WO2013125790A1 - Procédé de formation d'une texture d'une plaque en un alliage à base de fe et de co, et tôle d'acier magnétique doux ainsi fabriquée - Google Patents

Procédé de formation d'une texture d'une plaque en un alliage à base de fe et de co, et tôle d'acier magnétique doux ainsi fabriquée Download PDF

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WO2013125790A1
WO2013125790A1 PCT/KR2013/000459 KR2013000459W WO2013125790A1 WO 2013125790 A1 WO2013125790 A1 WO 2013125790A1 KR 2013000459 W KR2013000459 W KR 2013000459W WO 2013125790 A1 WO2013125790 A1 WO 2013125790A1
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plate
plane
sheet
phase
alloy
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Korean (ko)
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성진경
김낙준
이재상
심병열
최국선
구양모
권세균
허윤욱
진원
김장규
왕덕현
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포항공과대학교 산학협력단
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Publication of WO2013125790A1 publication Critical patent/WO2013125790A1/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
    • 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
    • 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
    • C21D6/007—Heat treatment of ferrous alloys containing Co
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • 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
    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
    • 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
    • C22C38/30—Ferrous alloys, e.g. steel alloys containing chromium with cobalt
    • 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
    • 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/16—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets
    • 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

Definitions

  • the present invention relates to a method of forming a ⁇ 100 ⁇ plane texture parallel to a plate surface in a plate made of a Fe-Co-based alloy, and a soft magnetic steel sheet manufactured using the same. More specifically, a method of forming particles of ⁇ 100 ⁇ plane parallel to the plate surface at a high density within a short time on a Fe-10 to 35% by weight Co alloy plate surface, by growing the surface ⁇ 100 ⁇ plane particles into the plate material
  • the present invention relates to a method for producing a soft magnetic steel sheet having a particle size of not less than half the thickness of a sheet and having a remarkably excellent magnetic property, and a soft magnetic steel sheet produced by the above methods and having an excellent ⁇ 100 ⁇ plane integration degree.
  • Soft magnetic materials with cobalt added to iron have the highest saturation magnetic flux density, which is one of the important properties required for soft magnetic materials, compared to other soft magnetic materials.
  • the saturation magnetic flux density of the Fe-Co alloy has a maximum value of about 25 to 35% by weight of cobalt, and the value is more than 2.4T.
  • a material having a Fe-25 to 35% by weight Co composition has a low specific resistance value, which is an important characteristic of a soft magnetic material, and thus cannot be used as it is.
  • the resistivity of iron is 10 ⁇ -cm and its value gradually increases until the cobalt content increases to 18% by weight, but the resistivity at this time depends on the amount of alloy added. It reaches a relatively low 20 ⁇ -cm.
  • the specific resistance decreases, and when the 27% by weight of cobalt is added, the specific resistance is 14 ⁇ -cm.
  • the soft magnetic material the low resistivity value is recognized as a problem to be overcome because the low resistivity value greatly increases the eddy current loss, which is a loss occurring when the sheet is magnetized.
  • the direction of development of Fe-Co alloy was to increase the specific resistance while minimizing the amount of expensive cobalt.
  • the first example is the Fe-17 wt% Co alloy system, which attempts to reduce the amount of expensive cobalt while maintaining a relatively high magnetic flux density.
  • a second example is the Fe-27 wt% Co alloy system, which attempts to maintain a high magnetic flux density even if the amount of expensive cobalt increases.
  • the specific resistance is low, in order to overcome this, chromium, molybdenum, vanadium, silicon, nickel, etc. are added to increase the specific resistance.
  • Fe-50wt% Co alloy is commercialized under the name of Supermendur.
  • This material has high magnetic flux density by forming intermetallic compound and has no magnetic anisotropy, so it has excellent magnetic properties but poor mechanical properties, so it has little workability.
  • This poor processability was overcome by adding 2% by weight vanadium.
  • Supermendur is therefore recognized as the best soft magnetic material.
  • Supermendur contains 50% of expensive cobalt, and is relatively poor in workability, so that the elongation is only about 10%.
  • Supermendur has a disadvantage in that nonmagnetic particles are precipitated and deteriorated in magnetic properties when exposed to high temperatures for a long time. . Therefore, there have been efforts to produce a plate having excellent soft magnetic properties while reducing the content of expensive cobalt in the Fe-10 ⁇ 35% by weight Co alloy system.
  • the method of improving the soft magnetic properties shown in the Fe-10 to 35% by weight Co alloy system can be achieved by appropriately adjusting the atomic arrangement of the steel sheet.
  • it has already been known since 1934 that the magnetic properties of the steel sheet are improved by controlling the texture of the steel sheets of a given composition. J. W. Shih, Magnetic Properties of Iron-Cobalt Single Crystals, Phys. Rev. 46, 139-142 (1934)
  • the optimal texture in the Fe-Co alloy is the cube-on-face texture.
  • Cube-on-face assembly is a ⁇ 100 ⁇ plane with ⁇ 100 ⁇ planes arranged parallel to the plate plane and the ⁇ 001> direction randomly arranged ( ⁇ 100 ⁇ ⁇ ovov >).
  • the reason for improving the magnetic properties of the iron-based soft magnetic alloy is that there are no ⁇ 111> directions, which are magnetization difficulty directions, and two ⁇ 001> directions, which are easy magnetization directions, on the ⁇ 100 ⁇ plane.
  • the Fe-Co alloy has magnetic anisotropy.
  • Magnetic anisotropy means that magnetic properties change depending on the direction of atomic arrangement. In alloys containing 10 to 35% by weight of cobalt, the ⁇ 001> direction is known as the easy magnetization direction and the ⁇ 111> direction is known as the magnetization difficulty direction. . Therefore, the soft magnetic material of the Fe-Co alloy used in the motor due to such magnetic anisotropy can greatly improve the magnetic properties of the plate by forming a cube-on-face texture. In the present invention, the cube-on-face aggregate will be described as ⁇ 100 ⁇ plane aggregate.
  • US Patent No. 3,977,919 to Foster et al. Discloses a method for manufacturing a steel sheet having a cube texture ((100) [001]).
  • US Patent No. 3,868,278 filed by the same inventor proposes an alloy composition having a cube texture.
  • the method of forming the cube aggregate suggested by the poster is as follows. Hot rolling of an alloy consisting of Fe-5 to 35% by weight of Co makes the thickness of the plate about 2 mm. After pickling the hot rolled sheet, the heat treatment is performed at 850 ° C. for 5 hours under a dry hydrogen gas atmosphere (dew point ⁇ -40 ° C.). The specimen thus treated is subjected to cold rolling so that the thickness reduction (pressure reduction rate) is 75% or more.
  • the plate is subjected to a heat treatment for 24 to 48 hours in a dry hydrogen gas atmosphere (dew point ⁇ -40 ° C.) at a temperature range of 850 ° C. to Ac at a stable temperature of the ferrite phase.
  • a dry hydrogen gas atmosphere dew point ⁇ -40 ° C.
  • the plate treated as described above is said to form a cube aggregate having a relatively high degree of integration.
  • the method of forming the texture to improve the magnetic properties has certain disadvantages.
  • the first is that the plate obtained as a result of the heat treatment has a cube aggregate rather than a cube-on-face.
  • Cube assemblies are directional and are not suitable as cores for rotating machines in which the magnetization direction is constantly changing.
  • the plate having a cube assembly is an assembly suitable for a transformer or the like that is magnetized only in a certain direction. If the plate having the cube assembly structure is to be used for a motor, such as a rotating machine, it should be carefully laminated so that the ⁇ 001> direction existing on the plate surface is evenly arranged in all directions when fabricating the core. This allows the core to exhibit the same magnetic properties in all directions.
