WO2022213853A1 - 一种无取向电工钢板及其制造方法 - Google Patents

一种无取向电工钢板及其制造方法 Download PDF

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WO2022213853A1
WO2022213853A1 PCT/CN2022/083918 CN2022083918W WO2022213853A1 WO 2022213853 A1 WO2022213853 A1 WO 2022213853A1 CN 2022083918 W CN2022083918 W CN 2022083918W WO 2022213853 A1 WO2022213853 A1 WO 2022213853A1
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oriented electrical
steel sheet
electrical steel
rolling
present
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PCT/CN2022/083918
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English (en)
French (fr)
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张峰
李国保
王波
姜全力
沈侃毅
张文岳
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宝山钢铁股份有限公司
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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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C21D1/26—Methods of annealing
    • 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
    • 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
    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • 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
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a steel sheet and a manufacturing method thereof, in particular to a non-oriented electrical steel sheet and a manufacturing method thereof.
  • non-oriented electrical steel In the existing industrial production, non-oriented electrical steel has a wide range of uses, and it can be used to make equipment such as small and medium-sized motors, compressors, EI iron cores, large generators, and new energy vehicle drive motors.
  • each device has different requirements for the electromagnetic properties of non-oriented electrical steel, but generally it is expected that the magnetic induction of the non-oriented electrical steel is as high as possible, and the iron loss is as low as possible.
  • the lower the grade of non-oriented electrical steel the higher the magnetic induction and the higher the iron loss; the higher the grade of the non-oriented electrical steel, the lower the magnetic induction and the lower the iron loss.
  • the equiaxed crystallinity rate in the continuous casting slab is often increased by adding a large amount of Si and Al to the steel and by means of electromagnetic stirring in steelmaking. , and normalized intermediate annealing method is adopted after hot rolling to improve the recrystallized microstructure of hot rolled steel coil.
  • the surface of the finished steel plate finally obtained by this improved process has no shingle-like defects, and has higher magnetic induction and lower iron loss.
  • the publication number is CN103305748A
  • the publication date is September 18, 2013,
  • the Chinese patent document entitled "a non-oriented electrical steel sheet and its manufacturing method" discloses a high magnetic A method for manufacturing a non-oriented electrical steel sheet with low iron loss and low iron loss.
  • the production process is steelmaking, hot rolling, pickling, cold rolling, and annealing in sequence, and the hot rolling process does not include the normalization process; 3)
  • the final rolling temperature of the hot rolling process FDT satisfies the following relationship: 830+42(Si+Al) ⁇ FDT ⁇ 880+23(Si+Al); 4)
  • the time interval t1 before rolling is controlled to be 20 s or more, and the time interval t2 after finish rolling of the intermediate billet until it is laminar cooling is controlled to be 5 s or more.
  • One of the objectives of the present invention is to provide a non-oriented electrical steel sheet free from normalizing intermediate annealing.
  • the non-oriented electrical steel sheet can ensure lower production costs by optimizing the chemical composition of the steel and cooperating with the improved manufacturing process. , improve the quality of the steel sheet, the non-oriented electrical steel sheet has the characteristics of high magnetic induction and low iron loss, and its iron loss P 10/50 ⁇ 3.2W/kg, for example, between 2.7W/kg ⁇ 3.2W/kg, and Magnetic induction B 50 ⁇ 1.72T, for example, between 1.72T and 1.74T, which has a very good promotion prospect and application value.
  • the present invention provides a non-oriented electrical steel sheet free from normalization intermediate annealing, and the mass percentage content of each chemical element is:
  • the mass percentage content of element C is controlled to be 0 ⁇ C ⁇ 0.004%.
  • Si element also affects the mechanical properties of the finished steel sheet, which can effectively reduce the iron loss and improve the mechanical strength of the steel sheet.
  • more than 1.0% Si needs to be added to the steel.
  • the Si element content in the steel should also not be too high.
  • the mass percentage content of Si element is controlled between 1.0 and 2.6%.
  • Mn element can effectively control the content of sulfide inclusions in the steel. In order to ensure that the Mn element can effectively play a role, it is necessary to add more than 0.2% Mn to the steel. In addition, the content of Mn element in the steel should also not be too high. When the content of Mn element in the steel is higher than 1.0%, the magnetic induction of the finished steel plate will be greatly deteriorated. Based on this, the mass percentage content of Mn element in the non-oriented electrical steel sheet of the present invention is controlled to be between 0.2 and 1.0%.
  • the Al element can improve the iron loss performance of the finished steel sheet. In order to ensure that the Al element can effectively play a role, more than 0.2% Al needs to be added to the steel. Of course, the content of Al element in the steel should also not be too high. When the content of Al element in the steel is higher than 1.6%, the magnetic induction of the finished steel plate will be significantly reduced. Based on this, the mass percentage content of Al element in the non-oriented electrical steel sheet of the present invention is controlled to be between 0.2 and 1.6%.
