EP2031079A1 - Tôle en acier électromagnétique à grande résistance et son procédé de fabrication - Google Patents
Tôle en acier électromagnétique à grande résistance et son procédé de fabrication Download PDFInfo
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- EP2031079A1 EP2031079A1 EP06767202A EP06767202A EP2031079A1 EP 2031079 A1 EP2031079 A1 EP 2031079A1 EP 06767202 A EP06767202 A EP 06767202A EP 06767202 A EP06767202 A EP 06767202A EP 2031079 A1 EP2031079 A1 EP 2031079A1
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- steel sheet
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- electrical steel
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Images
Classifications
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- 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
- 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
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
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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
- 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
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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
- 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
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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
- 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
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
- C21D8/1244—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest
- C21D8/1266—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest between cold rolling steps
-
- C—CHEMISTRY; METALLURGY
- 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
- C22C38/004—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
- C22C38/06—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
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
-
- 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
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
-
- 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
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- 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
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- 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
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- 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
- H01F1/147—Alloys characterised by their composition
- H01F1/14766—Fe-Si based alloys
- H01F1/14775—Fe-Si based alloys in the form of sheets
Definitions
- the present invention relates to high strength electrical steel sheet, more particularly high strength nonoriented electrical steel sheet, and relates to a magnetic material for a high speed rotary machine with a low iron loss, a high magnetic flux density, and a high strength, a magnetic material for an electromagnetic switch superior in wear resistance, and a method of production of the same.
- electromagnetic switches become worn at the contact surfaces along with use, so a magnetic material superior in not only the electromagnetic properties, but also the wear resistance is desired.
- Japanese Patent Publication (A) No. 1-162748 and Japanese Patent Publication (A) No. 61-84360 propose using as a material a slab raised in Si content and further containing one or more of Mn, Ni, Mo, Cr, and other solid solution strengthening ingredients, but sheet breakage is liable to frequently occur at the time of rolling. This causes a drop in productivity and a drop in yield, so there is room for improvement. Further, since Ni, Mo, and Cr are included in large amounts, the material becomes extremely expensive.
- 2006-070348 disclose nonoriented electrical steel sheet in which worked structures are left to obtain strength
- Japanese Patent Publication (A) No. 2006-009048 and Japanese Patent Publication (A) No. 2006-070296 disclose nonoriented electrical steel sheet in which additionally Nb etc. are incorporated in solid solution to suppress recrystallization.
- Nb etc. are incorporated in solid solution to suppress recrystallization.
- This technology was made based on the fact that even if leaving worked structures in the crystal structure, the magnetic properties do not deteriorate that much, that if considering the effect on raising the strength, the result is in no way inferior to a material strengthened by the conventional solid solution elements or precipitates and, not only that, if considering the productivity and the in-plane anisotropy of the magnetic properties, in particular the magnetic flux density, this is extremely useful technology.
- the clear metallurgy has not been established for how to improve the balance of magnetic properties and mechanical properties for electrical steel sheet having worked structures. On this point, no proof has been obtained that this technology is optimal.
- the present invention has as its object the stable on-line production of high strength nonoriented electrical steel sheet having a high strength of a tensile strength (TS) of for example 500 MPa or more and wear resistance and provided with superior magnetic properties of magnetic flux density (B50), iron loss, etc. particularly when used under a high frequency magnetic field, such as a motor rotating at a high speed, without, for example, being changed in cold rollability, annealing work efficiency, etc. from ordinary electrical steel sheet.
- TS tensile strength
- B50 magnetic flux density
- the present invention was made to solve the above problem and has as its gist the following:
- the present invention provides a steel sheet containing C: 0.060% or less, Si: 0.5 to 6.5%, Mn: 0.05 to 3.0%, P: 0.30% or less, S or Se: 0.040% or less, Al: 2.50% or less, and N: 0.040% or less and further containing, in accordance with need, one or both of Cu: 0.001 to 30.0% and Nb: 0.05 to 8.0%, wherein (1) the steel sheet structure is given worked structures and dislocation strengthening is used to increase the strength, (2) the crystal structure is coarsened right before forming the worked structures to finally remain in the steel sheet, and (3) the above crystal structure is limited from the viewpoint of the amount of Si to improve the processability so as to provide electrical steel sheet in which worked structures are left and formed wherein the balance of strength and magnetic properties is improved at a high productivity without causing trouble in work efficiency etc.
- the content is preferably 0.0031 to 0.0301%, more preferably 0.0051 to 0.0221%, more preferably 0.0071 to 0.0181%, more preferably 0.0081 to 0.0151%.
- Si increases the inherent resistance of the steel to reduce the eddy current and reduce the iron loss and raises the tensile strength, but if the amount added is less than 0.2%, that effect is small.
- the content is preferably 1.0% or more, more preferably 1.5% or more, more preferably 2.0% or more, more preferably 2.5% or more.
- the loss due to the eddy current becomes larger, but even in the invention steel containing worked structures, to suppress this eddy current loss, it is effective to raise the Si content.
- the content is made 6.5% or less, preferably 4.0% or less.