  • the second disadvantage is that the compositional limit when obtaining the cube texture by using the heat treatment, as shown in U.S. Patent No. 3,868,278 to Foster et al.,
  • the amount of chromium in the material should be limited to 0.3% by weight or less. Is that.
  • the Fe-Co alloy has a high magnetic flux density but has a low specific resistance. Therefore, in order to have excellent soft magnetic properties, the specific resistance value must be increased.
  • chromium is known as an important additive element in Fe-Co alloys that can effectively increase the resistivity without deteriorating mechanical properties. (K. Foster, DR Thornburg, Magnetic properties of oriented iron-cobalt alloys, AIP Conf. Proc.
  • 2007-0029013, 2004-0099347, and US Patent No. 5,919,319 also refer to Fe-Co steel sheets having a ⁇ 100 ⁇ plane texture in the claims. Has not been presented. If the conventional technology is judged comprehensively, a method of manufacturing a plate material having excellent soft magnetic properties has not been proposed by implementing a cube-on-face texture in Fe-Co-based alloys.
  • One problem to be solved by the present invention is to overcome the imperfections of the conventional methods as described above, and is effective, repeatable and reproducible in iron alloy containing 10 to 35% by weight of cobalt (Co) It is to provide a method for densely forming a cube-on-face texture having a ⁇ 100 ⁇ plane formed in parallel to the.
  • Another object of the present invention is to have a semi-penetrating microstructure in which an aggregate structure having a ⁇ 100 ⁇ plane formed parallel to the surface of the plate is efficiently grown into the plate to have a particle size of at least half the plate thickness. It is to provide a method for producing a soft magnetic Fe-Co steel sheet.
  • Another object of the present invention is to provide a Fe-Co-based soft magnetic steel sheet having a high density of the cube-on-face texture formed with a ⁇ 100 ⁇ plane parallel to the surface of the plate, the magnetic properties are improved.
  • the first aspect of the present invention for solving the above problems, in a plate made of iron (Fe) alloy containing 10 to 35% by weight of cobalt (Co), the ⁇ 100 ⁇ plane of the crystal structure parallel to the plate surface
  • Method of forming the formed texture (a) controlling the atmosphere so that the surface of the plate is not oxidized, and then heat-treating the plate to become an austenite phase and (b) ferrous phase of the austenite phase of the plate Phase transformation to form a cube-on-face texture in which a ⁇ 100 ⁇ plane is parallel to the plate surface.
  • the partial pressure of oxygen in step (a) is preferably 10 ⁇ 15 atm or less, and in the case where the iron (Fe) alloy further includes alloying elements other than the cobalt, the above (a)
  • the oxygen partial pressure of the step is preferably 10 -22 atm or less.
  • the step (a) is performed in a reducing gas atmosphere
  • the reducing gas may include one or more selected from hydrogen or hydrocarbon.
  • the phase transformation of the step (b) is made by a method of cooling the austenite phase plate, the cooling rate may be 600 ° C / hr or less, preferably 100 ° C / hr or less.
  • the iron (Fe) alloy includes an austenite phase stabilizing element, and the phase transformation of the step (b) is performed on the surface of the austenitic phase plate of the step (b). It can be made by the removal of the austenite phase stabilizing element included.
  • the iron (Fe) alloy includes an austenite phase stabilizing element, and the phase transformation of the step (b) is performed on the surface of the plate together with cooling of the austenitic phase plate. It can be made by the removal of the austenite phase stabilizing element included.
  • the iron (Fe) alloy, chromium (Cr), vanadium (V), molybdenum (Mo), nickel (Ni), silicon (Si), manganese (Mn) may include one or more elements selected from the group consisting of carbon (C).
  • the reducing gas may further include an inert gas as a carrier gas, the pressure of the reducing gas is preferably 0.1 atm or less.
  • step (a) may be performed under a hydrogen gas atmosphere having a dew point of -20 ° C or less.
  • step (a) may be performed under a vacuum atmosphere of 10 ⁇ 3 torr or less.
  • the step (a) may be made within 30 minutes.
  • a second aspect of the present invention for solving the other problem, in a plate made of an iron (Fe) alloy containing 10 to 35% by weight of cobalt (Co), ⁇ 100 ⁇ of the crystal structure parallel to the plate surface
  • a method of forming a surface-formed texture (a) adjusting the oxygen partial pressure so that the surface of the plate is not oxidized, and heat-treating the plate to become an austenite phase, (b) ferrite the austenite phase of the plate Transforming into phases, such that a cube-on-face texture is formed on the surface of the sheet parallel to the surface of the sheet; and (c) growing the texture formed on the surface of the sheet inwardly. It is to provide a method comprising a.
  • the step (c) may be made through continuous cooling of the plate.
  • the iron (Fe) alloy includes an austenite phase stabilizing element, and in the step (c), the surface of the plate is stable in the ferrite phase and the interior of the austenite phase in stable temperature.
  • austenite phase stabilizing elements can be made by removing from the plate surface.
  • the size of the thickness direction crystal grains of the plate may be at least 0.5 times the thickness of the plate.
  • the plate includes 2.0% by weight or less of manganese (Mn), and the continuous cooling of the plate may be performed at a rate of 100 ° C / h or less.
  • Mn manganese
  • the plate includes carbon (C), and the step (c) is carried out at a temperature at which the surface of the plate is stable in the ferrite phase and the inside of the austenite phase is stable, the plate Decarburizing may be included.
  • the third aspect of the present invention for solving the another problem is a soft magnetic steel sheet made of an iron alloy containing 10 to 35% by weight of cobalt (Co), the grain size of the steel sheet in the thickness direction of the plate thickness more than 0.5 times, and the following [formula 1] to ⁇ 100 ⁇ plane set coefficient P 100 obtained provide a soft magnetic steel sheet characterized in that not less than 6 in.
  • N hkl is the multiplicity factor
  • the soft magnetic steel sheet may further comprise 0.5 to 3% by weight of chromium (Cr).
  • the method according to the present invention forms a ⁇ 100 ⁇ plane texture (cube-on-face texture) parallel to the surface of the sheet, high magnetic properties can be realized.
  • the method according to the present invention can obtain a ⁇ 100 ⁇ plane cube-on face texture through a simple process (heat treatment-phase transformation) is suitable for mass production and very excellent in reproducibility.
  • the method according to the present invention can be applied universally to Fe-Co-based alloys and its utilization is very high.
  • the method according to the present invention can perform the formation of the surface texture and the growth in the thickness direction of the texture in a single heat treatment process, it is possible to improve the process efficiency compared to the conventional.
  • the method according to the present invention and the soft magnetic steel sheet produced by the present invention may include an alloying element such as chromium (Cr) in an amount of 0.5% by weight or more, so that the eddy current loss can be reduced, and the ⁇ 100 ⁇ plane High aggregate density enables high magnetic properties even with low use of expensive cobalt (Co), and can be mass-produced in a simple process, thereby providing a very innovative technology for the soft magnetic steel sheet industry.
  • the ripple effect is expected to be very large.
  • 1 is a graph showing the change of the aggregation coefficient with the change of the heat treatment temperature during the heat treatment of Fe-17% Co-2.0% Cr alloy sheet.
  • FIG. 2 is a graph showing the pole figure (200) of the Fe-17% Co-2.0% Cr alloy sheet after heat-treating the hydrogen gas atmosphere at a pressure of -50 ° C. for 30 minutes at a temperature of 1000 ° C.
  • ODF orientation distribution function
  • Figure 4 is a photograph showing the cross-sectional microstructure of the Fe-17% Co-2.0% Cr alloy plate was heat treated for 30 minutes at a temperature of 1000 °C and hydrogen gas atmosphere of 1 atmosphere with a dew point of -50 °C.