  • Ca element can play a good effect of controlling oxide inclusions.
  • more than 0.0003% of Ca needs to be added to the steel, 0.0003% and above
  • the Ca content of 0.0003% can effectively inhibit the formation of fine sulfide inclusions such as MnS and Cu x S in the steel.
  • the Ca content of 0.0003% will not significantly increase the manufacturing cost of the steel.
  • the Ca element content in the steel should not be too high.
  • the Ca element content in the steel is higher than 0.0035%, it will not only greatly increase the manufacturing cost, but also greatly prolong the RH refining operation time in the steel smelting process, resulting in the smelting process.
  • the mass percentage content of Ca element is controlled between 0.0003% and 0.0035%.
  • the mass percentage content of each chemical element also satisfies at least one of the following items:
  • Si 2 /Mn 0.017 to 0.17%.
  • Si, Al and Mn elements can also be controlled to satisfy Si+Al: 1.4-3.2% and/or Si 2 /Mn: 0.017-0.17 %.
  • Si, Al and Mn all represent the chemical element mass percentage content of their respective corresponding elements.
  • Si and Al elements are preferably controlled to satisfy Si+Al: 1.4-3.2%, because: when the Si+Al content is less than 1.4%, even if In the process of steelmaking and smelting, steelmaking electromagnetic stirring is not used.
  • the front end of dendrite growth is free crystals. Due to sufficient natural convection, these crystals can effectively grow at the solidification tip, and free crystals grow rapidly. Large and increased, it will prevent the formation of columnar crystals at the solidification front.
  • the fine equiaxed crystals are basically dominated, and the coarse and developed columnar crystals will not be formed, and the surface of the finished steel plate will not appear tile-shaped defects.
  • the convection of molten steel at the end of solidification is insufficient, the growth rate of free crystals is slow, and the number of increases is also small. Therefore, under this condition In the low magnification sample of the continuous casting slab, the coarse and well-developed columnar crystals are basically the main ones, and the fine equiaxed crystals are few.
  • Si element and Mn element can also be controlled to satisfy Si 2 /Mn: 0.017-0.17%.
  • the purpose of limiting the ratio of Si 2 /Mn content is that Si element is a ferrite-forming element, which has a good effect on promoting the growth of columnar crystals in continuous casting slabs, while Mn element is austenite-forming element, which can expand the austenite.
  • the intenite phase region and further, by controlling the transformation of the microstructure between austenite and ferrite, to reduce the proportion of columnar crystals in the continuous casting slab (for example, control the proportion of columnar crystals between 0 and 70%) , so as to improve the effect of shingle-shaped defects in the finished steel plate.
  • the ratio of Si 2 /Mn content is greater than 0.17%, under the condition of not adopting steelmaking electromagnetic stirring and not adopting hot rolling normalization intermediate annealing or bell furnace intermediate annealing, obvious corrugated defects will appear on the finished steel plate.
  • Si 2 /Mn can also be preferably controlled to be 0.017-0.17%.
  • non-oriented electrical steel sheet according to the present invention among other inevitable impurities: S ⁇ 0.0040%, O ⁇ 0.003%, N ⁇ 0.003%, P ⁇ 0.2%, Nb ⁇ 0.001%, V ⁇ 0.001%, Ti ⁇ 0.001%.
  • S, O, N, P, Nb, V and Ti are all inevitable impurity elements in the non-oriented electrical steel sheet of the present invention.
  • the content of impurity elements in the non-oriented electrical steel sheet should be reduced as much as possible.
  • S is an impurity element, and the content of S element in the steel should not be too high.
  • the content of S element in the steel is higher than 0.004%, the number of sulfides in the steel will increase rapidly. And the size is small, thereby deteriorating the electromagnetic properties of the finished steel plate. Therefore, in the non-oriented electrical steel sheet according to the present invention, it is necessary to strictly control the mass percentage of S to be S ⁇ 0.0040%.
  • the content of O element in the steel should not be too high.
  • the harmful inclusions such as Al, Si, and Ca of oxygen will be greatly increased. increase, which strongly hinders the grain growth of the finished steel sheet and deteriorates the electromagnetic properties of the finished steel sheet.
  • the mass percentage of O element is controlled to be O ⁇ 0.003%.
  • N is an impurity element, and the content of N element in the steel should not be too high.
  • the inclusions increase significantly, resulting in a large increase in the number of inclusions, which strongly hinders the grain growth of the finished steel sheet and deteriorates the electromagnetic properties of the finished steel sheet.
  • the mass percentage content of N element is controlled to be N ⁇ 0.003%.
  • the content of P element in the steel should not be too high.
  • the content of P element in the steel exceeds 0.2%, the stability of the cold rolling process will be significantly reduced, resulting in the appearance of cold rolled steel sheets. Abnormal conditions such as edge cracks and broken belts.
  • the mass percentage content of P element is controlled to be P ⁇ 0.2%.