- the optimum range of the amount of Si is determined considering also the crystal structure right before the formation of the worked structures to finally remain inside the steel sheet - an important factor of the present invention. While depending on this crystal structure, to reduce the concerns over embrittlement, 3.7% or less is preferable. If 3.2% or less, while there is also the balance with the amount of other elements, it no longer becomes necessary to consider embrittlement much at all. Further, the content may be made less than 2.0%, less than 1.5%, and less than 1.0%.
- Si is effective for suppressing the formation of the austenite phase at a high temperature, stabilizing the ferrite phase even at a high temperature, and making the effect of reduction of the eddy current loss by the solid solution Cu remarkable, but with an amount of addition of less than 1.5%, this effect is small.
- the effect of reduction of the eddy current loss by the solid solution C tends to become weaker, so preferably 2.1% or more, more preferably 2.6% or more Si is contained.
- Mn may be positively added to raise the strength of the steel, but is not particularly required for the purpose in the steel of the present invention utilizing the worked structures as the main means for increasing the strength. This is added for the purpose of raising the inherent resistance or enlarging the sulfides and promoting crystal grain growth and thereby reducing the eddy current loss and reducing the iron loss, but excessive addition not only causes a drop in the magnetic flux density, but also promotes the formation of the austenite phase at a high temperature, so the content is made 0.05 to 3.0%, preferably 0.5% to 2.5%, preferably 0.5% to 2.0%, more preferably 0.8% to 1.2%.
- P is an element with a remarkable effect in raising the tensile strength and contributes to stabilization of the ferrite phase at a high temperature, but in the same way as the above Mn, in the present invention steel, addition is not really required. If over 0.3%, the embrittlement becomes great and industrial scale hot rolling, cold rolling, and other processing become difficult, so the upper limit is made 0.30%.
- the amount is preferably 0.20% or less, more preferably 0.15% or less.
- S easily bonds with the Cu added in accordance with need in the invention steels, has an effect on the behavior in formation of a metal phase mainly comprised of Cu important for the purpose of addition of Cu, and sometimes causes reduction of the strengthening efficiency, so caution is required when including it in a large amount. Further, depending on the heat treatment conditions, it is possible to positively form fine Cu sulfides and promote higher strength. The produced sulfides sometime cause deterioration of the magnetic properties, in particular the iron loss. In particular, when the control value of the iron loss is strict, the content of S is preferably low and is limited to 0.040% or less. The content is preferably 0.020% or less, more preferably 0.010% or less. Se also has substantially the same effect as S.
- Al is usually added as a deoxidizing agent, but it is possible to keep down the addition of Al and use Si for deoxidation. In Si deoxidized steel with an amount of Al of 0.005% or so or less, AlN is not produced, so this also has the effect of reducing the iron loss. Conversely, it is also possible to positively add it to promote the coarsening of the AIN and use the increase in inherent resistance to reduce the iron loss, but if over 2.50%, the embrittlement becomes a problem, so the content is made 2.50% to less than 2.0% or less than 1.8%.
- solid solution Al is positively added to stabilize the ferrite phase at a high temperature and suppress the eddy current loss due to the increase in the electrical resistance. Further, this also has the effect of promoting the remarkable effect of reduction of the eddy current loss by the solid solution Cu.
- this is preferably positively added.
- the content is preferably 0.3% or more, more preferably 0.6% or more, more preferably 1.1% or more, more preferably 1.6% or more, more preferably 2.1% or more. However, if over 2.50%, the castability and embrittlement become problems, so the content is made 2.50% or less.
- N like C
- the content is made 0.040% or less.
- Si deoxidized steel with an Al content of 0.005% or so or less, like C it is an element having the effects of increasing the strength, in particularly raising the yield stress, improving the warm strength and creep strength, and improving the warm fatigue characteristics and, in the case of Nb-containing steel, retarding recrystallization by NbN, and also effective from the viewpoint of improving the texture.
- the content is preferably 0.0031 to 0.0301%, more preferably 0.0051 to 0.0221%, more preferably 0.0061 to 0.0200%, more preferably 0.0071 to 0.0181%, more preferably 0.0081 to 0.0151%.
- N should be 0.0040% or less.
- N is preferably as low as possible. If made 0.0027% or less, the effect of suppression of magnetic aging or deterioration of characteristics by AIN in Al-containing steel is remarkable.
- the content is more preferably 0.0022%, more preferably 0.0015% or less.
- Cu is included in the present invention in accordance with need.
- Cu if present as solid solution Cu, has the effect of raising the recrystallization degree of steel sheet and retarding recrystallization of the steel sheet. In the work strengthening of the present invention, such an effect appears from 0.001% or so.
- Cu is made 0.002% or more, 0.003% or more, 0.005% or more, 0.007% or more, 0.01% or more, 0.02% or more, 0.03% or more, 0.04% or more, 0.05% or more, further 0.1% or more, 0.5% or more, 1.0% or more, or 2.0% or more. If so, the effect appears more.
- the content of Cu is low, the recrystallization retardation effect becomes small, the heat treatment conditions for obtaining the recrystallization retardation effect are limited to a narrow range, and the freedom of management of the production conditions and adjustment of production becomes smaller in some cases.
- the content of Cu is excessively high, the effect on the magnetic properties becomes large and in particular the rise in the iron loss becomes remarkable in some cases, so the upper limit from this viewpoint is 8.0%, particularly preferably 5.5% or less. From the viewpoint of the cost of addition, the content may be made less than 0.1%, further less than 0.01.