  • FIG. 5 is a graph showing the change of the aggregation coefficient according to the change of dew point of hydrogen gas when the Fe-17% Co-2% Cr alloy plate is heat-treated in a 1 atm hydrogen atmosphere.
  • FIG. 6 is a graph showing a change in dew point of hydrogen gas in which oxidation occurs at different temperatures according to chromium content when heat treating an Fe-17% Co-X% Cr alloy.
  • the metal sheet is a temperature at which the austenite phase is stable. Under heat treatment.
  • a predetermined texture can be formed on the surface.
  • the atomic structure of the plate in the 900 ⁇ 1000 °C section is a phase transformation of the ferrite having a bcc structure to the austenitic phase having a fcc structure.
  • the present invention is a method of forming a surface texture by controlling the heat treatment atmosphere when the phase transformation phenomenon occurs in the austenite phase to the ferrite phase.
  • the phase of the metal plate When the transformation occurs, while controlling the oxygen partial pressure in a heat treatment atmosphere or the like so that oxidation does not occur on the surface of the plate, ii) the austenite phase is heat-treated under a stable temperature. iii) By phase-transforming the heat treated metal plate into a ferrite phase, particles having a ⁇ 100 ⁇ plane parallel to the metal plate surface may be formed on the surface of the metal plate.
  • the second aspect of the present invention after the ⁇ 100 ⁇ plane of the cube-on-face texture is formed on the surface of the plate made of Fe-10 ⁇ 35% by weight Co-based alloy according to the first aspect of the present invention, Alternatively, the ⁇ 100 ⁇ plane cube-on-face texture is formed on the surface of the plate and the surface ⁇ 100 ⁇ plane particles are grown therein.
  • phase transformation step and the internal growth step may be performed collectively or continuously without being carried out in a separate process in some cases.
  • the third aspect of the present invention is characterized in that i) is composed of Fe-10-35% Co alloy, and ii) at least 30% of the surface area has an aggregate structure composed of particles in which the ⁇ 100 ⁇ plane is parallel to the plate surface. , iii) To provide a soft magnetic steel sheet having a microstructure in which crystal grains having a ⁇ 100 ⁇ plane parallel to the sheet surface pass through or penetrate the sheet material.
  • Strictly controlling the process conditions according to the first and second aspects of the present invention may produce a plate having almost 100% of particles having a ⁇ 100 ⁇ plane parallel to the plate surface.
  • the method for forming a ⁇ 100 ⁇ surface texture on the surface of a metal plate made of Fe-10 to 35% by weight Co alloy according to the present invention heat treatment of the metal plate at a stable temperature of the austenite phase while largely preventing oxidation of the metal plate surface. And a heat treatment step of converting a phase of the Fe-10 to 35% by weight Co alloy into an austenite phase, and a phase transformation step of transforming the austenite phase into a ferrite phase.
  • an austenite phase is formed without an oxide film formed on the surface of the metal sheet, and the austenite phase is converted into a ferrite phase. It is for preventing an oxide film from forming on the surface of a metal plate even during transformation. Therefore, in the present invention, the heat treatment acts as a very important factor to control the oxygen partial pressure as well as the process conditions such as heat treatment temperature, heat treatment pressure and gas atmosphere, so the content of oxygen in the atmosphere must be strictly controlled.
  • Iron and cobalt constituting the Fe-Co binary alloy are both less oxidized at high temperatures compared to other metal elements.
  • the oxygen partial pressure in the heat treatment atmosphere should be adjusted to about 10 ⁇ 15 atm or less in order to prevent oxidation of the material. If it is converted into the dew point of 1 atmosphere of hydrogen, the dew point of room temperature hydrogen becomes a hydrogen atmosphere condition of 70 degrees C or less.
  • the hydrogen atmosphere having the dew point is naturally included as long as it is a general hydrogen atmosphere, meaning that no oxidation occurs in the Fe-Co binary alloy even in an atmosphere containing a small amount ( ⁇ 5%) of hydrogen.
  • the ⁇ 100 ⁇ plane forming method according to the present invention has the advantage that the metal plate can be applied universally to a metal plate containing various alloys in the composition as well as a metal plate made of iron containing 10 to 35% by weight of cobalt. .
  • Alloy elements that may be added to the Fe-Co-based alloy according to the present invention include chromium (Cr), vanadium (V), molybdenum (Mo), manganese (Mn), nickel (Ni), silicon (Si), Carbon (C) and the like. These elements may be added alone or in combination of two or more. The elements may be added to improve the physical properties of the metal plate, but in the present invention, the elements are added in consideration of the ⁇ 100 ⁇ plane density improvement and the internal growth of the ⁇ 100 ⁇ plane structure.
  • the alloying element is contained even in a small amount or exists in the form of a small amount of impurities in the alloy, and the oxygen affinity of the containing element is larger than that of iron or cobalt, when the ⁇ 100 ⁇ surface forming heat treatment is performed, these elements are It is selectively oxidized at the surface of the sheet. Surface oxidation of these alloying elements prevents the ⁇ 100 ⁇ plane from forming parallel to the plate surface. Therefore, in the material containing the intentionally added element and the impurity, the oxygen partial pressure of the atmosphere gas used as the heat treatment atmosphere must be more strictly controlled than the Fe-Co binary alloy so that oxidation does not occur on the surface of the plate.
  • Oxygen partial pressure at which oxidation starts to occur at the temperature conditions at which phase transformation occurs depends on the type and amount of the alloying elements added, but is maintained at about 10 -22 atm or less when it contains elements other than iron and cobalt. It is preferred that it is more preferably maintained below 10 -24 atm. Converting it to the dew point of a 1 atm hydrogen heat treatment atmosphere means that the dew point of room temperature hydrogen must be maintained at 100% hydrogen gas atmosphere conditions of -20 ° C or lower. That is, it means that the Fe—Co alloy is not oxidized in any atmosphere in a hydrogen atmosphere (dew point ⁇ -40 ° C.) which is generally called a dry hydrogen atmosphere.
  • the heat treatment step may be performed under a reducing gas atmosphere.
  • the reducing gas serves to remove oxygen from the metal sheet and further block oxygen so that the surface of the metal sheet does not react with oxygen.
  • Hydrogen gas, hydrocarbon gas, etc. are mentioned as an example of the said reducing gas.
  • the hydrogen gas may remove oxygen on the surface of the metal sheet by combining hydrogen atoms contained in the hydrogen gas with oxygen included in the surface of the metal sheet to form H 2 O gas.
  • hydrogen atoms in the hydrocarbon may combine with oxygen contained in the metal plate surface to form H 2 O gas
  • carbon atoms in the hydrocarbon may combine with oxygen contained in the metal plate surface.
  • the pressure of the reducing gas is not particularly limited, but it is preferably within about 1 atmosphere, and more preferably, 0.00001 atmospheres (7.6 ⁇ 10 -3 torr) to 0.1 atmospheres (76 torr). Keep it.
  • the reducing gas may be used alone or in a mixed state of hydrogen gas, hydrocarbon gas, or the like, and may be used in a state of further including an inert gas such as helium, argon, neon, or nitrogen for a carrier use.
  • an inert gas such as helium, argon, neon, or nitrogen for a carrier use.
  • the dew point is performed under a gas atmosphere having a dew point of -20 ° C. or lower. Because this can increase.
  • the heat treatment step may be performed not only in a reducing gas atmosphere but also in a vacuum atmosphere of 1 ⁇ 10 ⁇ 3 torr or less, and preferably performed at a high degree of vacuum of 5 ⁇ 10 ⁇ 5 torr or less, which maintains a low oxygen partial pressure. For that.
