 전기강판의 내접원과 외접원의 상대적인크기를측정하고그비어2/1）1）를나타낸표이다.  Table 2 is a table showing the relative sizes of the inscribed circle and the circumscribed circle of the grain-oriented electrical steel sheet shown in Fig. 3 and showing the vias 2/1) 1).
【표 2】  [Table 2]
Figure imgf000016_0001
2019/132356 1»(：1^1{2018/016033
Figure imgf000017_0002
표 2에서 나타나듯이, 비교제조예에서 제조한기재는조직이 긴 타원 형태의 결정립이므로敗/이의 값은본발명의 일 실시예에 의한기재 보다 작은값을나타나게 됨을확인할수있다.
Figure imgf000016_0001
2019/132356 1 »(: 1 ^ 1 {2018/016033
Figure imgf000017_0002
As shown in Table 2, it can be confirmed that the substrate prepared in the comparative example is a crystal having a long elliptical structure, so that the value of defects / values is smaller than that described in the embodiment of the present invention.
실시예 1  Example 1
제조예 및 비교제조예에서 제조한 방향성 전기강판 기재에 최종소둔된판은 80°（：에서 25\ 농도의 敗1 수용액을이용하여 20초간산세 과정을거쳤다. 산세 공정이 완료된 강판은 33.5중량% 함량의
Figure imgf000017_0001
계 분말을 소성 ¾ 0 분말과 에틸 알코올을 혼합하여 강판에 도포한 후 1100 내지 1200^에서 5시간을소둔하여 두께 1.7™의 코팅층을형성하였다. 소둔시간에 따른기재 전체의 함량， 확산층의 함량및 ^ 확산층의 두께를표 3에 나타내었다. Preparation and comparison of the final annealed sheet to a grain-oriented electrical steel sheet base material produced in Production Example was 80 ° (: using a solution of 25敗1 \ concentration from subjected to a pickling process for 20 seconds. The pickled steel plate had a content of 33.5% by weight
Figure imgf000017_0001
The powders of the system were mixed with a mixture of calcined powder and ethyl alcohol, and the coated powder was annealed at 1100 to 1200 ° C for 5 hours to form a coating layer having a thickness of 1.7 占 퐉. Table 3 shows the contents of the entire substrate, the content of the diffusion layer, and the thickness of the diffusion layer with respect to the annealing time.
철손 자속밀도를 此6 측정법을 이용하여 측정하였고， 50¾에서 1. 6313로자화될때까지의 철손 17/5ᄋ）및 1000쇼細자기장하에서 유도되는자속밀도犯1（））을측정하였다. 그결과를하기 표 3에 정리하였다. 【표 3] It had a core loss magnetic flux density measured by the measuring method此6, from 50¾ 1. 63 1 to measure the iron loss ᄋ 17/5) and the magnetic flux density犯1 ()) is derived under a magnetic field of up to 1000 show細3 Rosa flower when. The results are summarized in Table 3 below. [Table 3]
Figure imgf000017_0003
2019/132356 1»（：1^1{2018/016033
Figure imgf000017_0003
2019/132356 1 »(: 1 ^ 1 {2018/016033
Figure imgf000018_0001
Figure imgf000018_0001
표 3에서 나타나듯이， 기존의 2차 재결정 조직을 갖는 비교제조예의 기재를이용하여 ^ 확산을위한소둔을행할시， 의 확산이 잘일어나지 않을 뿐만 아니라 내부로 확산된 의 불균일성으로 인하여 철손이 열화되는것을확인할수있다. 그러나,본발명의 일실시예와같이 결정립 크기가 통상의 방향성 전기강판에 비하여 1/100이하이면서 외접원의 지름（1）1）과 내접원의 지름（敗）의 비犯2/1）1）가 큰 제조예를 기재로 이용한 경우에는 의 확산이 균일하게 잘 일어나 함량이 높을 뿐만 아니라 철손이 우수함을알수있다.  As shown in Table 3, when the annealing for diffusing is performed using the base material of the comparative production example having the existing secondary recrystallized structure, diffusion of not only hardly occurs but also iron loss is deteriorated due to nonuniformity of diffusion into the inside . However, as in one embodiment of the present invention, the grain size is less than 1/100 of that of a conventional grain-oriented electrical steel sheet, and the ratio of the diameter of the circumscribed circle 1) and the diameter of the inscribed circle 2/1) When a large production example is used as the substrate, it is found that the diffusion is uniformly and well caused, and the iron loss is excellent as well as the content.