- the iron loss is related to the interaction between dislocations remaining in the steel and the domain walls moving at the time of application of a magnetic field.
- the smaller this interaction the more the rise in iron loss is suppressed.
- the interaction with the dislocations becomes greater (or the remaining dislocations themselves become less active). If a large number of dislocations with small interaction with the domain walls are left, the yield strength-iron loss balance is improved.
- the magnitude of the interaction is basically considered to be related to the stress fields around the dislocations (strain of crystal lattice).
- the inventors already filed an application for technology forming a metal phase mainly comprised of Cu in electrical steel sheet (hereinafter in the Description described as a "Cu metal phase") to try to achieve higher strength.
- a Cu metal phase mainly comprised of Cu in electrical steel sheet
- the size of the Cu metal phase or Nb precipitates present in the invention steel is preferably 0.20 ⁇ m or less. If exceeding this, the efficiency of recrystallization retardation falls, a large amount of metal phase becomes necessary, and also the detrimental effect on the magnetic properties easily becomes larger.
- the numerical density of the Cu metal phase or Nb precipitates is limited to the range able to be handled in view of the relationship with the Cu, Nb, or C content and the size of the precipitated phase. 20/ ⁇ m 3 or more or so is desirable. This effect is achieved in the above range of concentration of Cu.
- the range of Cu for achieving good high frequency properties may be made 2.0 to 30.0%. If the content of Cu is low, the eddy current loss reduction effect becomes small. On the other hand, if the content of Cu is too high, suppressing production of the metal phases mainly comprised of Cu becomes difficult and the eddy current loss reduction effect becomes smaller. Not only this, when forming relatively coarse Cu metal phases, the hysteresis loss is liable to be greatly increased and cracks and defects in the steel sheet at the time of rolling are liable to become worse.
- the content of Cu in this case is preferably 2.1% or more, more preferably 2.6% or more, more preferably 3.1% or more, more preferably 3.6% or more, more preferably 4.1% or more, more preferably 4.6% or more.
- the upper limit considering also the cost of addition of Cu itself and the cost of addition of Ni added for the purpose of suppressing surface defects at the time of hot rolling due to Cu (Cu defects), is preferably 20.0%, more preferably 15.0%, more preferably 12.0%, more preferably 10.0%. Note that if the Cu added in the high Si steel in such a case is in the state of a solid solution, it will not cause embrittlement of the steel or deterioration of the cold rollability like Si or Al. Rather, it will have a preferable action in suppressing embrittlement due to Si etc. Further, it does not cause a great deterioration in the magnetic flux density like the later mentioned Cr and is of little harm even if included in a relatively large amount.
- Nb is added in accordance with need in the present invention. While depending on the amounts of C, N, and S contained, it forms carbides, nitrides, sulfides, and other fine precipitates in large amounts in steel sheet and causes a remarkable deterioration in the iron loss, promotes the growth of the ⁇ 111 ⁇ texture after cold rolling and annealing, and reduces the magnetic flux density, so in the present invention steel does not really have to be added. For this reason, it making the upper limit of Nb 8% or less, preferably 0.02% or less, more preferably 0.0050% or less, still more preferably 0.0030% or less, it becomes possible to obtain good iron loss.
- Nb precipitates carbides and nitrides of Nb (hereinafter in this Description referred to as "Nb precipitates”) have the action of retarding the recrystallization of steel sheet, so it is possible to actively use this in the present invention. Further, the fine Nb precipitates also have the effect of increasing the strength in a range not exerting a detrimental effect on the magnetic properties. Further, the Nb can also be utilized as solid solution Nb for strengthening. The range is limited to 0.05 to 8.0%. The content is preferably 0.08 to 2.0%.
- Ti, Zr, and V are elements which form fine precipitates of carbides, nitrides, sulfides, etc. in steel sheet and have the effect of increasing the strength as well, but compared with Nb, the effects are small yet the tendency to cause deterioration of the iron loss is stronger. Further, when forming a partial recrystallized structure in the annealing step after cold rolling, there is a strong effect of promoting alignment in the ⁇ 111 ⁇ orientation disadvantageous to improvement of the magnetic flux density, so in the present invention steel, this rather can become harmful elements. For this reason, when not intending strengthening by precipitates, it is preferable to make the contents 1.0% or less. By making the contents preferably 0.50% or less, more preferably 0.30% or less, still more preferably 0.010% or less, further 0.0050% or less, good iron loss can be obtained.
- Nb, Zr, Ti, V, and other carbide, nitride, and sulfide forming elements should be prevented from precipitating in the present invention so long as not utilizing the precipitating effects of this as explained above.
- Nb+Zr+Ti+V is less than 0.1%, preferably less than 0.08%, more preferably 0.002 to 0.05%.
- Ni is also recognized as having the effect of raising the recrystallization degree from about 0.001%. Even with a content of 0.01% or less, it has a certain effect in fixing dislocations, but preferably is contained in 0.05%, 0.1%, 0.5%, 1.0%, 2.0%, or further 3.0% whereby its effects are manifested more clearly.