  • the heat treatment step is performed within a temperature range in which the austenite phase of the metal sheet is stable.
  • the Fe-Co-based alloy containing 10 to 35% by weight of cobalt is stable in the ferrite phase at room temperature, but when the temperature increases, only the austenite phase undergoes a phase transformation process.
  • the heat treatment is carried out in a temperature range corresponding to the austenitic phase region described above.
  • the temperature range corresponding to the stable region of the austenite phase is variable depending on the type and content of alloying elements included in the metal sheet.
  • the phase transformation step is a step in which a ⁇ 100 ⁇ plane texture parallel to the metal plate surface is formed on the metal plate surface while transforming the metal plate made of the austenite phase into a ferrite phase through heat treatment.
  • the phase transformation method is a method of cooling the Fe-10-35 wt% Co alloy to a stable temperature of a ferrite phase to generate a ferrite transformation (cooling method), and changing the composition of the Fe-10-35 wt% Co alloy to ferrite transformation.
  • the 'composition change' means that the austenite stabilizing elements included in the metal sheet include various forms such as reacting with oxygen atoms to generate oxides or evaporating into a heat treatment atmosphere.
  • the cooling rate of the section in which the phase transformation takes place is very important, the cooling rate is preferably maintained at 600 ° C / h or less, more preferably at 100 ° C / h or less, the cooling rate This is because when the content exceeds 600 ° C / h, the formation of the ⁇ 100 ⁇ plane texture parallel to the plate surface becomes difficult.
  • the composition change method is a method of changing the composition of the surface of the metal plate at a constant temperature (that is, constant temperature) in which an austenite phase is stable.
  • a constant temperature that is, constant temperature
  • the element that causes the composition change include carbon (C) and manganese (Mn).
  • the carbon (C) is an austenite stabilizing element
  • the ferrite-austenite phase transformation temperature is lowered.
  • the austenite phase is present as a stable phase.
  • the heat treatment is performed in a temperature section in which the ferrite phase is present as a stable phase.
  • the heat treatment atmosphere is subjected to heat treatment in a slightly decarburized atmosphere (hydrogen atmosphere having a vacuum degree of 1 ⁇ 10 ⁇ 3 torr or less or a dew point corresponding thereto).
  • the austenite particles on the surface undergo constant temperature transformation into ferrite particles through surface decarburization of the metal sheet transformed into the austenite phase.
  • the meaning of the plundered atmosphere means a condition in which decarburization occurs but does not oxidize the metal surface.
  • the reason why decarburization occurs on the metal surface but does not occur when the oxygen partial pressure is appropriate is that the carbon on the surface of the material and the oxygen in the atmosphere combine to form carbon monoxide on the metal surface rather than the oxidation of the metal element on the metal surface. This is because it occurs more easily.
  • the carbon on the metal surface reacts with oxygen in the atmosphere to form a carbon monoxide gas and disappears into the atmosphere, thereby lowering the carbon concentration on the surface of the plate, and at the same time, the metal surface is present in the metal state which is not oxidized with FeO, CoO, or the like.
  • the metal surface is transformed into ferrite by a decrease in carbon concentration, which is an austenite stabilizing element. That is, since the surface of the plate is a state in which the metal Fe is not oxidized and at the same time a phase transformation occurs, the ⁇ 100 ⁇ plane texture is formed on the surface of the metal plate parallel to the plate surface.
  • the content of carbon (C) is preferably 0.03 to 0.3% by weight, which is less than 0.03% by weight of the transformation temperature range is difficult to control the constant temperature transformation, when exceeding 0.3% by weight, a lot of time for decarburization Because it takes.
  • Manganese (Mn) is also an austenite stabilizing element. Therefore, when the manganese (Mn) is added, the phase transformation temperature is lowered. At this time, the heat treatment atmosphere is a vacuum atmosphere (manganese Mn) is easy to vaporize (vacuum of 1x10 -3 torr or less), and at the same time, the heat treatment temperature is a stable phase in the austenite phase in the composition when the manganese is not vaporized, When Mn) is vaporized and the manganese (Mn) concentration on the surface of the sheet is lowered, heat treatment is performed at a temperature section in which the ferrite phase is present as a stable phase. When the heat treatment is performed under the above conditions, the concentration of the manganese (Mn) is lowered through vaporization on the surface of the plate, and the austenite particles phase change into ferrite particles.
  • the concentration of the manganese (Mn) is lowered through vaporization on the surface of the plate, and the austenite particles phase
  • the reason why the ⁇ 100 ⁇ plane reinforcement occurs in the phase transformation of the manganese (Mn) -added Fe-Co alloy is because the oxygen partial pressure in the atmosphere near the plate surface is very low.
  • the reason why the oxygen partial pressure near the surface of the plate is low may be explained by oxidation of evaporated manganese (Mn).
  • Manganese (Mn) is more than 1000 times its vapor pressure compared to other metals and vaporizes at a very high speed in a high temperature vacuum atmosphere, thereby reducing the concentration of manganese (Mn) on the surface of the plate.
  • manganese (Mn) is an element that stabilizes the austenite phase. Therefore, when the concentration of manganese on the surface of the plate becomes low, this part eventually transforms into ferrite.
  • vaporization of manganese (Mn) serves to prevent the metal surface oxidation phenomenon.
  • Metal manganese (Mn) vaporized from the plate is reacted with oxygen present in the heat treatment atmosphere. This results in a relatively low oxygen partial pressure around the metal plate surface.
  • the partial pressure of oxygen around the surface of the plate will have a value close to its equilibrium value (2.2 ⁇ 10 ⁇ 27 atm). . This corresponds to a dew point of -64 ° C. or higher in a 1 atm hydrogen atmosphere. Therefore, the vacuum condition of 1 ⁇ 10 ⁇ 3 torr or lower in which manganese is volatilized corresponds to a sufficiently low oxygen partial pressure condition to prevent oxidation of the metal surface.
  • the manganese (Mn) When the manganese (Mn) is used, it is preferable to add 0.3 to 2.0% by weight, if less than 0.3% by weight change in the transformation temperature range is difficult to control the constant temperature transformation and also the effect of small manganese, 2.0% by weight If exceeded, the mechanical property is deteriorated.
  • the cooling and composition change method is a method of simultaneously performing cooling in combination with the composition change, wherein the above-described phase transformation mechanism according to the cooling and composition change acts at the same time.
  • Formation of the ⁇ 100 ⁇ surface texture according to the present invention can be performed by heat treatment in a relatively short time, depending on the heat treatment conditions surface ⁇ 100 ⁇ surface assembly having a high aggregation degree even at very short time within 30 minutes Formation of tissues is possible.
  • the control of oxygen during the heat treatment is very important for the formation of the surface ⁇ 100 ⁇ surface texture according to the present invention, and the heat treatment should be performed under the condition that the oxide film is not substantially formed on the surface of the metal plate.
  • the degree of aggregation of the ⁇ 100 ⁇ plane may be remarkably changed depending on the presence of oxide on the surface during heat treatment.
  • surface particles having a ⁇ 100 ⁇ plane parallel to the plate surface may be grown into the plate, and the microstructure may be through-type (the grain size of grain in the thickness direction is the same as thickness) or at least a semi-penetrating type. It is necessary to make the structure (the grain size of grain in the thickness direction is 0.5 times the thickness or more). If the microstructure of the metal sheet is a semi-penetrating or penetrating structure, it has the same atomic arrangement as the surface of the plate as well as the surface. This is because it exhibits excellent magnetic properties.
