WO2017082621A1 - Tôle d'acier électrique à grains orientés et son procédé de fabrication - Google Patents

Tôle d'acier électrique à grains orientés et son procédé de fabrication Download PDF

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Publication number
WO2017082621A1
WO2017082621A1 PCT/KR2016/012851 KR2016012851W WO2017082621A1 WO 2017082621 A1 WO2017082621 A1 WO 2017082621A1 KR 2016012851 W KR2016012851 W KR 2016012851W WO 2017082621 A1 WO2017082621 A1 WO 2017082621A1
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Prior art keywords
steel sheet
grain
annealing
oriented electrical
less
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PCT/KR2016/012851
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English (en)
Korean (ko)
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송대현
박준수
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주식회사 포스코
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Priority to CN201680065834.8A priority Critical patent/CN108350545A/zh
Priority to JP2018524277A priority patent/JP2019501282A/ja
Priority to US15/775,311 priority patent/US20180327879A1/en
Publication of WO2017082621A1 publication Critical patent/WO2017082621A1/fr

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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
    • 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
    • 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
    • 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
    • C21D8/1272—Final recrystallisation annealing
    • 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
    • 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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
    • 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
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—Pretreatment of the material to be coated
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/24—Nitriding
    • C23C8/26—Nitriding 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
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80—After-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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • 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
    • C21D8/1283—Application of a separating or insulating coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • It relates to a grain-oriented electrical steel sheet and a method of manufacturing the same.
  • a grain-oriented electrical steel sheet exhibits a Goss texture having a texture of ⁇ 110 ⁇ ⁇ 001> with respect to the rolling direction, and is a soft magnetic material having excellent magnetic properties in one direction or in the rolling direction.
  • complex processes such as component control in steelmaking, slab reheating and hot rolling process factor control in hot rolling, hot roll annealing heat treatment, primary recrystallization annealing, and secondary recrystallization annealing are required. It must also be very precise and strictly controlled.
  • the inhibitor which is one of the factors expressing goth aggregates, that is, the grain growth inhibitor that suppresses indiscriminate growth of primary recrystallized grains and allows only goth aggregates to grow when secondary recrystallization occurs.
  • the inhibitor In order to obtain goth aggregates in the final annealing, the growth of all primary recrystallized grains must be suppressed until the second recrystallization occurs. In order to obtain sufficient restraining force, the amount of inhibitor must be large enough and the distribution must be uniform. .
  • the thermal stability of the inhibitor should be excellent and not easily decomposed.
  • Secondary recrystallization occurs when the inhibitor that inhibits the growth of the primary recrystallized grains during final annealing is decomposed or loses its inhibitory power in the appropriate temperature range.In this case, specific grains such as Goth grains grow rapidly in a relatively short time. .
  • the quality of oriented electrical steel sheet can be evaluated by the magnetic flux density and iron loss, which are typical magnetic properties.
  • high-quality oriented electrical steel sheet is capable of manufacturing high-efficiency power equipment due to its re-characteristics, thereby achieving miniaturization of power equipment and high efficiency.
  • the present invention provides a grain-oriented electrical steel sheet having low iron loss and excellent magnetic flux density and a method of manufacturing the same.
  • One embodiment of the present invention by weight, Si: 2.0% or more and 5.0% or less, acid-soluble Al: 0.005% or more and 0.04% or less, Mn: 0.01% or more and 0.2% or less, N: 0.01% or less (0% is S: 0.01% or less (excluding 0%), Sb: 0.01% or more and 0.05% or less, C: 0.02% or more and 0.08% or less, P: 0.0005% or more and 0.045% or less, Sn: 0.03% or more and less than 0.08% , Cr: 0.01% or more and 0.2% or less and provides a grain-oriented electrical steel sheet composed of the balance Fe and other unavoidable impurities.
  • the steel sheet may be a grain-oriented electrical steel sheet that satisfies the following formula 1 calculated by the content (% by weight) of each component.
  • the steel sheet may be a grain-oriented electrical steel sheet that satisfies the following formula 2 calculated by the content (% by weight) of each component.