- Ni further is known to be effective for the prevention of surface defects at the time of hot rolling due to the Cu as an element included in accordance with need in the invention steel (Cu defects). This may also be positively added for this objective as well. Further, it is relatively small in detrimental effects on the magnetic properties and has the effect of improvement of the magnetic flux density and is further recognized as being effective for increasing the strength, so is an element often used in high strength electrical steel sheet. When using Ni for the purpose of preventing Cu defects, it is as a rough standard added in an amount of 1/8 to 1 ⁇ 2 or so of the amount of Cu.
- Ni is also effective for improving the corrosion resistance, but considering the cost of addition and the detrimental effect on the magnetic properties, the upper limit is preferably made 15%, further 10%, still further 5.0%.
- the upper limit is preferably made 15.0%.
- trace amount elements in addition to the amounts unavoidably included from the ore, scraps, etc., even if added in various known ways, the effect of the present invention is not impaired in any way. Further, even if the amounts are small, these are elements forming fine carbides, sulfides, nitrides, oxides, etc. and exhibiting not insignificant recrystallization retardation effects or strength increasing effects, but these fine precipitates also have large detrimental effects on the magnetic properties. Further, in the present invention steel, the residual worked and restored structures enable a sufficient recrystallization retardation effect to be obtained, so these elements need not really be added.
- the unavoidable content of these trace amount elements is usually 0.005% or less for each element, but addition of 0.01% or so or more is also possible for various purposes not described in this description.
- the one or more types of Bi, Mo, W, Sn, Sb, Mg, Ca, Ce, and Co are made a total of 0.5% or less.
- the steel including the above ingredients is melted by a converter in the same way as ordinary electrical steel sheet, is continuously cast into a slab, then is hot rolled.
- the hot rolled sheet is annealed, cold rolled, final annealed, etc. to be produced. Going through steps for formation of an insulating coating or decarburization etc. in addition to these steps does not detract from the effects of the present invention in any way. Further, there is also no problem even if produced not by the usual steps, but by the steps of production of strip by rapid cooling and solidification, the continuous casting of thin slabs without any hot rolling step, etc.
- the “worked structures” in the present invention are differentiated from the “recrystallized structures” accounting for almost the entire steel sheet in ordinary electrical steel sheet. In general, this indicates structures where the strain accumulated in the steel sheet due to cold rolling etc. has not fully disappeared. More specifically, in the process of annealing cold rolled steel sheet, structures deformed by cold rolling and containing a high density of dislocations are encroached upon by structures with a low density of dislocations formed by holding the steel at a high temperature in the annealing step ("recrystallized structures”) resulting in progression of recrystallization.
- the regions not encroached upon by these "recrystallized structures” are defined as the "worked structures".
- the worked structures generally become lower in density of dislocations due to the so-called restoration etc. during annealing, but do not become as low as the recrystallized structures.
- the "worked structures” may be obtained by further working the recrystallized structures. In this case, if viewed overall, the state becomes one where uniform strain remains in the structure.
- the worked structures are utilized to achieve the targeted higher strength.
- the average crystal grain size d of the steel sheet right before the step of forming the worked structures to finally remain inside the steel sheet characterizing the present invention will be explained.
- this grain size will be called the “grain size before working”.
- the present invention basically coarsens the "grain size before working” to greatly improve the properties after working, in particular the strength-iron loss balance.
- the "grain size before working” becomes the grain size at the point of time of the hot rolled sheet when cold rolling the hot rolled sheet, then suppressing recrystallization in the subsequent annealing so as to leave worked structures in the final product. At this time, if annealing the hot rolled sheet as generally performed in electrical steel sheet, the grain size after annealing the hot rolled sheet becomes the "grain size before working".
- this "grain size before working" d ( ⁇ m) is defined as a specific range in relation to the amount of Si and the amount of Al. That is, by satisfying the following formula (1) or (2) and further (3) and (4), the superior strength-iron loss balance characteristic of the present invention is achieved: d ⁇ 20 ⁇ m d ⁇ 220 - 50 ⁇ Si % - 50 ⁇ Al % d ⁇ 400 - 50 ⁇ Si % and d ⁇ 820 - 200 ⁇ Si %
- Formula (1) simply shows the case where the "grain size before working" is coarser than a specific size.
- the crystal grain size of usual steel sheet is controlled to a range of several ⁇ m to several hundreds of 100 ⁇ m, but to obtain the effect of the present invention, it must be made 20 ⁇ m or more.
- the size is preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more, more preferably 150 ⁇ m or more, more preferably 200 ⁇ m or more, more preferably 250 ⁇ m or more.
- Formula (2) defines the "grain size before working" obtained by the effect of the invention in relation to the amount of Si and the amount of Al.
- the higher the amount of Si and the amount of Al in steel sheet the better the strength-iron loss balance, so the higher the Si and the higher the Al in the material, the easier it is to obtain an excellent strength-iron loss balance even if the "grain size before working" is small.
- d ⁇ (200-50 ⁇ Si%-50 ⁇ Al%), d ⁇ (180-50 ⁇ Si%-50 ⁇ Al%), further d ⁇ (150-50 ⁇ Si%-50 ⁇ Al%) are possible.
- d ⁇ (220-50 ⁇ Si%) is also possible.
- Formula (3) and Formula (4) give rough standards for the upper limit of the "grain size before working".
- This upper limit depends not only the steel ingredients other than the amount of Si and the heat history up until working, but also the method of working the steel sheet and the properties aimed at.