  • Nb In the non-oriented electrical steel sheet of the present invention, the content of Nb element in the steel should not be too high. When the content of Nb element in the steel exceeds 0.001%, the harmful precipitates such as C and N of Nb will be greatly increased, hindering the The grains grow and deteriorate the magnetic properties of the steel. Based on this, in the non-oriented electrical steel sheet according to the present invention, the mass percentage content of Nb element is controlled to be Nb ⁇ 0.001%.
  • V In the non-oriented electrical steel sheet of the present invention, the content of V element in the steel should not be too high. When the content of V element in the steel exceeds 0.001%, the harmful precipitates such as C and N of V will be greatly increased, hindering the The grains grow and deteriorate the magnetic properties of the steel. Based on this, in the non-oriented electrical steel sheet of the present invention, the mass percentage content of V element is controlled to be V ⁇ 0.001%.
  • the content of Ti element in the steel should not be too high.
  • the harmful precipitates such as C and N of Ti will be greatly increased, hindering the The grains grow and deteriorate the magnetic properties of the steel.
  • the mass percentage content of Ti element is controlled to be Ti ⁇ 0.001%.
  • Nb+V+Ti ⁇ 0.0025% is also satisfied.
  • Nb, V and Ti in the formula are all substituted into the corresponding mass percentage of each element.
  • Nb, V and Ti elements can be controlled to satisfy Nb+V+Ti ⁇ 0.0025%.
  • Nb, V and Ti elements are strong C, O, N compound forming elements, which will combine with C, O, N elements to generate small-sized and numerous harmful inclusions. Therefore, from the viewpoint of the convenience of production control, in the present invention, it is desirable that the total amount of Nb, V and Ti elements be as low as possible, and it is preferable to control Nb+V+Ti ⁇ 0.0025%.
  • R Ca/(O+1/2S).
  • Ca, O, and S are all substituted into the mass percentages of the chemical elements corresponding to each element, respectively.
  • the content of Ca is 0.0005% to 0.0025%.
  • the non-oriented electrical steel sheet of the present invention has no corrugated defects, no internal and external oxide layer defects, and has excellent quality.
  • another object of the present invention is to provide a method for manufacturing a non-oriented electrical steel sheet free from normalization and intermediate annealing. And the characteristics of low iron loss, its iron loss P 10/50 ⁇ 3.2W/kg, magnetic induction B 50 ⁇ 1.72T.
  • the present invention proposes a method for manufacturing the above-mentioned non-oriented electrical steel sheet, comprising the steps of:
  • Hot rolling including the steps of rough rolling, finishing rolling, coiling and heat preservation; wherein the temperature of the intermediate billet after rough rolling and before finishing rolling is controlled to be ⁇ 950°C;
  • the specific process flow of smelting and continuous casting may include: blast furnace molten iron ⁇ molten iron pretreatment ⁇ converter smelting ⁇ RH refining (liquid steel vacuum cycle degassing method) ⁇ continuous casting.
  • blast furnace molten iron after the blast furnace molten iron has undergone the "three de-sulfurization" (desulfurization, desiliconization, and dephosphorization) pretreatment steps of molten iron, it can be mixed with an appropriate amount of scrap steel into the furnace in proportion, and then smelted in a top-bottom re-blowing converter, and then refined in RH.
  • the steps of deep decarburization, deoxidation and alloying are carried out in sequence to adjust the chemical composition of the molten steel.
  • the molten steel after RH refining is transported for continuous casting.
  • the technical solution provided by the present application not only obtains the ratio of equiaxed crystal rate and columnar crystal rate equivalent to that of electromagnetic stirring without using electromagnetic stirring, but also effectively solves the problem of the surface of the finished steel plate that does not use electromagnetic stirring in the prior art.
  • the problem of corrugated defects also reduces equipment investment and production costs, so that the average manufacturing cost per ton of steel can be saved from tens to hundreds of yuan.
  • step (1) of the present invention based on the control of harmful inclusions in the steel and the improvement of electromagnetic properties, calcium treatment is performed by adding Ca alloy in the RH refining process, and the content of Ca element in the steel is controlled. .
  • Appropriate calcium treatment effect can effectively inhibit the formation of fine sulfide inclusions in the steel, improve the composition and distribution of large-particle oxide inclusions in the steel, and then ensure the smoothness and stability of the continuous casting process. Excellent performance.
  • the research shows that the root cause of the abnormality such as liquid level fluctuation and nozzle blockage in the continuous casting step is that there are a certain number of large-particle oxide inclusions in the molten steel, and the chain-like and dendrite-like Al 2 O Type 3 inclusions are predominant.
  • oxide inclusions are dense and hard, with high melting point and high viscosity.
  • it is more and more difficult to float and remove, but to suspend.
  • oxide inclusions stay in the molten steel, during the casting process of molten steel, these oxide inclusions will collide with the wall of the immersed nozzle, resulting in the gradual reduction of the inner diameter of the nozzle wall, which in turn causes the liquid level fluctuation during the molten steel casting, or the steel Unsmooth liquid casting, in severe cases, will lead to surface quality defects of steel and interruption of continuous casting and casting production.