  • the steel sheet may be a grain-oriented electrical steel sheet that satisfies the following formula 1 and formula 2 calculated by the content (% by weight) of each component.
  • the grain-oriented electrical steel sheet may be a grain-oriented electrical steel sheet in which a fraction of the austenite phase in the steel sheet is 20 to 30%.
  • the grain-oriented electrical steel sheet may have an area of grains having a ratio between the longest diameter and the shortest diameter of the grains of 1.0 or more among the grains having the shortest diameter of 3 mm or more and 5% or more with respect to the total grains.
  • Another embodiment of the present invention by weight, Si: 2.0% or more and 5.0% or less, acid-soluble Al: 0.005% or more and 0.04% or less, Mn: 0.01% or more and 0.2% or less, N: 0.01% or less (0 % Is excluded), S: 0.01% or less (0% is excluded), Sb: 0.01% or more and 0.05% or less, C: 0.02% or more and 0.08% or less, P: 0.0005% or more and 0.045% or less, Sn: 0.03% or more and 0.08 Reheating a steel slab comprising less than%, Cr: 0.01% or more and 0.2% or less and consisting of the balance Fe and other unavoidable impurities; Manufacturing a steel sheet by performing hot rolling, hot rolled sheet annealing, and cold rolling on the reheated steel slab; Performing decarbonization and nitride annealing on the cold rolled steel sheet; And finally annealing the decarbonized and nitrided annealed steel sheet. It provides
  • the steel slab may be a method for producing a grain-oriented electrical steel sheet that satisfies the following formula 1 calculated by the content (% by weight) of each component.
  • the steel slab may be a method of manufacturing a grain-oriented electrical steel sheet that satisfies the following Equation 2 calculated by the content (% by weight) of each component.
  • the steel slab may be a method of manufacturing a grain-oriented electrical steel sheet that satisfies the following Equations 1 and 2 calculated by the content (% by weight) of each component.
  • the reheating; the temperature may be a method for producing a grain-oriented electrical steel sheet that is 1000 to 1250 °C.
  • the hot-rolled sheet annealing temperature of the reheated steel slab is subjected to hot rolling, hot rolled sheet annealing, and cold rolling to produce a steel sheet.
  • Hot rolling, hot rolling annealing, and cold rolling of the reheated steel slab to produce a steel sheet; cold rolling thickness of 0.10mm or more may be a method of manufacturing a grain-oriented electrical steel sheet 0.50mm or less.
  • Decarburizing annealing and nitriding annealing of the cold rolled steel sheet the decarburizing annealing and nitriding annealing at the same time, or performing annealing nitriding after decarbonization annealing or independently denitrification after nitriding annealing. It may be a method for producing a grain-oriented electrical steel sheet.
  • Final annealing with respect to the decarbonized and annealed steel sheet may be a method of manufacturing a grain-oriented electrical steel sheet further comprising the step of applying an annealing separator to the previously decarbonized and nitrided annealing steel sheet.
  • Final annealing of the decarbonized and nitrided annealed steel sheet; the final annealing temperature may be a method for producing a grain-oriented electrical steel sheet is 800 to 1250 °C.
  • Final annealing with respect to the decarbonized and annealed steel sheet is performed in an atmosphere containing at least one of nitrogen or hydrogen, but after the final annealing temperature is reached in a 100% hydrogen atmosphere of the grain-oriented electrical steel sheet It may be a manufacturing method.
  • a grain-oriented electrical steel sheet having low iron loss and excellent magnetic flux density, and a method of manufacturing the same.
  • % means weight percent unless otherwise defined.
  • One embodiment of the present invention by weight, Si: 2.0% or more and 5.0% or less, acid-soluble Al: 0.005% or more and 0.04% or less, Mn: 0.01% or more and 0.2% or less, N: 0.01% or less (0% is S: 0.01% or less (excluding 0%), Sb: 0.01% or more and 0.05% or less, C: 0.02% or more and 0.08% or less, P: 0.0005% or more and 0.045% or less, Sn: 0.03% or more and less than 0.08% , Cr: 0.01% or more and 0.2% or less and provides a grain-oriented electrical steel sheet composed of the balance Fe and other unavoidable impurities.