- high temperature long term hot rolled sheet annealing is simple, but it is also possible to make the precipitates coarser and improve the grain growth at the time of annealing by low temperature slab heating or high temperature coiling in the hot rolling or high temperature hot rolled sheet annealing conditions. Specifically, for example, it is preferable to make the annealing step right before forming the worked structures any one of the following.
- the crystal grain size and recrystallization rate are found by observation of the structure of the sheet cross-section by etching as usually performed in observation of the structure of ferrous metals.
- the grain size is the diameter found from the area per crystal grain observed when assuming the cross-sectional area of the grain is a circle, while the recrystallization rate is found from the area rate of not yet recrystallized parts in the observed area. Needless to say the measurement has to be performed for a sufficiently average region without segregation.
- the mechanism for the effect of the "grain size before working” is not certain, but the effects of the change of the dislocation structure, the change of the texture, further the change in the dislocation structure after working due to the difference in texture before working, etc. may be considered. While the details are unclear, it is conjectured that in the end, the dislocation structures in the worked structures change to structures acting as powerful obstructions to dislocations trying to move due to external stress and not easily acting as obstructions to domain walls trying to move due to the external magnetic field.
- the steel sheet covered by the present invention has a tensile strength of 500 MPa or more. If a steel sheet with a tensile strength of an extent lower than this, even with a steel sheet mainly strengthened by the usual Si, Mn, and other solid solution elements and structurally completely occupied by recrystallized structures, production becomes possible without causing the productivity to deteriorate that much. This is because such a material gives sheet remarkably superior in magnetic properties.
- the present invention is limited to high strength materials mainly strengthened by the usual solid solution strengthening and unable to be produced without deterioration of the productivity. To enjoy the merits of the present invention more, the invention should be applied to preferably 600 MPa or more steel sheet, more preferably 700 MPa or more, more preferably 800 MPa or more steel sheet. Even production of 900 MPa or more steel sheet not being produced at all at the present is possible. Further, even 1000 MPa or more steel sheet not even imagined for production in the future can be produced with a high productivity.
- the yield stress when used as the rotor of a motor, a slight deformation means the end of the life of the part, so not the tensile strength, but the yield stress should be used for evaluation.
- the invention steels have worked structures remaining in them, so compared with solid solution strengthened steel or precipitation strengthened steel, if the same strength, the yield stress is higher and, in comparison with these conventional materials, more desirable properties are exhibited. That is, the yield ratio becomes a relatively high value of 0.7 to 1.0 or so.
- the correlation between the yield stress and the tensile strength becomes extremely strong in the material. For this reason, even if using the yield stress for evaluation, the superiority of the invention steels does not change at all.
- the effect of the invention is exhibited without problem even for applications like rotors where the yield stress becomes a problem.
- the worked structures are present in an area rate in observation of the cross-sectional structure of steel sheet of 1% or more.
- the cross-sectional area is observed in the present invention by a cross-section where one side of the cross-section becomes the steel sheet rolling direction and the other side becomes the steel sheet thickness direction.
- the method performed with ordinary steel sheet of using Nital or another chemical to etch and expose the structure is used, but the invention is not particularly limited in method of observation. Any technique enabling differentiation of the recrystallized structure and the worked structures may be used.
- the area rate of the worked structures is 1% or less, the effect of increasing the strength becomes smaller.
- the result becomes the ordinary steel sheet itself.
- the area rate of the worked structures is controlled to preferably 5% or more, more preferably 10% or more, more preferably 20% or more, more preferably 30% or more, more preferably 50% or more, more preferably 70% or more.
- the structure is adjusted in accordance with the strength and magnetic properties needed, but this adjustment can be performed by the steel ingredients, hot rolling history, cold rolling rate, annealing temperature, annealing time or heating speed, cooling rate, etc.
- a person skilled in the art can perform this without any problem at all by repeated trials.
- steel sheet annealed so that the recrystallized structures account for the entire weight may be given strain by repeated cold rolling etc. to form worked structures. In this case, usually the strain is given macroscopically evenly, so the entire amount of the structure becomes worked structures or corresponding to 100% worked structures.
- the steel ingredients, heat history, properties, etc. before working are considered and the amount of work is used to control the strength and magnetic properties. This is also possible for a person skilled in the art without problem by several trials.
- the temperature is not over 700°C, while even with so-called ordinary high grade electrical steel sheet with an amount of Si of 3% or so, the temperature is not over 800°C or so, but for example by adding suitable amounts of Cu, Nb, etc., it is possible to obtain invention steels of completely restored structures not recrystallizing at all even at a temperature of 900°C or so or more.
- annealing at a temperature very different from ordinary electrical steel sheet requires a major change in the furnace temperature and not only invites a drop in the work efficiency, but also causes problems in safety as well as mentioned above due to the production of unburned gas.
- the lower limit of the annealing temperature for avoiding these problems due to extremely low temperature annealing is 400°C or so or more.
- the rough standard for the annealing time depends on the temperature as well, but at least 5 seconds or so is required for giving an annealing effect.
- the annealing time cannot be unambiguously explicitly shown since it depends on the ingredients, production history up to the heat treatment, etc., but the rough standard is, if 850°C, within 5 minutes, if 750°C, within one hour, and, if 600°C, without 10 hours.