  • the internal growth of the surface ⁇ 100 ⁇ plane particles may be performed by a continuous process simultaneously with the surface ⁇ 100 ⁇ plane particle formation heat treatment, or discontinuously in the chickenpox process by separating the surface ⁇ 100 ⁇ plane particle formation heat treatment and the internal growth heat treatment. This may be done discontinuously.
  • the internal growth of the surface ⁇ 100 ⁇ plane particles is made by growing the surface particles inside while the plate material is gradually cooled from the surface to the inside during the above-described surface ⁇ 100 ⁇ plane texture forming heat treatment, or included in the plate material. It is made through the process of growing the surface ⁇ 100 ⁇ plane particles inside by a concentration gradient (surface low concentration inner high concentration) formed in the process of removing the austenite phase stabilizing element to the surface of the metal plate, cooling and It can also be achieved through simultaneous changes in composition changes.
  • a concentration gradient surface low concentration inner high concentration
  • phase transformation occurring upon cooling in the Fe-Co alloy plate occurs first on the surface. This is because the surface temperature is the lowest and because the surface particles are not stressed in the vertical direction, ferrite nucleation is easy. If the phase transformation occurs on the surface, the effect of oxygen on the surface is minimized so that the oxide film is not present, the ferrite particles formed on the surface has a ⁇ 100 ⁇ plane selectively.
  • the ferrite particles formed from the austenitic particles present on the surface of the austenitic / ferrite phase interface are moved inward as the plate material is sequentially cooled from the surface to the inside of the surface ferrite particles to grow inside. Cooling the plate at an appropriate cooling rate (600 ° C./h or less) in a Fe—Co alloy with a suitable composition causes the surface ⁇ 100 ⁇ plane ferrite particles to grow to more than half the plate thickness.
  • Fe-Co alloys for soft magnetic materials are relatively low in impurities, since soft magnetic materials should be relatively low in impurities to improve magnetic properties.
  • the alloy with less impurities has a high moving speed of the austenite / ferrite phase interface. Therefore, as a result of the heat treatment, the Fe—Co alloy sheet material is composed of particles in which the ⁇ 100 ⁇ plane is parallel to the sheet surface as well as the surface thereof.
  • the surface ⁇ 100 ⁇ surface forming step and the internal growth step by cooling according to the present invention may be performed within a total of 30 minutes, depending on the process conditions may be within a few minutes to several ten minutes. Therefore, a separate step for internal growth is unnecessary, and thus Fe-Co steel sheet having a cube-on-face texture can be produced very efficiently.
  • the cooling rate for phase transformation should be relatively lowered to grow the ⁇ 100 ⁇ plane particles formed on the surface as described above, so that the Fe-Co-Mn sheet may be surfaced.
  • the ⁇ 100 ⁇ plane to the inside is composed of particles parallel to the plate surface.
  • the temperature inside the plate reaches a faster temperature range where the ferrite is stable than the rate at which ⁇ 100 ⁇ plane particles formed on the surface grow inside, thus forming new ferrite nuclei within the plate. That is, the plate does not form a semi-penetrating microstructure, and the texture inside the plate has a different texture than the ⁇ 100 ⁇ plane texture on the surface of the plate. Therefore, the magnetic properties are lowered.
  • the internal growth step may grow the surface ⁇ 100 ⁇ plane particles therein by decarburizing the metal plate having the surface ⁇ 100 ⁇ plane formed thereon.
  • the decarburizing of the metal plate may be performed efficiently in the presence of moisture.
  • the surface of the metal plate should be made at a temperature where the ferrite phase is stable and the austenite phase is stable inside.
  • a strong ⁇ 100 ⁇ plane should be formed on the surface already, and the surface should be in the temperature zone where the ferrite phase is stable in the decarburization temperature section. And the inside of the plate can be grown inside the particles having a ⁇ 100 ⁇ plane present on the surface through decarburization only when the austenite phase is stable.
  • ⁇ 100 ⁇ plane particles may grow while decarburization occurs under a hydrogen gas atmosphere.
  • the decarburization rate is slow but water is not used, so even if the phase of the surface of the plate is not limited to ferrite, the ⁇ 100 ⁇ plane particles formed at a high density on the surface may be gradually grown inward.
  • Decarburization occurs even in vacuum.
  • the vacuum atmosphere depending on the degree of vacuum, there is a small amount of oxygen, which combines with the carbon present in the sheet to form carbon monoxide and decarburize. Therefore, the ⁇ 100 ⁇ plane particles can be grown while maintaining the ⁇ 100 ⁇ plane already formed on the surface even in a vacuum atmosphere.
  • Heat treatment conditions for growing the ⁇ 100 ⁇ plane particles formed on the surface in the vacuum using decarburization in the vacuum the surface should be in a temperature zone where the ferrite phase is stable in the decarburization temperature section and the austenite phase inside the plate.
  • the ⁇ 100 ⁇ plane texture forming method according to the present invention can be applied to the Fe-Co alloy system in a general and source. In the following, it is generalized to form a surface ⁇ 100 ⁇ plane parallel to the plate face in several types of Fe-Co alloy plate. The following types may be specifically identified through embodiments to be described later.
  • Each of the elements described below is not an ingredient as an impurity contained in iron itself, but an active ingredient element that is intentionally included in iron, and describes only the actual addition content ignoring the content as an impurity.
  • the Fe-Co alloy plate is heat-treated under a temperature of ⁇ ⁇ , ii) under any one of a vacuum of 1 ⁇ 10 ⁇ 3 torr or less and a reducing gas atmosphere of 760 torr or less.
  • the heat-treated Fe-Co alloy plate is cooled or changed in the composition of the metal plate so that the phase transformation into a ferrite phase.
  • Table 1 shows the chemical composition of the plate used in the embodiment according to the present invention. These plates are cast into ingots through a vacuum induction melting process to have the composition shown in Table 1, then made into a hot rolled sheet of 2mm thickness, and then made of cold rolled sheet of various thickness through cold rolling.
  • Equation 1 is an index for indirectly evaluating the degree of formation of the aggregate structure of a specific crystal plane through the intensity of each crystal plane, in the present invention is referred to as the aggregate coefficient (P hkl ).
  • N hkl is the multiplicity factor
  • I R, hkl X-ray intensity of the (hkl) plane of random specimens.
  • the P hkl means a roughly showing how many times the (hkl) plane exists in the target specimen compared to the (hkl) plane in the non-directional random specimen.
  • the face index value is 20.33 if the ⁇ 100 ⁇ plane of all particles is parallel to the plate plane.
  • the present embodiment relates to the texture change of the Fe-Co alloy sheet according to the heat treatment temperature change.
  • 1 is a graph showing the change of the surface strength according to the change in the heat treatment temperature when heat-treating the Fe-17% Co-2% Cr alloy.
  • the heat treatment of Figure 1 was carried out for 15 minutes in a 3.4 ⁇ 10 -1 torr hydrogen atmosphere.
  • the heat treatment was carried out as follows. First, the metal specimen was mounted in a sample boat at room temperature. When the heat treatment furnace reached the heat treatment temperature, the specimen at room temperature was pushed into the center of the furnace. After maintaining 15 minutes under a given atmosphere and temperature conditions, the sample was cooled to a cooling rate of 100 ° C./h up to 800 ° C., and then the specimen was removed to a room temperature chamber and cooled to reach a temperature of the specimen.
  • Figure 2 shows the texture of the Fe-17% Co-2% Cr alloy specimens, the heat treatment atmosphere in a hydrogen atmosphere where the dew point is -50 °C, the heat treatment temperature after heat treatment at 1000 °C stable austenite for 30 minutes (200) pole figure graph.
  • ODF orientation distribution function
  • the diameter of the particle has a semi-penetrating and penetrating microstructure more than half of the plate thickness.