  • the conversion coefficient of S element is defined as 1/2.
  • R value of the index is lower than 0.11, it means that the amount of Ca added in the steel is insufficient.
  • Ca cannot compound the chain-like and dendrite-like Al 2 O 3 , SiO 2 , and MgO. Oxidized inclusions are effectively denatured to reduce their size and reduce their melting point; when the index R value is higher than 0.71, it indicates that the amount of Ca added in the steel is too high.
  • the oxide inclusion index R can be preferably controlled to satisfy 0.11 ⁇ R ⁇ 0.71.
  • step (2) of the present invention after the continuous casting slab obtained in the step (1) is heated in a heating furnace and enters the hot rolling step, rough rolling is first required.
  • the coarse and developed columnar crystals can be broken and fine equiaxed crystals can be formed by appropriately reducing the rolling passes and increasing the reduction ratio of the rough rolling passes.
  • 6 or more passes are used in the rolling process, while 2 to 4 passes can be used in the present application.
  • the reduction ratio between passes needs to be increased accordingly.
  • the above rolling process can also reduce the temperature drop of the continuous casting billet from the heating furnace to the finishing rolling step, so as to ensure the highest possible finishing rolling inlet temperature under the same continuous casting billet exit temperature condition.
  • it is required to ensure that the temperature of the intermediate slab after rough rolling and before finishing rolling is controlled to be ⁇ 950°C, for example, 950 to 1020°C.
  • the temperature of the intermediate slab after rough rolling and before finishing rolling can also be controlled to be ⁇ 980°C.
  • the phase transformation of austenite to ferrite in the hot-rolled steel sheet will be advanced to the front stand with a large reduction ratio, and further. It promotes the crushing of columnar crystals, and improves the grain uniformity in the microstructure of the hot-rolled steel sheet under subsequent high temperature conditions, so that the shingle-shaped defects of the finished steel sheet can be eliminated.
  • a heat preservation device for heat preservation and protection.
  • the use of the heat of the hot-rolled steel coil and the time-to-temperature method can still promote the formation of grains with a size of 10-80 ⁇ m in the hot-rolled steel sheet.
  • a recrystallized microstructure and average grain size comparable to normalization or bell furnace intermediate annealing can be obtained.
  • the heat preservation time of the hot-rolled steel coil in the heat preservation step can be preferably controlled to be 1 h to 120 h.
  • the holding time of the hot-rolled steel coil can also be controlled to be 1 h to 48 h.
  • a protective atmosphere such as a 100% pure nitrogen atmosphere, is required for heat preservation.
  • the hot-rolled steel coil after the heat preservation step does not need to be normalized or annealed in a bell furnace, and can be directly subjected to pickling, cold rolling and continuous annealing.
  • step (2) the temperature of the intermediate slab after rough rolling and before finishing rolling is ⁇ 980°C.
  • step (2) in the heat preservation step, the heat preservation time of the hot-rolled steel coil is 1 h to 120 h, and the protective atmosphere is a pure nitrogen atmosphere.
  • the holding time of the hot-rolled steel coil in step (2) is 1 h to 48 h.
  • the non-oriented electrical steel sheet without normalization intermediate annealing and the manufacturing method thereof of the present invention have the following advantages and beneficial effects:
  • the manufacturing method of the non-oriented electrical steel sheet without normalization intermediate annealing provides a new chemical composition design system and corresponding control requirements for harmful impurities, reduces the number of hot rolling rough rolling passes and improves rough rolling.
  • the pass reduction rate is used to increase the temperature of the intermediate billet after rough rolling and before finishing rolling, and after the final rolling and coiling of hot rolling, the hot-rolled steel coil is heat-insulated in a protective atmosphere with a heat-preserving device to obtain a hot-rolled steel coil.
  • the invention can further reduce the burden of steel-making, hot-rolling and other production processes without using steel-making electromagnetic stirring and normalized intermediate annealing, reduce the difficulty of controlling harmful elements and inclusions in the steel-making process, and reduce the complexity of the hot-rolling process.
  • the difficulty of controlling the crystalline microstructure significantly improves the manufacturing cost of steel and reduces the production process flow.
  • the finished steel sheet produced by this manufacturing method has extremely high magnetic induction, extremely low iron loss, and has no corrugated shape on the surface of the steel sheet under the conditions of no electromagnetic stirring in steelmaking, no normalization intermediate annealing or no bell furnace annealing. defect.
  • the non-oriented electrical steel sheet without normalization intermediate annealing according to the present invention has low production cost, good surface quality, high magnetic induction and low iron loss, and its iron loss P 10/50 ⁇ 3.2W/kg, Magnetic induction B 50 ⁇ 1.72T, can be used to make small and medium motors, compressors, EI iron cores, large generators, new energy vehicle drive motors and other equipment, with very good promotion prospects and application value.