- the temperature and time conditions enabling the effect of the invention to be enjoyed can be found without problem by a person skilled in the art by several trials. The point is confirmation of the recrystallization behavior of the steel sheet covered.
- the above working is usually performed by cold rolling, but there is no need to insist on this so long as there is a change in amount of strain or material quality with the prescription of the present invention.
- Warm rolling, hot rolling of an extent where the worked structures do not disappear, tensile deformation by imparting tension, bending deformation by a leveler etc., shot blasting, forging, or another method may be used. Rather, due to the method of imparting strain, the dislocation structure is made to change to one preferable for the present invention explained later, so further improvement in properties becomes possible.
- the rough standard of the reduction rate can be easily estimated from the ratio of the size of the crystal grains, but is 10 to 70% or so.
- the material can easily be made thinner and the productivity of the very thin electrical steel sheet which had been difficult to make in the past is also improved.
- Such very thin electrical steel sheet according to the present invention enables suppression of the eddy current loss in the case of use under a high frequency magnetic field, so also has the merit of being effective for reduction of the iron loss.
- the present invention inherently differs from this steel sheet and method. It basically does not perform any heat treatment after working the sheet into the part of the electrical equipment. Even when performing some sort of heat treatment by bonding the steel sheet or surface control etc., the worked structures prescribed in the present invention will not disappear and will remain in the range prescribed by the present invention. This is because if the worked structures disappear or deviate from the prescribed range of the present invention, the strength of the steel sheet required in the state of use as an actual motor will become insufficient.
- the rough standard of the temperature of this heat treatment is the same as the temperature conditions in the above step of annealing the steel sheet.
- the optimal conditions for enjoying the effect of the invention can be found with the cooperation of persons skilled in the art of production of steel sheet or, even without such cooperation, without any problem by several trials by a usual manufacturer of electrical equipment.
- the effect of the "worked structures" explained above can also be evaluated by the dislocation density in the "worked structures".
- the average dislocation density in the worked structures is 1 ⁇ 10 13 /m 2 or more, more preferably 3 ⁇ 10 13 /m 2 or more, more preferably 1 ⁇ 10 14 /m 2 or more, more preferably 3 ⁇ 10 14 /m 2 or more.
- This dislocation density is measured by a transmission type electron microscope.
- the average dislocation density is 1 ⁇ 10 12 /m 2 or so or less, so is 10 times or more the difference sufficient for discrimination of the worked structures.
- the dislocations form relatively stable cell structures.
- the cells are normally of a diameter of 1 ⁇ m to 0.1 ⁇ m or so. Except for the fact that the cell boundaries are formed by dislocations and the difference in crystal orientations with adjacent cells is small, they have structures similar to general crystal grains. They can be viewed as one type of superfine crystal grains and are believed not to easily obstruct domain wall movement. Further, such superfine crystal grains are high in strength and have corresponding ductility when working is required. When considering the balance of strength and magnetic properties, this is believed to be of a level sufficiently enabling practical use.
- solid solution Cu strengthening it is also possible to introduce solid solution Cu and obtain electrical steel sheet superior in high frequency magnetic properties without inviting the deterioration of the magnetic properties or productivity accompanying the addition of conventional alloy elements (below, referred to as "solid solution Cu strengthening"). In this case, by the measures of
- the electrical steel sheet is made one containing, by mass%, C: 0.06% or less, Si: 1.5 to 6.5%, Mn: 0.05 to 3.0%, P: 0.30% or less, S or Se: 0.040% or less, Al: 2.50% or less, Cu: 2.0 to 30.0%, and N: 0.0400% or less, having a balance of Fe and unavoidable impurities, and not containing any metal phase made of Cu inside it.
- it may further contain one or more of Nb: 8% or less, Ti: 1.0% or less, B: 0.010% or less, Ni: 15.0% or less, and Cr: 15.0% or less.
- the transformation of the steel matrix phase at the time of heat treatment not only results in a great change in the solubility of Cu, but also ends up causing the structures preferable for magnetic flux density to disappear, so when utilizing solid solution Cu strengthening, basically transformation at the time of heat treatment should be avoided.
- a single ferrite phase at the temperature region from room temperature to 1150°C or satisfaction, by mass%, of 980 - 400 ⁇ C + 50 ⁇ Si - 30 ⁇ Mn + 400 ⁇ P + 100 ⁇ A ⁇ 1 - 20 ⁇ Cu - 15 ⁇ Ni - 10 ⁇ Cr > 900 is preferable. If off from this range, unpreferable transformation occurs during the heat treatment and the possibility increases of the effect of solid solution Cu strengthening being obstructed.
- solid solution Cu strengthening can be clearly shown even with comparison of the properties with general materials.
- the Cu is 0.1%, and the crystal grain size is the same, a solid solution Cu strengthened steel sheet having an iron loss W 10/400 of 0.8 or less, 0.7 or less, 0.6 or less, 0.5 less, 0.4 less, more preferably 0.30 or less, is obtained.
- the tensile strength is 2.0 times or less than of the comparative steel.
- the solid solution strengthening causes the strength to rise. If the amount of solid solution is large as with solid solution Cu strengthening, depending on the element, the rise in strength also becomes remarkable, but the solid solution Cu in high Si steel characteristic of solid solution Cu strengthened steel does not harden the material that much.