  • the ⁇ 100 ⁇ plane strength was changed according to the dew point.
  • Changing the dew point in the hydrogen atmosphere means controlling the oxygen partial pressure. Since hydrogen reacts with oxygen, pure hydrogen can be viewed as a reducing gas. However, if moisture is present in the hydrogen, an equilibrium must be formed between the moisture and the hydrogen, and thus oxygen may exist on the metal surface to be heat-treated. Therefore, as the dew point increases, the moisture increases, which is equivalent to the increase of the oxygen partial pressure. That is, as the dew point decreases, the oxygen partial pressure decreases, and as the dew point increases, the oxygen partial pressure in the heat treatment atmosphere increases.
  • FIG. 5 is a graph showing the change of the surface strength according to the dew point change of the hydrogen atmosphere when the Fe-17% Co-2% Cr alloy specimen is heat-treated in a hydrogen atmosphere of 1 atmosphere.
  • the heat treatment temperature and time was 1000 °C 15 minutes, after the heat treatment is completed by cooling to 800 °C to 100 °C / h by the cooling to complete the phase transformation and then to remove the specimen into the chamber of room temperature to cool the temperature of the specimen to reach room temperature I was.
  • the alloy used in the experiment had a composition of Fe-17% Co-2% Cr, in which the austenite phase was stable at temperatures above 930 ° C. Therefore, all specimens subjected to heat treatment undergo ⁇ ⁇ ⁇ phase transformation.
  • the dew point of hydrogen in order to strengthen the ⁇ 100 ⁇ plane texture in 100% hydrogen atmosphere, the dew point of hydrogen should be below -20 ° C.
  • such dew point conditions coincide with the conditions under which oxidation will not occur on the surface of the sheet when the sheet is heat treated in a given hydrogen heat treatment atmosphere and at a temperature at which phase transformation occurs.
  • FIG. 6 shows the critical dew point condition at which the Fe-17% Co-X% Cr alloy starts to oxidize in a 1 atm hydrogen gas atmosphere. Referring to FIG.
  • the Fe-17% Co-2% Cr composition is 1.5x10 -22 atm or more in terms of oxygen partial pressure to be oxidized at 930 ° C in which phase transformation occurs. If this is expressed as the dew point of room temperature 1 atm hydrogen gas corresponds to approximately -22 °C. That is, the ⁇ 100 ⁇ plane texture strengthening phenomenon found below -20 ° C shown in FIG. 5 shows that the phenomenon occurs when the phase transformation occurs under the condition that oxidation does not occur on the metal surface.
  • the plate is subjected to heat treatment in a stable temperature range in which the austenite phase is stable under low oxygen partial pressure, and then the plate is transformed into ferrite. This was done to confirm that the ⁇ 100 ⁇ cotton aggregate was effectively formed.
  • Heat treatment was carried out as follows.
  • the metal specimen was mounted in a sample boat at room temperature.
  • the heat treatment furnace reached the desired heat treatment temperature and the heat treatment atmosphere reached the desired value, the specimen at room temperature was pushed into the center of the furnace.
  • the heat treatment was completed by cooling to 100 °C / h to 750 °C by the cooling to complete the phase transformation, and the sample was taken out to the chamber at room temperature and cooled to reach the temperature of the specimen.
  • Table 2 shows the surface ⁇ 100 ⁇ texture of the Fe-10 ⁇ 35% Co alloy to which various elements are added.
  • the austenite phase undergoes heat treatment in a stable temperature range under the condition that oxidation does not occur at low oxygen partial pressure in the Fe-Co alloy system, it is not significantly influenced by the alloying components. It is a phenomenon that appears. Even if Cr, Si, Ni, Mo, and V are added in the Co content of 10 ⁇ 35%, the plate is heat-treated under the condition that the austenite phase is not oxidized at a stable temperature range and low oxygen partial pressure. Phase transformation resulted in the formation of a strong ⁇ 100 ⁇ cotton texture.
  • the heat treatment atmosphere satisfies the low oxygen partial pressure and no oxidation occurs, the ⁇ 100 ⁇ plane texture is strongly formed.
  • the heat treatment atmosphere in which the ⁇ 100 ⁇ plane texture was strengthened occurred in a vacuum atmosphere having a high degree of vacuum, a 1 atm hydrogen atmosphere having a low dew point, and a low pressure hydrogen atmosphere having a low dew point.
  • Ar, N 2, or the like is used as a carrier gas in a hydrogen heat treatment atmosphere, if the oxygen partial pressure is satisfied and no oxidation occurs on the surface of the Fe-Co alloy plate, the plate may experience phase transformation. When formed a strong ⁇ 100 ⁇ plane.
  • This embodiment is an example showing that the Fe-Co alloy can effectively form the ⁇ 100 ⁇ plane texture even in the case of a phase transformation caused by the composition change.
  • the composition change that occurs when the heat treatment is performed in the Fe-Co alloy refers to the composition change that is caused by decarburization and manganese vaporization in the material containing carbon, manganese, or carbon and manganese, which are austenite stabilizing elements.
  • Table 3 shows the surface reinforcement phenomenon of the surface ⁇ 100 ⁇ surface of the carbon, manganese, or Fe-10 ⁇ 35% by weight Co alloy plate containing carbon and manganese at the same time.
  • the carbon-containing Fe-17% Co-0.2% C alloy plate showed relatively strong ⁇ 100 ⁇ cotton texture at 1x10 -3 torr vacuum and Ar + 10% H 2 at -10 ° C. Formed.
  • the vacuum degree of the heat treatment atmosphere was lowered to 2x10 -1 torr, the ⁇ 100 ⁇ plane hardening did not occur. This phenomenon shows that surface oxidation, as shown in Example 2, prevents ⁇ 100 ⁇ plane hardening.
  • the austenite phase is present as a stable phase when carbon is present, and at the same time, when decarburization occurs and the concentration of carbon is reduced to 0.01 wt% or less on the surface of the plate, the ferrite phase is present as a stable phase. Done.
  • the heat treatment atmosphere is heat-treated with Ar + 10% H 2 having a dew point of -10 ° C., which is a plundering atmosphere, the carbon concentration of the metal surface is very low compared to the inside of the plate through surface decarburization, and thus the austenite of the surface The particles will undergo constant phase transformation into ferrite particles.
  • the decarburization reaction appearing at this time serves to remove oxygen from the metal surface. That is, the carbon on the metal surface reacts with oxygen in the atmosphere to form carbon monoxide gas and disappears into the atmosphere. Therefore, the metal surface is present in the metal state without being oxidized to FeO, CoO, or the like. If too much oxygen is present in the heat treatment atmosphere (strong decarburized atmosphere, 2x10 -1 torr vacuum), excess oxygen remaining even after surface decarburization oxidizes the surface of the metal sheet, so that the ⁇ 100 ⁇ plane hardening phenomenon Does not occur.
  • plundered atmosphere means a condition in which decarburization occurs but does not oxidize the metal surface. Due to the surface oxygen removal effect of carbon, the carbon-rich material exhibits a ⁇ 100 ⁇ plane strengthening under higher oxygen partial pressure conditions than that of a low carbon material.
  • the Fe-17% Co-1.5% Cr-1.5% Mn alloy plate containing manganese formed a strong ⁇ 100 ⁇ plane texture at 2x10 -4 torr vacuum.
  • the vacuum degree of the heat treatment atmosphere was lowered to 2x10 -1 torr, the ⁇ 100 ⁇ plane hardening did not occur.
  • This phenomenon shows that surface oxidation, as shown in Example 2, prevents ⁇ 100 ⁇ plane hardening.