  • FIG. 1 schematically shows the relationship between the inclusion index R and the iron loss P 15/50 in the non-oriented electrical steel sheet according to the present invention.
  • Figure 2 schematically shows the relationship between the mass percentage of Nb+V+Ti and the magnetic induction B 50 of the non-oriented electrical steel sheet when the mass percentage of Si is 1.0%, 1.8%, and 2.6%, respectively.
  • FIG. 3 schematically shows the relationship between the addition amount of calcium alloy M Ca and the inclusion index R in the non-oriented electrical steel sheet according to the present invention.
  • FIG. 4 is a microstructure diagram of the non-oriented electrical steel sheet of Example 2.
  • FIG. 5 is a microstructure diagram of the comparative steel sheet of Comparative Example 3.
  • FIG. 5 is a microstructure diagram of the comparative steel sheet of Comparative Example 3.
  • Table 1-1 and Table 1-2 list the mass percentage of each chemical element in the non-oriented electrical steel sheets of Examples 1-10 and the comparative steels of Comparative Examples 1-3.
  • non-oriented electrical steel sheets of Examples 1-10 of the present invention and the comparative steels of Comparative Examples 1-3 are all prepared by the following steps:
  • the calcium content in the molten steel should be reasonably controlled; on the other hand, the index R of oxide inclusions in the molten steel should be controlled.
  • the molten steel after RH refining is transported for the continuous casting step, and a continuous casting slab with a thickness of 170-250 mm and a width of 800-1400 mm is obtained without using steel-making electromagnetic stirring.
  • Hot rolling including the steps of rough rolling, finishing rolling, coiling and heat preservation; adjusting the rough rolling passes and the reduction ratio between passes to control the temperature of the intermediate billet after rough rolling and before finishing rolling ⁇ 950°C , preferably, the temperature of the intermediate billet can be controlled to be ⁇ 980°C; then, after finishing rolling and coiling the intermediate billet, the hot-rolled steel coil is subjected to heat preservation treatment under a protective atmosphere with the help of a heat preservation device.
  • the heat preservation time of the hot-rolled steel coil can be controlled to be between 1h and 120h, preferably between 1h and 48h, and the protective atmosphere is a pure nitrogen atmosphere.
  • Table 2 lists the specific process parameters of the manufacturing methods of the non-oriented electrical steel sheets of Examples 1-10 and the comparative steels of Comparative Examples 1-3.
  • the " ⁇ " in the “Electromagnetic Stirring” column means that the electromagnetic stirring process is used in the manufacturing process, and “ ⁇ ” means that the electromagnetic stirring process is not used in the manufacturing process;
  • "normalized intermediate annealing or bell furnace intermediate annealing” indicates that the normalized intermediate annealing or bell furnace intermediate annealing treatment process is used in the manufacturing process, and " ⁇ ” indicates that the normalized intermediate annealing or bell furnace intermediate annealing treatment process is not used in the manufacturing process.
  • the present invention has carried out detection and analysis on the continuous casting slabs of the Examples and Comparative Examples obtained after the smelting and continuous casting operations of step (1), and the final step (4). ) after the continuous annealing of each embodiment and the finished steel sheet of the comparative example were also observed and tested, and the relevant observation and testing results are listed in Table 3 below.
  • the three indexes in Table 3 are equivalent to the equiaxed crystallinity rate of continuous casting slabs that can be achieved by electromagnetic stirring of 30 to 100%, the recrystallization rate of 100%, and the average grain size of 50 to 75 ⁇ m.
  • Iron loss performance test Based on the national standard GB/T 3655-2008, the iron loss performance test is carried out by the Epstein square ring method. The test temperature is 20 °C constant temperature test, the sample size is 30mm ⁇ 300mm, and the target mass is 0.5kg. The test parameter was P 15/50 .
  • Magnetic induction performance test Based on the national standard GB/T 3655-2008, the iron loss performance test is carried out by the Epstein square ring method.
  • the test temperature is 20 °C constant temperature test, the sample size is 30mm ⁇ 300mm, and the target mass is 0.5kg.
  • the test parameter is B50 .
  • Table 4 lists the observations and related performance test results of the non-oriented electrical steel sheets of Examples 1-10 and the comparative steels of Comparative Examples 1-3.
  • Comparative Example 2 and Comparative Example 3 there is also a chemical composition design system that does not meet the design requirements of the present invention, or other key parameters related to the design control requirements of the present invention do not meet the control requirements, which eventually leads to the electromagnetic properties of the finished steel sheet. Do not match, or there are corrugated defects on the surface.
  • FIG. 1 schematically shows the relationship between the inclusion index R and the iron loss P 15/50 in the non-oriented electrical steel sheet according to the present invention.
  • the iron loss P 15/50 decreases rapidly, and when the R value is greater than or equal to 0.11, the iron loss P 15/50 can reach 3.2W/kg or less. Then, as the R value continues to increase, before reaching 0.71, the iron loss P 15/50 is basically stable and controllable, and after the R value is higher than 0.71, the iron loss P 15/50 will exceed 3.2W/ kg, and began to deteriorate substantially and continuously.