- the ratio is more preferably suppressed to 1.7 or less, more preferably 1.5 or less. If the amount of solid solution Cu is increased, while the result can be said to be solid solution Cu strengthened steel, the strength becomes higher. It is not that the smaller the rise in strength the better, but if compared with the Si, Cr, etc. used as the solid solution element, the rise in strength is small and embrittlement is also suppressed.
- the sheet is held in the temperature region of 800°C or more for 5 sec or more and the conditions are set so that no austenite phase is produced in the steel material even at the peak temperature in this heat treatment.
- the temperature is preferably 900°C or more, more preferably 1000°C or more, more preferably 1050°C or more, Further, the time is preferably 10 sec or more, more preferably 30 sec or more, more preferably 60 sec or more, but if a temperature and time where sufficiently solubility of Cu occurs in the balance with the Cu content, the characterizing effect of the present invention can be sufficiently obtained. However, it is of course necessary to control this taking into account the viewpoint of controlling the crystal grain size having a large effect on the magnetic properties as well.
- the crystal grain size is too fine or too coarse, the magnetic properties will sometimes be degraded. It is well known that there is an optimal grain size in the usage conditions. Further, the peak temperature has to be set to a temperature region where no austenite phase is produced. If a small amount is produced, the detrimental effect in the properties will be small, but the annealing is preferably performed with a complete ferrite phase.
- the temperature depends mainly on the steel ingredients, so no specific temperature can be described, but the above formula 1 is a general standard. Further, a person having knowledge of general metallurgy would be able to set a suitable temperature range without any difficulty by the generally performed experiments in heat treatment and observation of structure or recent remarkable advances in thermodynamic computations.
- the cooling rate in the heat treatment step also becomes an important control factor. The reason is that the Cu sufficiently dissolved by holding the steel at a high temperature becomes supersaturated during cooling, so depending on the cooling rate will end up precipitating as a metal Cu phase and sometimes reduce the effect of the present invention.
- the preferable conditions are made a cooling step after holding the steel in the temperature region of 800°C or more for 5 sec or more of cooling by a cooling rate of 40°C/sec or more to 300°C or less. From the object of the present invention, there is nothing better than a high cooling rate, but if cooling too rapidly, the properties sometimes deteriorate due to the heat history etc., so caution is required.
- the rate is preferably 60°C/sec or more, more preferably 80°C/sec or more, more preferably 100°C/sec or more.
- the residence time at 700 to 400°C becomes important. At 700°C or more, the degree of supersaturation of Cu is small and precipitation is difficult to occur, while at 400°C or less, diffusion of Cu is suppressed, so precipitation becomes hard. If the time is made 5 sec or less, preferably 3 sec or less, more preferably 2 sec or less, precipitation of the metal Cu phase can be suppressed and a sufficient amount of solid solution Cu for obtaining the effect of the invention can be secured.
- the steel is preferably held at a temperature region of over 400°C for 30 sec or more. This is because by such heat treatment, the precipitation of the metal Cu phase is promoted and the eddy current loss is increased.
- the above heat treatment may be annealing in a range 350 to 700°C for 10 sec to 360 minutes so that the Cu metal phases finely precipitate while recrystallization remains suppressed.
- the Cu metal phases end up coarsening by annealing at a high temperature for a long time and the strengthening ability falls.
- attention must be paid so that the annealing time does not become too long. The lower the temperature, the longer the annealing possible.
- the present invention is characterized by the lack of any metal Cu phases in the steel material. This can be identified and confirmed by the diffraction pattern of an electron microscope etc. or an attached X-ray analysis device. Of course, confirmation is also possible by a method other than this such as chemical analysis.
- the "metal phase mainly comprised of Cu” covers ones with a diameter of 0.010 ⁇ m or more. The reason is that if less than 0.005 ⁇ m, it is too fine, so even using the current highest precision analysis equipment, it would be hard to identify the metal Cu phases covered by the present invention.
- the effects of present invention do not depend on the presence or type of the surface coating formed on the surface of ordinary electrical steel sheet or further on the production steps, so the invention can be applied to nonoriented or grain-oriented electrical steel sheet.
- the invention steel can give features very different from steel sheet of conventional recrystallized structures in the in-plane anisotropy of properties. If viewing the magnetic flux density, in the as cold rolled full hard state, the properties of the direction 45° from the coil rolling direction (D direction) are higher than the properties in the rolling direction (L direction) or coil width direction (C direction). Electrical steel sheet having ordinary recrystallized structures in almost all cases have properties in the D direction lower than the properties in the L or C direction.
- the applications are not particularly limited. In addition to the applications for rotors of motors used in household electrical appliances, automobiles, etc., the invention may also be applied to all applications where strength and magnetic properties are sought.
- a slab of 200 mm thickness having the ingredients of 0.002%C-3.0%Si-0.5%Mn-0.03%P-0.001%S-0.3%Al-0.002%N was hot rolled by a slab heating temperature of 1100°C and a coiling temperature of 700°C.
- the hot rolled sheets were annealed to 800, 950, and 1050°C to change the grain sizes to 10, 100, and 200 ⁇ m.