실시예 2  Example 2
중량%로 :2.0%， （：:0.20%를함유하고잔부 근및 불가피한불순물로 이루어진 슬라브를 1250°（:의 온도에서 가열한 다음 1.6™ 두께로 열간압연하고，이어 소둔온도 870°（: ,이슬점 온도 60°〔에서 120초간소둔후， 수소,이슬점 온도 0°（그이하수소,질소혼합가스분위기에서소둔온도 1100^ 및 30초간 열연판 소둔을 실시하고 냉각한 후 산세를 실시하고， 60%의 압하율로냉간압연하였다.  The slabs containing 2.0% by weight, 0.20% by weight, and the remainder of the slabs and inevitable impurities were heated at a temperature of 1250 DEG C, followed by hot rolling to a thickness of 1.6 DEG C, followed by annealing at a temperature of 870 DEG C: After annealing at a dew point temperature of 60 ° C for 120 seconds, hot rolled sheet annealing was carried out under hydrogen and a dew point temperature of 0 ° C (hydrogen and nitrogen gas mixture atmosphere at an annealing temperature of 1100 ° and 30 seconds, By cold rolling.
넁간압연된판은다시 소둔온도 870°（:，이슬점 온도 60°（:에서 60초간 소둔 후， 수소, 이슬점 온도 0°0；이하 수소, 질소 혼합가스 분위기에서 소둔온도 1100^및 50초간탈탄소둔을실시하고냉각한후산세를실시하고， 60%의 압하율로냉간압연하였다.  The hot-rolled sheet was subjected to decarburization annealing at a temperature of 870 ° (dew point: 60 °) for 60 seconds, followed by hydrogen and dew point temperature 0 ° 0 , Cooled, pickled, and then cold-rolled at a reduction ratio of 60%.
이후 최종 소둔시에는 900。（:의 온도에서 수소， 질소의 습윤 （이슬점 온도 60° 혼합가스 분위기에서 60초간 탈탄 소둔을 실시한 후 1050°（:의 Then, at the final annealing step, decarburization annealing was performed at a temperature of 900 ° C. for 60 seconds in a mixed gas atmosphere of hydrogen and nitrogen (dew point temperature: 60 °), and then 1050 °
100% 분위기에서 3분동안소둔을실시하였다. Annealing was performed for 3 minutes in a 100% atmosphere.
최종소둔된 판은 80°（:의 25% 농도의 1€1 수용액을 이용하여 20초간 산세 과정을 거쳤다. 산세 공정이 완료된 강판은 33.5 중량% 함량의 분말을소성 ¾!요0 ?）0¾년6와 시（：0^101을혼합하여 강판에 도포하여 The final annealed plate was subjected to a pickling process for 20 seconds using a 1% aqueous solution of 80% (: 25% strength). For the steel sheet after the pickling process, 33.5% by weight of the powder was mixed with steel (0: 101) at 0,
2.1쌔！두께의 코팅층을 형성하였다. 이후， 1150^ 에서 1 내지 10시간 소둔하여 를 확산시켰다. 소둔 시간에 따른 기재 전체의 함량. 확산층의 함량및 확산층의 두께를표 4에 나타내었다. 2.1 A thick coating layer was formed. Thereafter, it was annealed at 1150 캜 for 1 to 10 hours to diffuse it. The total content of the substrate according to the annealing time. Table 4 shows the content of the diffusion layer and the thickness of the diffusion layer.
【표 4]
Figure imgf000019_0001
[Table 4]
Figure imgf000019_0001
표 4에서 나타나듯이， 의 확산이 균일하게 잘 일어나 함량이 높을뿐만아니라철손이 우수함을알수있다.  As shown in Table 4, it can be seen that the diffusion is uniformly and uniformly spread, and the iron loss is excellent as well as the content.
이상 첨부된 도면을 참조하여 본 발명의 실시예를 설명하였지만, 본 발명이 속하는기술분야에서 통상의 지식을가진자는본발명이 그기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수있다는것을이해할수있을것이다.  While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, You will understand.
그러므로 이상에서 기술한실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다. 본 발명의 범위는 상기 상세한 설명보다는후술하는특허청구범위에 의하여 나타내어지며， 특허청구범위의 의미 및 범위 그리고 그 균등 개념으로부터 도출되는 모든 변경 또는 변경된형태가본발명의 범위에 포함되는것으로해석되어야한다.  It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present invention.