  • Figure 2 schematically shows the mass percentage of Nb+V+Ti and the magnetic induction B when the mass percentage of Si in the non-oriented electrical steel sheet according to the present invention is 1.0%, 1.8%, and 2.6%, respectively. 50 relationship.
  • the sum of the chemical element mass percentages of Nb, V and Ti in the steel, Nb+V+Ti, and the magnetic induction of the steel sheet are basically in a linear relationship.
  • the magnetic induction line of the steel plate on the ordinate decreases, and the sum of the chemical elements of Nb, V and Ti in the steel reaches 0.0025%.
  • the magnetic induction of the steel plate will be lower than 1.73T, or even lower.
  • FIG. 3 schematically shows the relationship between the addition amount of calcium alloy M Ca and the inclusion index R in the non-oriented electrical steel sheet according to the present invention.
  • the value of the inclusion index R increases correspondingly.
  • a reasonable matching relationship needs to be maintained between the two to meet the needs of continuous casting castability.
  • the addition amount of calcium iron alloy M Ca is low, the R value will be lower than 0.11; on the contrary, when the addition amount of calcium iron alloy M Ca is high, the R value will be higher than 0.71. In both cases, it is not conducive to maintaining the stability of continuous casting, which will cause abnormal conditions such as blockage of the continuous casting nozzle and fluctuation of the molten steel level.
  • FIG. 4 is a microstructure diagram of the non-oriented electrical steel sheet of Example 2.
  • the microstructure of the non-oriented electrical steel sheet of Example 2 of the present invention has been completely recrystallized, and the recrystallized grains are all equiaxed grains, and the grain size is equiaxed. Coarse and even.
  • FIG. 5 is a microstructure diagram of the comparative steel sheet of Comparative Example 3.
  • FIG. 5 is a microstructure diagram of the comparative steel sheet of Comparative Example 3.
  • the microstructure of the comparative steel of Comparative Example 3 has not been completely recrystallized, and there are many fibrous incompletely recrystallized structures in the middle, and the recrystallized microstructure has been achieved. Grain equiaxed grain ratio is low, and the grain size is not uniform.