  • the Fe-17% Co-1.5% Cr alloy plate containing manganese as a trace impurity was heat-treated in a 2x10 -4 torr vacuum atmosphere, ⁇ 100 ⁇ plane hardening was not found.
  • the phase change Since the phase change does not occur due to the change in composition, the phase change is induced through cooling.
  • the cooling is performed after cooling to 100 ° C./h up to 750 ° C. by heat cooling to complete the phase transformation.
  • the specimen was removed into the chamber and cooled to reach room temperature. Looking at the composition of the two alloys with different manganese contents, the content of other elements is almost the same except for the case of manganese. This result means that when manganese is added to the Fe—Co alloy, ⁇ 100 ⁇ plane hardening occurs even at relatively high oxygen partial pressures.
  • the Fe-17% Co-1.5% Cr-1.5% Mn alloy plate containing the manganese is subjected to heat transformation at 900 ° C. for 30 minutes in a vacuum atmosphere of 2 ⁇ 10 ⁇ 4 torr, resulting in phase transformation due to surface composition change. 100 ⁇ surface hardening occurs. Looking at it in detail as follows. Manganese is an austenite stabilizing element. Therefore, the addition of 1.5% by weight of manganese lowers the phase transformation temperature of the alloy.
  • the austenite phase is present as a stable phase when manganese is present, and at the same time, when the manganese vaporization occurs and the manganese is removed from the surface, the ferrite phase is present as a stable phase.
  • the heat treatment is performed under a 2 ⁇ 10 ⁇ 4 torr vacuum atmosphere, the manganese on the surface of the plate is vaporized while the manganese concentration on the metal surface is very low compared to the inside of the plate.
  • the concentration of manganese decreases to 0.3 wt% or less on the surface of the plate, the austenite particles on the surface of the plate are transformed to constant temperature by ferrite particles.
  • manganese evaporates at high temperatures is that manganese has a vapor pressure 1000 times greater than that of other metals.
  • the vaporization of manganese at this time serves to lower the oxygen partial pressure near the metal surface. That is, the metal manganese vaporized into the atmosphere reacts with oxygen present around the specimen surface. The vaporized manganese thus removes oxygen present around the metal surface relatively quickly, leaving the metal surface at a relatively low oxygen partial pressure.
  • the condition that vaporized metal manganese will not oxidize at 900 ° C. corresponds to a dew point of -64 ° C. or lower in a 1 atmosphere hydrogen atmosphere.
  • the partial pressure of oxygen around the metal surface will have a value close to its equilibrium value (2.2x10 -27 atm). If the heat treatment atmosphere has such an oxygen partial pressure, it corresponds to a sufficiently low oxygen partial pressure condition to prevent oxidation of the metal surface. If too much oxygen is present in the heat treatment atmosphere (strong oxidizing atmosphere, 2 ⁇ 10 ⁇ 1 torr vacuum), all of the manganese vaporized in the sheet will be oxidized, and the remaining excess oxygen will oxidize the metal sheet surface. Accordingly, the ⁇ 100 ⁇ plane hardening does not occur. Due to the atmospheric oxygen removal effect of manganese, the material containing manganese shows a ⁇ 100 ⁇ plane strengthening even at a higher oxygen partial pressure condition than the material containing less manganese.
  • the Fe-17% Co-1.5% Mn-0.1% C alloy plate containing manganese and carbon forms a strong ⁇ 100 ⁇ plane texture at 1x10 -3 torr vacuum.
  • the Fe-17% Co-1.5% Mn-0.1% C alloy plate containing manganese and carbon is subjected to heat transformation at 900 ° C. for 30 minutes in a 1 ⁇ 10 -3 torr vacuum atmosphere, resulting in phase transformation due to surface composition change. ⁇ 100 ⁇ plane hardening occurs on the surface.
  • Manganese and carbon are austenite stabilizing elements. Therefore, when 1.5% by weight of manganese and 0.1% by weight of carbon are added, the phase transformation temperature of the alloy is lowered.
  • the austenite phase is present as a stable phase in the presence of manganese and carbon, and at the same time, when manganese vaporizes and decarburizes and the concentration of manganese and carbon decreases at the surface, the phase becomes a ferrite phase. Perverted.
  • the heat treatment is performed using a 1 ⁇ 10 ⁇ 3 torr vacuum atmosphere, the manganese and carbon concentration of the metal surface is very low compared to the inside of the plate through surface manganese vaporization and decarburization, and thus the austenite particles on the surface become ferrite particles. It is transformed to constant temperature.
  • the metal surface corresponds to a sufficiently low oxygen partial pressure condition capable of preventing oxidation. Due to the atmospheric oxygen removal effect of manganese and the metal surface oxygen removal effect of carbon, manganese and carbon-containing materials show a ⁇ 100 ⁇ plane strengthening phenomenon.
  • phase transformation is caused by a change in composition to form particles having a ⁇ 100 ⁇ plane texture on the surface of the plate, but the surface ⁇ 100 ⁇ plane particles must be grown inside.
  • a plate having a ⁇ 100 ⁇ facet assembly can be completed.
  • a method of growing the surface particles having the ⁇ 100 ⁇ plane texture formed by the composition change inward will be described.
  • the phase ⁇ 100 ⁇ plane formation phase transformation step and the surface ⁇ 100 ⁇ plane particle internal growth step may be performed separately or in some cases, may be performed collectively or continuously without being performed in a separate process.
  • Table 4 above illustrates the internal growth of surface ⁇ 100 ⁇ plane particles formed by compositional changes. First, a continuous method of growing internally the surface particles having the ⁇ 100 ⁇ plane texture formed by the composition change will be described.
  • the carbon present in the plate diffuses and comes out to the surface to grow the austenite / ferrite phase interface into the plate to form a plate having a semi-penetrating particle structure.
  • the surface of the ⁇ 100 ⁇ plane particles should be in a temperature zone in which the ferrite phase is stable in the decarburization temperature section, and the austenite phase should be stable in the inside of the plate.
  • the Fe-17% Co-1.5% Cr-1.5% Mn alloy sheet was heat-treated at 900 ° C for 30 minutes in a 1x10 -4 torr vacuum atmosphere, and the cooling rate of the sheet was lowered to 100 ° C / hr or less. If the microstructure of the plate is semi-penetrating and ⁇ 100 ⁇ plane surface strength is excellent can be produced. As described above, when the Fe-17% Co-1.5% Cr-1.5% Mn alloy sheet is heat treated at 900 ° C for 30 minutes in a 1x10 -4 torr vacuum atmosphere, particles having ⁇ 100 ⁇ planes on the surface can be strongly integrated. .
  • the austenite / ferrite phase interface of the particles formed on the surface grows into the plate to form a plate having a semi-penetrating particle structure.
  • the reason why the cooling rate is important is that if the cooling rate is too fast, the rate at which the ferrite is stabilized inside the plate is faster than the rate at which ⁇ 100 ⁇ plane particles formed on the surface grow inside, forming a new ferrite nucleus inside the plate. Therefore, the semi-penetrating microstructure cannot be formed so that the texture inside the plate has a different texture than the ⁇ 100 ⁇ plane texture on the surface of the plate. Therefore, the magnetic properties are not excellent.
  • the carbon present in the plate diffuses to the surface and the austenite / ferrite phase interface grows into the plate to form a plate having a semi-penetrating particle structure.
  • the surface of the ⁇ 100 ⁇ plane particles should be in a temperature zone in which the ferrite phase is stable in the decarburization temperature section, and the austenite phase should be stable in the inside of the plate.
  • the heat treatment is characterized in that the heat treatment by laminating the ten sheets of the plate material, each plate was separated by SiO 2 paper.