- These hot rolled sheets were cold rolled, then either not annealed or annealed at 400 to 1000°C for 30 sec to produce product sheets of sheet thicknesses of 0.5 mm differing in recrystallization rate and strength. These were evaluated for mechanical properties using JIS No. 5 test pieces and properties of iron loss W 10/400 by 55 mm square SST tests.
- X 0 , X 45 , X 90 are the characteristics in the coil rolling direction, 45° direction, and direction perpendicular to that.
- the present invention it is possible to stably produce hard high strength electrical steel sheet superior in magnetic properties. That is, the present invention enables the targeted strength to be obtained even with relatively low amounts of the added elements used for solid solution strengthening and precipitation strengthening, so the cold rollability is improved, the productivity of the cold rolling step is improved, and annealing in the usual operating range becomes possible, so the work efficiency in the annealing step also is improved. Further, by cold rolling again after annealing, it becomes possible to simply produce extremely thin materials which were difficult to produce in the past.
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WO2013038020A1 (fr) | 2011-09-16 | 2013-03-21 | Voestalpine Stahl Gmbh | Bande magnétique de résistance supérieure, à grains non orientés et de polarisation élevée, et procédé de production associe |
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EP2474636A4 (fr) * | 2009-09-03 | 2017-05-17 | Nippon Steel & Sumitomo Metal Corporation | Tôle d'acier électromagnétique non orienté |
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- 2006-06-16 JP JP2008521083A patent/JPWO2007144964A1/ja active Pending
- 2006-06-16 KR KR1020087030461A patent/KR101177161B1/ko active IP Right Grant
- 2006-06-16 CN CN2006800549991A patent/CN101466851B/zh active Active
- 2006-06-16 WO PCT/JP2006/312552 patent/WO2007144964A1/fr active Application Filing
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US9595376B2 (en) | 2009-06-03 | 2017-03-14 | Nippon Steel & Sumitomo Metal Corporation | Non-oriented electrical steel sheet and manufacturing method thereof |
US9085817B2 (en) | 2009-06-03 | 2015-07-21 | Nippon Steel & Sumitomo Metal Corporation | Non-oriented electrical steel sheet and manufacturing method thereof |
RU2497973C2 (ru) * | 2009-06-03 | 2013-11-10 | Ниппон Стил Корпорейшн | Нетекстурованный лист из электротехнической стали и способ его получения |
EP2474636A4 (fr) * | 2009-09-03 | 2017-05-17 | Nippon Steel & Sumitomo Metal Corporation | Tôle d'acier électromagnétique non orienté |
US9627116B2 (en) | 2011-09-16 | 2017-04-18 | Voestalpine Stahl Gmbh | Method for producing a non-grain-oriented higher-strength electrical strip and use thereof |
WO2013038008A1 (fr) | 2011-09-16 | 2013-03-21 | Voestalpine Stahl Gmbh | Procédé de production d'une bande magnétique de résistance supérieure et à grains non orientés, et son utilisation |
DE102011053722B3 (de) * | 2011-09-16 | 2013-01-03 | Voestalpine Stahl Gmbh | Verfahren zum Herstellen eines höherfesten Elektrobandes, Elektroband und dessen Verwendung |
WO2013038020A1 (fr) | 2011-09-16 | 2013-03-21 | Voestalpine Stahl Gmbh | Bande magnétique de résistance supérieure, à grains non orientés et de polarisation élevée, et procédé de production associe |
DE102011053722C5 (de) * | 2011-09-16 | 2020-12-24 | Voestalpine Stahl Gmbh | Verfahren zum Herstellen eines höherfesten Elektrobandes, Elektroband und dessen Verwendung |
EP2818564A4 (fr) * | 2012-02-23 | 2015-08-19 | Jfe Steel Corp | Procédé de production d'une tôle d'acier électronique |
US9761359B2 (en) | 2012-02-23 | 2017-09-12 | Jfe Steel Corporation | Method of producing electrical steel sheet |
US9570219B2 (en) | 2012-03-29 | 2017-02-14 | Nippon Steel & Sumitomo Metal Corporation | Non-oriented electrical steel sheet and method of manufacturing non-oriented electrical steel sheet |
EP2832882A4 (fr) * | 2012-03-29 | 2015-12-16 | Nippon Steel & Sumitomo Metal Corp | Tôle d'acier électromagnétique non orientée et procédé de production de cette dernière |
EP3118336A4 (fr) * | 2014-09-28 | 2017-07-12 | Northeastern University | Procédé de préparation d'acier à haute teneur en silicium à grains orientés |
DE102015112215A1 (de) * | 2015-07-27 | 2017-02-02 | Salzgitter Flachstahl Gmbh | Hochlegierter Stahl insbesondere zur Herstellung von mit Innenhochdruck umgeformten Rohren und Verfahren zur Herstellung derartiger Rohre aus diesem Stahl |
Also Published As
Publication number | Publication date |
---|---|
KR20090014383A (ko) | 2009-02-10 |
EP2031079A4 (fr) | 2016-07-06 |
US20100158744A1 (en) | 2010-06-24 |
WO2007144964A1 (fr) | 2007-12-21 |
CN101466851B (zh) | 2012-08-22 |
EP2031079B1 (fr) | 2021-01-13 |
KR101177161B1 (ko) | 2012-08-24 |
JPWO2007144964A1 (ja) | 2009-10-29 |
CN101466851A (zh) | 2009-06-24 |
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