  • the grain-oriented electrical steel sheet may be a grain-oriented electrical steel sheet that satisfies the following formula 1 calculated by the content (% by weight) of each component.
  • the grain-oriented electrical steel sheet may be a grain-oriented electrical steel sheet that satisfies the following formula 2 calculated by the content (% by weight) of each component.
  • the grain-oriented electrical steel sheet may be a grain-oriented electrical steel sheet that satisfies the following formula 1 and formula 2 calculated by the content (% by weight) of each component.
  • Mn, Si, and C are in weight percent, and are controlled to satisfy Equation 1 above. This is to maintain the phase transformation fraction of the austenite phase, which inevitably occurs in the temperature range of steel slab reheating, hot rolling and subsequent hot-rolled sheet annealing, in the manufacture of the grain-oriented electrical steel sheet. If the austenite phase is too small, the hot rolled sheet microstructure may remain in the final product after high temperature annealing, which may lead to inferior magnetic properties. If there are too many austenite phases, ⁇ + ⁇ phase transformation may be excessively activated during primary recrystallization annealing (decarbonization annealing), thereby causing damage to Goss aggregates.
  • the content of Sn, Sb, Cr is in weight percent, and is controlled to satisfy Equation 2 above. This is to allow the oxide layer of the decarbonized annealing plate, which is the base of the base coating, to be appropriately formed.
  • the grain-oriented electrical steel sheet may be a grain-oriented electrical steel sheet having an area of grains having a ratio between the longest diameter and the shortest diameter of the grains of 1.0 or more among the grains having the shortest diameter of 3 mm or more and 5% or more with respect to the total grain size. have.
  • a grain-oriented electrical steel sheet having more grains grown in the rolling direction may have better magnetism in the rolling direction required by the grain-oriented electrical steel sheet itself.
  • % Means weight%.
  • Si 2.0% or more and 5.0% or less
  • Si is a basic composition of electrical steel sheet to increase the specific resistance of the material serves to lower the core loss (core loss). If the Si content is less than 2.0%, the resistivity decreases and the eddy current loss increases, thereby deteriorating iron loss characteristics. In addition, the phase transformation between ferrite and austenite becomes active during decarbonation, which severely damages the primary recrystallized texture. In addition, high temperature annealing causes phase transformation between ferrite and austenite, which not only makes the secondary recrystallization unstable, but also severely damages the ⁇ 110 ⁇ goth aggregation structure.
  • the Si content is greater than 5.0%, the SiO 2 and Fe 2 SiO 4 oxide layers are excessively and densely formed during the decarburization annealing, thereby delaying the decarburization behavior.
  • phase transformation between ferrite and austenite occurs continuously during the decarbonation annealing treatment, which severely damages the primary recrystallization texture.
  • the nitriding behavior is delayed, and thus nitrides such as (Al, Si, Mn) N and AlN are not sufficiently formed, and thus sufficient grain restraint force necessary for secondary recrystallization at high temperature annealing is obtained. It cannot be secured.
  • the Si content exceeds 5.0%, the brittleness, which is a mechanical property of the electrical steel sheet, increases, and the toughness decreases, thereby increasing the occurrence rate of plate break during the rolling process. As a result, the interplate weldability is inferior, and thus easy workability cannot be secured.
  • Si is preferably limited to 2.0% or more and 5.0% or less.
  • Acid Soluble Al 0.005% or more and 0.04% or less
  • Al forms AlN which precipitates finely during hot rolling and annealing, or in the annealing process after cold rolling, nitrogen ions introduced by ammonia gas are combined with Al, Si, and Mn in solid solution in steel.
  • nitrogen ions introduced by ammonia gas are combined with Al, Si, and Mn in solid solution in steel.
  • nitrides of the form (Al, Si, Mn) N and AlN will act as potent grain growth inhibitors.