【부호의 설명】  DESCRIPTION OF REFERENCE NUMERALS
100 : 방향성 전기강판 10 : 기재  100: directional electric steel sheet 10: base material
11 : 확산층 20 : 코팅층  11: diffusion layer 20: coating layer

Claims

2019/132356 1»（：1^1{2018/016033 【청구범위】 2019/132356 1 (: 1 ^ {2018/016033)
【청구항 1】  [Claim 1]
중량%로, : 1.0%내지 4.0%, 0：0.1%내지 0.4%및 잔부는 6및기타 불가피하게혼입되는불순물을포함하는슬라브를제조하는단계; By weight,: 1.0% to 4.0%, 0: 0.1% to 0.4% and the remainder being 6 and other inevitably incorporated impurities;
상기 슬라브를가열하는단계;  Heating the slab;
상기 슬라브를열간압연하여 열연강판을제조하는단계;  Hot-rolling the slab to produce a hot-rolled steel sheet;
상기 열연강판을열연판소둔하는단계 ;  Annealing the hot-rolled steel sheet by hot-rolling;
상기 열연판소둔된 열연강판을 1차냉간압연하는단계 ;  Subjecting the hot-rolled steel sheet annealed to a primary cold-rolling;
상기 1차냉간압연된강판을탈탄소둔하는단계 ;  Decarbonizing the primary cold-rolled steel sheet;
상기 탈탄소둔이 완료된강판을 2차냉간압연하는단계;  Subjecting the steel sheet after the decarburization annealing to secondary cold rolling;
상기 2차냉간압연이 완료된강판을최종소둔하는단계 ;  Final annealing the steel sheet after completion of the secondary cold rolling;
최종 소둔이 완료된 강판에 분말포함하는 조성물을코팅하여 코팅층을형성하는단계 ; 및  Forming a coating layer by coating a composition including powder on the steel sheet after final annealing; And
코팅층이 형성된 강판을 소둔하여 강판 내부에 확산층을 형성하는단계를포함하는방향성 전기강판의 제조방법 .  And annealing the steel sheet on which the coating layer is formed to form a diffusion layer inside the steel sheet.
【청구항 2]  [Claim 2]
제 1항에 있어서，  The method according to claim 1,
상기 열연판 소둔하는 단계에서 탈탄과정을 포함하는 방향성 전기강판와제조방법 .  And a decarburization step in the step of annealing the hot-rolled steel sheet.
【청구항 3]  [3]
제 1항에 있어서，  The method according to claim 1,
상기 열연판 소둔하는 단계는 850” 내지 1000
Figure imgf000020_0001
온도 및 이슬점 내지 70°（：에서 소둔하는방향성 전기강판의 제조방법 .Wherein the annealing of the hot-rolled sheet comprises:
Figure imgf000020_0001
A method for producing a directional electrical steel sheet which is annealed at a temperature and a dew point to 70 ° (:).
【청구항 4] [4]
제 1항에 있어서，  The method according to claim 1,
상기 1차 냉간 압연된 강판을 탈탄 소둔하는 단계는 850” 내지 10001： 온도 및 이슬점 온도
Figure imgf000020_0002
내지 701：에서 소둔하는 방향성 전기강판의 제조방법. The step of decarbonizing the primary cold-rolled steel sheet comprises the steps of: 850 "to 10001:
Figure imgf000020_0002
To 701 &lt; RTI ID = 0.0 &gt;:&lt; / RTI &gt;
【청구항 5]  [Claim 5]
제 1항에 있어서， 2019/132356 1»（：1^1{2018/016033 The method according to claim 1, 2019/132356 1 »(: 1 ^ 1 {2018/016033
상기 1차 냉간 압연된 강판을 탈탄 소둔하는 단계 및 상기 탈탄 소둔이 완료된강판을 2차냉간압연하는단계는 2회 이상반복되는방향성 전기강판의 제조방법. Wherein the step of decarburization annealing the primary cold-rolled steel sheet and the step of secondary cold-rolling the steel sheet after the decarburization annealing are repeated twice or more.
【청구항 6]  [Claim 6]
제 1항에 있어서，  The method according to claim 1,
상기 최종소둔하는 단계는 850
Figure imgf000021_0001
내지 1000
Figure imgf000021_0002
온도 및 이슬점 온도 70方이하에서 소둔하는제 1단계 및 1000
Figure imgf000021_0003
내지 12001： 온도및 ¾ 50부피% 이상의 분위기에서 소둔하는 제 2 단계를 포함하는 방향성 전기강판의 제조방법. The final annealing may be performed at 850
Figure imgf000021_0001
To 1000
Figure imgf000021_0002
A first step of annealing at a temperature and a dew point temperature of 70 degrees or less,
Figure imgf000021_0003
To 12001: a temperature and a second step of annealing in an atmosphere of ¾ 50 vol% or more.