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Abstract

本发明公开了一种无取向电工钢板，其各化学元素质量百分含量为：0＜C≤0.004％、Si：1.0～2.6％、Mn：0.2～1.0％、Al：0.2～1.6％、Ca：0.0003％～0.0035％，余量为Fe和其他不可避免的杂质。此外本发明还公开了上述无取向电工钢板的制造方法，其包括步骤：(1)冶炼和连铸，在该步骤不采用电磁搅拌；(2)热轧，其包括：粗轧、精轧、卷取和保温；控制粗轧之后、精轧之前的中间坯温度≥950℃；(3)冷轧，上述热轧步骤后不进行常化中间退火或罩式炉中间退火而直接进行冷轧；(4)连续退火。本发明所述的无取向电工钢板通过采用合理的化学成分和工艺设计，可以在保证较低生产成本的同时，获得高磁感和低铁损的特性。

Description

一种无取向电工钢板及其制造方法 技术领域
本发明涉及一种钢板及其制造方法，尤其涉及一种无取向电工钢板及其制造方法。
背景技术
在现有的工业生产中，无取向电工钢的用途很广，其可以用于制作中小型电机、压缩机、EI铁芯、大型发电机、新能源汽车驱动电机等设备。相应地，根据应用环境的不同，各设备对于无取向电工钢的电磁性能要求也不相同，但通常均希望无取向电工钢的磁感越高越好、铁损越低越好。
通常情况下，无取向电工钢的牌号越低，意味着磁感就越高、铁损也越高；无取向电工钢的牌号越高，则意味着磁感越低、铁损也越低。为了使无取向电工钢同时获得高磁感、低铁损的性能，现有技术中往往通过采用向钢中加入大量的Si、Al、借助炼钢电磁搅拌提高连铸坯中的等轴晶率、并在热轧之后采用常化中间退火方式，以改善热轧钢卷的再结晶显微组织。采用这种改进工艺最终所获得的成品钢板的表面没有瓦棱状缺陷，且具有较高的磁感和较低的铁损。
然而，现有技术中采用的这种电磁搅拌技术和常化中间退火处理，势必会造成钢的制造成本大大增加，这对于部分无取向电工钢板而言，会大大降低产品的性价比。因此，为了进一步地降低生产成本，开发一种免常化中间退火的无取向电工钢板及其制造方法就很有现实意义。
例如：公开号为CN103305748A，公开日为2013年9月18日，名称为“一种无取向电工钢板及其制造方法”的中国专利文献，公开了一种不需要常化中间退火的，高磁感、低铁损无取向电工钢板制造方法。其特征在于1)C：0.008％以下、Si：0.1％～2.0％、Al：0.1％～1.0％、Mn：0.1％～1.0％、P：0.2％以下、S：0.005％以下、N：0.005％以下、Ti：0.008％以下；2)生产工序依次为炼钢、热轧、酸洗、冷轧、退火工序，其热轧过程不包括常化处理工序；3)热轧工序的终轧温度FDT满足如下关系：830+42(Si+Al)≤FDT≤880+23 (Si+Al)；4)在所述热轧工序中，在对中间坯粗轧后到对其在F1机架精轧前的时间间隔t1控制在20s或以上，并且在对中间坯精轧后到对其进行层流冷却前的时间间隔t2控制在5s或以上。
又例如：公开号为特開2007-154271，公开日2007年6月21日，名称为“无取向电工钢板的制造方法”的日本专利文献，公开了一种免常化中间退火处理、电磁性能优良的无取向电工钢板的制造方法。其特征在于1)C：0.008％以下、Si：1.5％～3.5％、Al：0.2％～3.0％、Si+Al：1.9％以上、Mn：0.02％～1.0％、S：0.0015％以下、N：0.0020％以下、Ti：0.008％以下；2)热轧连铸坯加热温度为1050℃～1150℃，粗轧、精轧之间中间坯温度为1050～1150℃，精轧前端温度为1050℃～1150℃，精轧末端温度为1000℃；3)精轧之后的1～7s不投入除磷水，然后，再投入除磷水直至钢卷冷却至700℃以下进行卷取。该方法借助热轧粗轧、精轧之间，投入感应加热装置以解决温度控制问题，同时，对钢中的有害元素S、N、Ti等含量加以严格限制，从而改善了在不采用热轧常化退火处理条件下的钢板电磁性能。
再例如：公开号为特開2006-291346，公开日为2006年10月26日，名称为“磁感应强度高的无取向性电工钢板制造方法”的日本专利文献，公开了一种高磁感无取向电工钢板的制造方法。其特征在于1)C：0.004％以下、Si：1.5％～3.5％、Al：0.2％～3.0％、Si+Al：1.9％以上、Mn：0.02％～1.0％、S：0.0030％以下、N：0.0030％以下，Sn+Sb：0.02％～0.4％，Ca+Mg+REM：0.0005％～0.020％；2)热轧之后常化退火，钢板平均晶粒尺寸在300μm以上；3)冷轧时，采用温轧模式，钢板温度限制在180℃～350℃之间，并且轧制时，M值在0.1～5之间，冷轧压下率为85％～93％。
发明内容
本发明的目的之一在于提供一种免常化中间退火的无取向电工钢板，该无取向电工钢板通过优化钢材的化学成分，并配合改进后的制造工艺，可以在保证较低生产成本的同时，改善钢板的质量，该无取向电工钢板具有高磁感和低铁损的特性，其铁损P 10/50≤3.2W/kg，例如在2.7W/kg～3.2W/kg之间，且磁感B 50≥1.72T，例如在1.72T～1.74T之间，具有十分良好的推广前景和应用价值。
为了实现上述目的，本发明提供了一种免常化中间退火的无取向电工钢板， 其各化学元素质量百分含量为：
0＜C≤0.004％、Si：1.0～2.6％、Mn：0.2～1.0％、Al：0.2～1.6％、Ca：0.0003％～0.0035％，余量为Fe和其他不可避免的杂质。本申请中各组分如无相反说明，均应理解为包含端点值。