  • the Al content is more than 0.04%, coarse nitrides are formed to lower grain growth inhibition. Therefore, the Al content is limited to 0.005% or more and 0.04% or less.
  • Mn 0.01% or more and 0.2% or less
  • Mn like Si, reduces the total iron loss by increasing the specific resistance and reducing the eddy current loss.
  • S sulfur
  • Si silicon
  • nitrogen introduced by nitriding nitrogen introduced by nitriding to form precipitates of (Al, Si, Mn) N. Therefore, it is an important element for suppressing growth of primary recrystallized grains and causing secondary recrystallization.
  • the Mn content is more than 0.2%, a large amount of (Fe, Mn) and Mn oxides are formed on the surface of the steel sheet in addition to Fe 2 SiO 4 , thereby preventing the formation of the base coating formed during high temperature annealing, thereby decreasing the surface quality.
  • the content of Mn is limited to 0.01% or more and 0.2% or less.
  • N is an important element that reacts with Al and B to form AlN and BN, and is preferably added at 0.01% or less in the steelmaking step.
  • N is added in excess of 0.01%, the surface defect called Blister by nitrogen diffusion in the post-hot rolling process is caused.
  • Blister by nitrogen diffusion in the post-hot rolling process is caused.
  • too much nitride is formed in the slab state, rolling becomes difficult, which may cause a complicated process and increase manufacturing costs.
  • N needed to form nitrides such as (Al, Si, Mn) N, AlN, (B, Si, Mn) N, (Al, B) N, BN, etc. is ammonia gas in the annealing process after cold rolling. Reinforce by nitriding in steel using.
  • C is an element that causes phase transformation between ferrite and austenite to refine the grains and improve the elongation.
  • C is an element which is essential for improving the rolling property of an electrical steel sheet having poor brittleness and poor rollability.
  • the carbide formed due to the magnetic aging effect is an element that precipitates in the product plate and deteriorates the magnetic properties.
  • the content of C is limited to 0.02% or more and 0.08% or less.
  • the content of S is preferably made 0.01% or less.
  • P segregates in the grain boundary and may serve as a secondary role in inhibiting grain movement and at the same time inhibiting grain growth.
  • the content of P is less than 0.0005%, there is no addition effect.
  • the content of P is more than 0.045%, brittleness is increased and the rolling property is greatly deteriorated. Therefore, the content of P is preferably limited to 0.0005% or more and 0.045% or less.
  • Sb segregates at grain boundaries like P and has the effect of suppressing the growth of grains and stabilizing secondary recrystallization.
  • due to the low melting point it is easy to diffuse to the surface during primary recrystallization annealing, which may prevent decarburization, oxidation layer formation and nitriding by nitriding. Therefore, when Sb is added above a certain level, there is an upper limit of addition because it inhibits decarburization and suppresses formation of an oxide layer that is the basis of base coating.
  • Sb has a range of 0.01% or more and 0.05% or less.
  • Sn like P
  • Sn is known as a grain growth inhibitor because it is an element that prevents the movement of grain boundaries as a grain boundary segregation element.
  • the grain growth inhibiting force for smooth secondary recrystallization behavior at high temperature annealing is insufficient. For this reason, Sn which necessarily disturbs the movement of a grain boundary by segregating to a grain boundary is essential.
  • the present inventors have continued to study that when the Sn is added less than 0.03%, the magnetic properties are improved compared to the case where none, but the effect is insignificant.
  • the content of Sn is preferably made 0.03% or more and less than 0.08%.
  • Cr promotes the formation of the hard phase in the hot rolled annealing plate to promote the formation of ⁇ 110 ⁇ ⁇ 001> of Goss aggregates during cold rolling.
  • the austenite phase transformation retention time is reduced, thereby preventing damage to the aggregated tissue.
  • it promotes the formation of the oxide layer on the surface formed during the decarbonization process to compensate for the disadvantage that the oxide layer formation is inhibited due to Sn and Sb.