【청구항 7]  [7]
제 1항에 있어서，  The method according to claim 1,
상기 최종 소둔하는 단계 이후, 5 내지 50 중량%의 산 수용액을 이용하여， 50내지 1001： 온도에서 20초내지 100초동안산세하는단계를 더 포함하는방향성 전기강판의 제조방법.  Further comprising the step of pickling at a temperature of 50 to 1001: for 20 seconds to 100 seconds using an aqueous acid solution of 5 to 50% by weight after the final annealing step.
【청구항 8】  8.
제 1항에 있어서,  The method according to claim 1,
상기 코팅층을 형성하는 단계에서， 상기 조성물은
Figure imgf000021_0004
더 포함하는방향성 전기강판의 제조방법 . In the step of forming the coating layer,
Figure imgf000021_0004
Wherein the method further comprises the steps of:
【청구항 9]  9]
제 1항에 있어서，  The method according to claim 1,
상기 코팅층을형성하는단계에서，상기 분말은 를 20내지 80 중량%포함하는방향성 전기강판의 제조방법 .  Wherein the step of forming the coating layer comprises 20 to 80 wt% of the silver powder.
【청구항 10】  Claim 10
제 1항에 있어서,  The method according to claim 1,
상기 확산층을 형성하는 단계에서， 상기 온도는 1100 내지 In the step of forming the diffusion layer,
1200 이고， 소둔시간은 3시간이상인방향성 전기강판의 제조방법 . 1200 and the annealing time is 3 hours or more.
【청구항 11】  Claim 11
제 1항에 있어서，  The method according to claim 1,
상기 1차넁간압연하는단계 내지 상기 확산층을형성하는단계는 연속하여 이루어지는방향성 전가강판의 제조방법 . 2019/132356 1»（：1^1{2018/016033 Wherein the step of rolling the primary die to the step of forming the diffusion layer is performed continuously. 2019/132356 1 »(: 1 ^ 1 {2018/016033
【청구항 12] [12]
중량%로, : 2.0%내지 8.0%, 0：0.002%이하（0%를포함하지 않는다）및 잔부는 6및 기타불가피하게혼입되는불순물을포함하는기재 및 By weight, from 2.0% to 8.0%, 0: 0.002% or less (excluding 0%) and the balance of 6 and other inevitably incorporated impurities; and
상기 기재의 표면상에 형성된 코팅층을포함하고，  A coating layer formed on the surface of the substrate,
상기 기재는 강판의 두께 방향과 수직하는 면에 대하여, 외접원의 지름 0）1）과 내접원의 지름이2）의 비（02/1）1）가 0.5이상인 고스 결정립이 전체고스결정립 중 95면적%이상포함하고，  1)) of 0.5 or more of the diameter of the circumscribed circle 0) and the diameter of the inscribed circle is 2 or more with respect to the plane perpendicular to the thickness direction of the steel sheet is 95% Or more,
상기 기재는 기재의 표면에서부터 기재의 내부 방향으로 형성된 확산층을포함하는방향성 전기강판.  Wherein the substrate comprises a diffusion layer formed from the surface of the substrate to the inside of the substrate.
【청구항 13]  [13]
제 12항에 있어서，  13. The method of claim 12,
상기 코팅층은 를 20내지 80중량%및 £를 20내지 60중량% 포함하는방향성 전기강판. Wherein the coating layer comprises 20 to 80% by weight and the pellet is 20 to 60% by weight.
【청구항 14】  14.
제 13항에 있어서，  14. The method of claim 13,
상기 코팅층은 및 6의 합량 100중량부에 대하여， 1 0를 60내지 200중량부더 포함하는방향성 전기강판. Wherein the coating layer comprises 60 to 200 parts by weight of 10 to 100 parts by weight of the sum of 6 and 6 .
【청구항 15】  15.
제 12항에 있어서,  13. The method of claim 12,
상기 ^코팅층의 두께는 0.5내지 3.0_인방향성 전기강판.  Wherein the thickness of the &lt; RTI ID = 0.0 &gt; ^ coating &lt; / RTI &gt;
【청구항 16】  Claim 16
제 12항에 있어서，  13. The method of claim 12,
상기 확산층은 를 4.0내지 8.0중량%포함하는방향성 전기강판.  And the diffusion layer comprises 4.0 to 8.0 wt%.
【청구항 17】 17.
제 12항에 있어서，  13. The method of claim 12,
상기 확산층의 두께는 30내지 150™인방향성 전기강판.  Wherein the thickness of the diffusion layer is 30 to 150 占 퐉.
【청구항 18】  Claim 18
제 12항에 있어서，  13. The method of claim 12,
상기 기재는 결정립 크기가 20_ 내지 500_인 결정립의 비율이 80%이상인방향성 전기강판.  Wherein the base material has a ratio of crystal grains having a grain size of 20 to 500 and not less than 80%.
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