  • the reason for such heat treatment is that the heat treatments are not suitable for mass production because the heat treatment time is very long. That is, the internal growth of particles using a change in composition has a disadvantage in that the process time is too long to use a continuous process.
  • the Fe-Co alloy sheet must be laminated or heat-treated in the form of a coil so that mass production is possible.
  • the problem is that even when laminating, decarburization and demanganization occur and it is not known whether the surface ⁇ 100 ⁇ plane particles grow inside.
  • the plate material which is the technique disclosed in the present invention, was separated into ceramic paper made of SiO 2 or the like, and the process was performed, a steel sheet having a ⁇ 100 ⁇ plane texture could be produced.
  • the following example illustrates a method of forming an ⁇ 100 ⁇ plane texture by a composition change and performing an additional grain growth heat treatment to grow surface particles inward.
  • the process of continuously growing the surface ⁇ 100 ⁇ plane particles using the composition change takes a long time. Therefore, continuous process is not possible and only intermittent batch process is possible.
  • the surface ⁇ 100 ⁇ plane formation heat treatment and the heat treatment for distinguishing the surface ⁇ 100 ⁇ plane particle internal growth steps may be performed to increase the efficiency of the process.
  • the Fe-17% Co-0.2% C alloy plate may be heat-treated at 920 ° C. for 15 minutes in a 1 ⁇ 10 ⁇ 4 torr vacuum atmosphere to aggregate particles having a strong ⁇ 100 ⁇ plane on the surface.
  • the texture of the plate surface is a cube-on-face
  • the microstructure is a half in which the size of the crystal grains is at least half the minimum plate thickness.
  • a through magnetic soft magnetic steel sheet can be obtained. That is, the Fe-10-35% Co soft magnetic steel sheet having the cube-on-face texture includes perforated or semi-perforated ⁇ 100 ⁇ plane crystal grains. Referring back to Figure 4, it can be seen the presence of these through-type ⁇ 100 ⁇ plane particles.
  • the Fe-10-35% Co soft magnetic steel sheet having the cube-on-face texture may have a ⁇ 100 ⁇ plane strength of at least 5, and when optimizing the process, it has a ⁇ 100 ⁇ plane parallel to the plate plane. You can make a plate with almost 100% particle size.
  • Fe-10-35% Co soft magnetic steel sheet having a cube-on-face texture may include 0.5 to 3% by weight of chromium.
  • the Fe-10-35% Co soft magnetic steel sheet having the cube-on-face texture may include vanadium, molybdenum, nickel, and silicon, and may preferably include 0.5 wt% or less of vanadium. It may comprise up to 1.0% by weight of molybdenum, may include up to 1.0% by weight of nickel, and may include up to 1.0% by weight of silicon.
  • the Fe-10 ⁇ 35% Co soft magnetic steel sheet having the cube-on-face texture may include manganese, and may preferably include 2.0 wt% or less of manganese.

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Abstract

La présente invention concerne un procédé de fabrication d'une plaque de métal pourvue de particules ayant des plans {100} parallèles à une surface de la plaque de métal contenant un alliage de Co comportant de 10 à 35 % en poids de Fe. La présente invention concerne également un procédé de formation d'une texture de plans {100} de la surface de la plaque de métal. Un tel procédé comprend les étapes consistant à : traiter thermiquement la plaque de métal au-dessous de la température de prévention d'une oxydation d'une surface de métal dans un groupe d'alliage de Co comportant de 10 à 35 % en poids de Fe, puis stabiliser la température de la phase d'austénite ; et transformer en phase la plaque de métal traitée thermiquement jusqu'à obtenir une phase de ferrite. La présente invention concerne en outre une tôle d'acier magnétique doux fabriquée selon le procédé. Le procédé permet d'accroître considérablement et rapidement la résistance de la texture de plans {100} de la plaque en un alliage de Co comportant de 10 à 35 % en poids de Fe.
PCT/KR2013/000459 2012-02-22 2013-01-21 Procédé de formation d'une texture d'une plaque en un alliage à base de fe et de co, et tôle d'acier magnétique doux ainsi fabriquée WO2013125790A1 (fr)

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KR1020120017872A KR101376507B1 (ko) 2012-02-22 2012-02-22 Ｆｅ-Ｃｏ계 합금 판재의 집합조직 형성 방법 및 이를 이용하여 제조된 연자성 강판

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Cited By (5)

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EP3730286A1 (fr) * 2019-04-26 2020-10-28 Vacuumschmelze GmbH & Co. KG Paquet de tôles et procédé de fabrication d'un alliage magnétique souple à haute perméabilité
CN113564465A (zh) * 2021-07-05 2021-10-29 北京科技大学 一种兼具拉伸和冲击韧性的锻造FeCo合金及制备方法
CN113604643A (zh) * 2021-07-05 2021-11-05 北京科技大学 一种高冲击韧性的高饱和磁感FeCo合金的制备方法
CN114156079A (zh) * 2017-10-27 2022-03-08 真空融化股份有限公司 高磁导率软磁合金和制造高磁导率软磁合金的方法
US11827961B2 (en) 2020-12-18 2023-11-28 Vacuumschmelze Gmbh & Co. Kg FeCoV alloy and method for producing a strip from an FeCoV alloy

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US5919319A (en) * 1996-01-11 1999-07-06 Imphy S.A. Iron-cobalt alloy, process for manufacturing a strip made of iron-cobalt alloy, and strip obtained
US20070029013A1 (en) * 2000-05-12 2007-02-08 Imphy Ugine Precision Iron-cobalt alloy, in particular for the moving core of electromagnetic actuators
US20090184790A1 (en) * 2007-07-27 2009-07-23 Vacuumschmelze Gmbh & Co. Kg Soft magnetic iron/cobalt/chromium-based alloy and process for manufacturing it

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US3892604A (en) * 1972-02-22 1975-07-01 Westinghouse Electric Corp Method of producing normal grain growth (110) {8 001{9 {0 textured iron-cobalt alloys
JPH0517804A (ja) * 1991-01-30 1993-01-26 Sumitomo Cement Co Ltd 鉄−コバルト系焼結磁性材料の製造方法
US5919319A (en) * 1996-01-11 1999-07-06 Imphy S.A. Iron-cobalt alloy, process for manufacturing a strip made of iron-cobalt alloy, and strip obtained
US20070029013A1 (en) * 2000-05-12 2007-02-08 Imphy Ugine Precision Iron-cobalt alloy, in particular for the moving core of electromagnetic actuators
US20090184790A1 (en) * 2007-07-27 2009-07-23 Vacuumschmelze Gmbh & Co. Kg Soft magnetic iron/cobalt/chromium-based alloy and process for manufacturing it

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114156079A (zh) * 2017-10-27 2022-03-08 真空融化股份有限公司 高磁导率软磁合金和制造高磁导率软磁合金的方法
EP3730286A1 (fr) * 2019-04-26 2020-10-28 Vacuumschmelze GmbH & Co. KG Paquet de tôles et procédé de fabrication d'un alliage magnétique souple à haute perméabilité
CN111926268A (zh) * 2019-04-26 2020-11-13 真空融化股份有限公司 板材叠层和制造高磁导率软磁合金的方法
US11827961B2 (en) 2020-12-18 2023-11-28 Vacuumschmelze Gmbh & Co. Kg FeCoV alloy and method for producing a strip from an FeCoV alloy
CN113564465A (zh) * 2021-07-05 2021-10-29 北京科技大学 一种兼具拉伸和冲击韧性的锻造FeCo合金及制备方法
CN113604643A (zh) * 2021-07-05 2021-11-05 北京科技大学 一种高冲击韧性的高饱和磁感FeCo合金的制备方法

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