  • the present inventors have found that when the Cr is added at less than 0.01%, the above-mentioned effect appears slightly but no effect at all when no Cr is added. In addition, when it is added in excess of 0.2% it was found that a more dense oxide layer is formed when the oxide layer is formed during the decarbonization annealing process. Because of this, the oxide layer formation is inferior and there is a disadvantage that hinders decarburization and deposition. In addition, since Cr is an expensive alloying element, it is preferable to limit to 0.2% or less.
  • the above-described electrical steel sheet of the present invention may be manufactured by a method for manufacturing electrical steel sheet well known in the art, but it is more preferable to manufacture the following manufacturing method. Hereinafter, a more preferable manufacturing method is demonstrated.
  • the condition which is not specifically described below should be regarded as following normal conditions.
  • Another embodiment of the present invention by weight, Si: 2.0% or more and 5.0% or less, acid-soluble Al: 0.005% or more and 0.04% or less, Mn: 0.01% or more and 0.2% or less, N: 0.01% or less (0 % Is excluded), S: 0.01% or less (0% is excluded), Sb: 0.01% or more and 0.05% or less, C: 0.02% or more and 0.08% or less, P: 0.0005% or more and 0.045% or less, Sn: 0.03% or more and 0.08 Reheating a steel slab comprising less than%, Cr: 0.01% or more and 0.2% or less and consisting of the balance Fe and other unavoidable impurities; Manufacturing a steel sheet by performing hot rolling, hot rolled sheet annealing, and cold rolling on the reheated steel slab; Performing decarbonization and nitride annealing on the cold rolled steel sheet; It provides a method for producing a grain-oriented electrical steel sheet comprising a; and the final annea
  • the steel slab may be a method for producing a grain-oriented electrical steel sheet that satisfies the following formula 1 calculated by the content (% by weight) of each component.
  • the steel slab may be a method of manufacturing a grain-oriented electrical steel sheet that satisfies the following formula 2 calculated by the content (% by weight) of each component.
  • the steel slab may be a method of manufacturing a grain-oriented electrical steel sheet that satisfies the following formula 1 and formula 2 calculated by the content (wt%) of each component.
  • the precipitates of Al-based nitrides or Mn-based sulfides are incompletely or completely dissolved in accordance with chemical equivalent relationships of Al, N, Mn, and S to be dissolved.
  • the precipitate is incomplete solution, it is possible to cold roll once even if the amount of precipitation is large because the size of the precipitate is larger than that of the complete solution.
  • the content of N and S that is re-stocked in the steel through slab reheating is preferably 20 to 50 ppm and 20 to 50 ppm, respectively.
  • the reusable N and S content should take into account the Al and Mn content in the steel. This is because the nitrides and sulfides used as grain growth inhibitors are (Al, Si, Mn) N, AlN and MnS.
  • the theoretical employment temperature according to the Iwayama equation is 1258 ° C. In order to heat the slab of such an electrical steel sheet, it must be heated to 1300 ° C.
  • Fayalite which is a compound of low melting point silicon and iron, known metal, is formed on the steel sheet.
  • Fayalite which is a compound of low melting point silicon and iron, known metal, is formed on the steel sheet.
  • the surface of the steel sheet melts, and thus the hot rolling work becomes very difficult, and the repair of the heating furnace due to the melted molten water increases.
  • the temperature may be 900 ° C to 1250 ° C, 900 ° C to 1200 ° C, 900 ° C to 1150 ° C, 1000 ° C to 1250 ° C, 1100 ° C to 1250 ° C, 1000 ° C to 1250 ° C, and 1000 ° C to 1200 ° C.
  • Iwayama also proposed the following correlation with respect to the employment of Mn and S in pure 3% silicon steel.
  • the theoretical employment temperature based on the Iwayama equation is 1126 ° C.
  • heating to 1150 ° C. makes it possible to completely melt the Mn-based sulfide.
  • the theoretical employment temperature is 1130 ° C. Accordingly, when the electrical steel slab is heated at 1150 ° C., the Mn-based sulfide may be completely dissolved.
  • the theoretical employment temperature is 1163 ° C.
  • the electrical steel slab is heated to 1150 ° C, the Mn-based sulfide cannot be completely dissolved, but it can be almost completely dissolved.
  • the hot rolled hot rolled sheet there is a strain structure drawn in the rolling direction by stress, and AlN, MnS, etc. precipitate during hot rolling. Therefore, in order to have a uniform recrystallized microstructure and fine AlN precipitate distribution before cold rolling, the hot rolled sheet is once again heated to below the slab heating temperature. It is important to recrystallize the deformed tissues by heating and to obtain a sufficient austenite phase to promote the employment of grain growth inhibitors such as AlN and MnS.
  • hot-rolled sheet annealing temperature 900-1200 degreeC in order to take the austenite fraction to the maximum.
  • cold rolling is performed with a thickness of 0.10mm or more and 0.50mm or less using a reverse rolling mill or a tandem rolling mill. It is preferable to perform one cold rolling, which does not perform annealing heat treatment of the deformed structure in the intermediate process, but directly to the thickness of the final product from the initial hot rolled thickness.
  • the low-density orientations of the ⁇ 110 ⁇ ⁇ 001> bearings are rotated into the deformation bearings.
  • only goth crystal grains arranged in the ⁇ 110 ⁇ ⁇ 001> orientation are present in the cold rolled plate.
  • orientations with low integration are also present in the cold rolled plate.
  • orientations of low integration are also re-determined during final annealing, resulting in poor magnetic flux density and iron loss characteristics. Therefore, it is preferable that cold rolling rolls by 87% or more of cold rolling by one strong cold rolling once.
  • the cold rolling rate is 87% to 90%, 87% to 91%, 87% to 92%, 87% to 93%, 87% to 94%, 87% to 95%, 87% to 96%, 87% To 97%, 87% to 98%, 87% to 99%.
  • This cold rolled plate is subjected to decarburization, recrystallization of deformed tissue, and nitriding with ammonia gas.
  • the decarburization and nitriding process is problematic in that either the method of nitriding with ammonia gas after decarburization and recrystallization or using ammonia gas simultaneously to perform nitriding at the same time as decarburization is effective. none.
  • the annealing temperature of the steel sheet is preferably heat-treated within the range of 800 to 950 ° C. If the annealing temperature of the steel sheet is lower than 800 °C it takes a long time to decarburize. If the annealing temperature is higher than 950 ° C, the recrystallized grains grow coarse and the driving force for crystal growth is lowered. As a result, stable secondary recrystallization is not formed. And the annealing time is not a big problem in achieving the effect of the present invention, but in view of productivity it is usually preferred to treat within 5 minutes.
  • the oxide layers present in the external oxide layer formed on the surface of the decarburization annealing steel sheet in the reducing atmosphere may be reduced and removed.
  • the ⁇ 110 ⁇ plane of the steel sheet is parallel to the rolling surface, and the ⁇ 001> direction is parallel to the rolling direction. 110 ⁇ It is possible to form an aggregate. Thus, it is possible to manufacture a grain-oriented electrical steel sheet excellent in magnetic properties.
  • the purpose of the final annealing is to broaden the formation of ⁇ 110 ⁇ ⁇ 001> texture by secondary recrystallization, the formation of a glassy film by the reaction of the oxide layer and MgO formed during decarburization, to impart insulation, and to remove impurities that impair magnetic properties.
  • the final annealing temperature is equal to or higher than the decarbonation annealing temperature and 1250 ° C or lower. Specifically, the temperature may be 800 ° C to 1250 ° C, 850 ° C to 1250 ° C, and 900 ° C to 1250 ° C.
  • an atmosphere containing at least one of nitrogen and hydrogen may be maintained in a temperature rising section before secondary recrystallization occurs.
  • the secondary recrystallization may be well developed by protecting nitride, which is a particle growth inhibitor. After the second recrystallization is completed, it is maintained in a 100% hydrogen atmosphere for a long time to remove impurities.
  • the hot rolled annealing plate is pickled and rolled once to a thickness of 0.23mm, and the cold rolled plate is degassed simultaneously to maintain 170ppm of nitrogen by maintaining it at a temperature of 860 ° C for 200 seconds in a humid hydrogen, nitrogen and ammonia mixed gas atmosphere. Nitride annealing heat treatment.
  • MgO an annealing separator
  • the content of C is -0.32xMn (wt%) + 0.012xSi (wt%) + 0.016 ⁇ C (wt%) ⁇ ⁇ 0.014xMn (wt%), which is a content relationship between Si, Mn and C. It can be seen that the invention having satisfactory (+) + 0.02xSi (wt%) has a significant improvement in magnetic properties when compared with the comparative material.
  • Si 3.35%
  • C 0.061%
  • Mn 0.061%
  • S 0.004%
  • N 0.004%
  • Sol-Al 0.029%
  • P 0.032%
  • Sn, Sb, Cr are changed as shown in Table 2
  • the remaining components were vacuum-dissolved after quenching of the grain-oriented electrical steel sheet containing the remaining Fe and other inevitable impurities, and then heated to a temperature of 1140 °C and hot rolled to a thickness of 2.3mm.
  • the hot rolled sheet was heated to a temperature of 1080 °C and then maintained at 915 °C for 162 seconds and quenched in water.
  • the hot rolled annealing plate is pickled and rolled once to a thickness of 0.23 mm, and the cold rolled plate is degassed simultaneously to maintain a nitrogen content of 180 ppm by holding it at a temperature of 850 ° C. for 200 seconds in a humid hydrogen, nitrogen and ammonia mixed gas atmosphere. Nitride annealing heat treatment.
  • MgO an annealing separator

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Abstract

La présente invention concerne une tôle d'acier électrique à grains orientés et son procédé de fabrication. La présente invention peut permettre de produire une tôle d'acier électrique à grains orientés et un procédé de fabrication de cette dernière, la tôle d'acier électrique à grains orientés comprenant : 2,0 % en poids à 5,0 % en poids de Si ; 0,005 % en poids à 0,04 % d'Al soluble dans l'acide ; 0,01 % en poids à 0,2 % en poids de Mn ; 0,01 % en poids ou moins (à l'exclusion de 0 %) de N ; 0,01 % ou moins (à l'exclusion de 0 %) de S ; 0,01 % en poids à 0,05 % en poids de Sb ; 0,02 % en poids à 0,08 % en poids de C ; 0,0005 % en poids à 0,045 % en poids de P ; 0,03 % en poids à moins de 0,08 % en poids de Sn ; 0,01 % en poids à 0,2 % en poids de Cr ; le reste comprenant du Fe et d'autres impuretés inévitables.
PCT/KR2016/012851 2015-11-10 2016-11-09 Tôle d'acier électrique à grains orientés et son procédé de fabrication WO2017082621A1 (fr)

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CN201680065834.8A CN108350545A (zh) 2015-11-10 2016-11-09 取向电工钢板及其制造方法
JP2018524277A JP2019501282A (ja) 2015-11-10 2016-11-09 方向性電磁鋼板及びその製造方法
US15/775,311 US20180327879A1 (en) 2015-11-10 2016-11-09 Grain-oriented electrical steel sheet and method for manufacturing same

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KR102176348B1 (ko) * 2018-11-30 2020-11-09 주식회사 포스코 방향성 전기강판 및 그의 제조방법
KR102142511B1 (ko) * 2018-11-30 2020-08-07 주식회사 포스코 방향성 전기강판 및 그의 제조방법
KR102164329B1 (ko) * 2018-12-19 2020-10-12 주식회사 포스코 방향성의 전기강판 및 그 제조 방법
CN109988896A (zh) * 2019-02-18 2019-07-09 安徽工业大学 一种取向电工纯铁的塑性加工方法
KR102305718B1 (ko) * 2019-12-18 2021-09-27 주식회사 포스코 방향성 전기강판 및 그 제조방법

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