在本发明所述的免常化中间退火的无取向电工钢板中，各化学元素的设计原理如下所述：
C：在本发明所述的无取向电工钢板中，当钢中C元素含量高于0.004％时，则容易与Nb、V、Ti等有害元素结合，从而形成大量有害的微细夹杂物，引起成品钢板的磁时效大幅增加。基于此，在本发明所述的无取向电工钢板中，控制C元素的质量百分含量为0＜C≤0.004％。
Si：在本发明所述的无取向电工钢板中，Si元素同样会影响成品钢板的机械性能，其可以有效降低铁损并提高钢板机械强度。为了保证Si元素能有效起到作用，钢中需要添加1.0％以上的Si。当然，钢中Si元素含量同样也不宜过高，当钢中Si元素含量高于2.6％时，则会显著劣化成品钢板的磁感，降低冷轧可轧性。基于此，在本发明所述的无取向电工钢板中，控制Si元素的质量百分含量在1.0～2.6％之间。
Mn：在本发明所述的无取向电工钢板中，Mn元素可以有效控制钢中硫化物夹杂物的含量。为了保证Mn元素能有效起到作用，钢中需要添加0.2％以上的Mn。此外，钢中Mn元素含量同样也不宜过高，当钢中Mn元素含量高于1.0％时，会大幅劣化成品钢板的磁感。基于此，在本发明所述的无取向电工钢板中控制Mn元素的质量百分含量在0.2～1.0％之间。
Al：在本发明所述的无取向电工钢板中，Al元素可以起到改善成品钢板铁损性能的作用，为了保证Al元素能有效起到作用，钢中需要加入0.2％以上的Al。当然，钢中Al元素含量同样也不宜过高，当钢中Al元素含量高于1.6％时，则会显著降低成品钢板的磁感。基于此，在本发明所述的无取向电工钢板中控制Al元素的质量百分比含量在0.2～1.6％之间。
Ca：在本发明所述的无取向电工钢板中，Ca元素可以起到良好的氧化类夹杂物控制效果，为了保证Ca元素的作用效果，钢中需要加入0.0003％以上的Ca，0.0003％及以上的Ca含量，已经可以有效的抑制钢中的MnS、Cu xS等微细的硫化类夹杂物生成，同时，0.0003％的Ca含量也不会显著增加钢的制 造成本。当然，钢中Ca元素含量同样也不宜过高，当钢中Ca元素含量高于0.0035％时，不仅会大大增加制造成本，还会大幅延长在钢材冶炼过程中的RH精炼作业时间，造成冶炼过程不稳定，工艺参数异常波动，甚至导致生产延迟或者停止等问题。此外，随着Ca含量的逐渐增加，钢的晶粒尺寸呈倒抛物线形式变化，不利于钢的电磁性能改善，阻碍晶粒长大，恶化钢材的磁性。基于此，在本发明所述的无取向电工钢板中，控制Ca元素的质量百分含量在0.0003％～0.0035％之间。
进一步地，在本发明所述的无取向电工钢板中，各化学元素质量百分含量还满足下述各项的至少其中之一：
Si+Al：1.4～3.2％；
Si 2/Mn：0.017～0.17％。
在本发明所述的无取向电工钢板中，在控制单一化学元素含量的同时，还可以控制Si、Al和Mn元素满足Si+Al：1.4～3.2％和/或Si 2/Mn：0.017～0.17％。其中，式中Si、Al和Mn均分别表示其各自对应元素的化学元素质量百分含量。
需要说明的是，在本发明所述的无取向电工钢板中，优选地控制Si元素和Al元素满足Si+Al：1.4～3.2％，是因为：当Si+Al含量低于1.4％时，即使在炼钢冶炼过程中不采用炼钢电磁搅拌，钢液在凝固过程中，枝晶生长的前端为自由晶，由于充分自然对流的缘故，这些结晶在凝固末梢能够有效生长，自由晶的迅速长大、增加，会在凝固前沿阻止柱状晶的生成。因而在该条件下的连铸坯低倍试样中，基本上以细小的等轴晶为主，不会形成粗大、发达的柱状晶，成品钢板表面也就不会出现瓦棱状缺陷。但是，随着Si+Al含量逐渐升高，在没有炼钢电磁搅拌的前提下，凝固末梢钢液对流不充分，自由晶的长大速度缓慢，增加的数量也很少，因此在该条件下的连铸坯低倍试样中，基本上以粗大、发达的柱状晶为主，细小的等轴晶很少。如果这部分柱状晶在热轧过程中不能通过轧制有效破碎的话，由于遗传效应，成品钢板上会生成瓦棱状缺陷。当Si+Al含量高于3.2％时，即使采用炼钢电磁搅拌，也无法有效获得合适的等轴晶比例，需要采用常化或者罩式炉中间退火的方式，促进热轧钢板晶粒尺寸之间的均匀性，以改善成品钢板表面的瓦楞状缺陷。因此，考虑到Si+Al含量对钢材性能的影响，在本发明所述的无取向电工钢板中，在控制单一化学元素质量百分含量的同时，还可以优选地控制Si+Al：1.4～3.2％。需 要说明的是，本申请在连铸过程不采用任何形式的搅拌，虽然目前钢液搅拌方式只有电磁搅拌一种，但不应理解为将未来可能产生的其他搅拌方式排除在外。
相应地，在本发明所述的无取向电工钢板中，还可以控制Si元素和Mn元素满足Si 2/Mn：0.017～0.17％。限制Si 2/Mn含量之比的目的是，Si元素是铁素体形成元素，对连铸坯中柱状晶的生长有良好的促进作用，而Mn元素则是奥氏体形成元素，能够扩大奥氏体相区，进而，通过控制显微组织在奥氏体与铁素体之间的转变，以减少连铸坯中的柱状晶比例(例如将柱状晶比例控制在0～70％之间)，从而起到改善成品钢板瓦棱状缺陷的效果。研究表明，调整钢中Si、Mn的含量，并将其控制在合适范围，能够在一定程度上改善成品钢板的瓦棱状缺陷。当Si 2/Mn含量之比大于0.17％时，在不采用炼钢电磁搅拌和不采用热轧常化中间退火或罩式炉中间退火的条件下，成品钢板上会出现明显的瓦棱状缺陷；而当Si 2/Mn含量之比小于0.017％时，在本发明设计要求Si元素含量大于1.0％的条件下，钢中Mn元素含量太高，会大幅改变成品钢板的机械性能，劣化成品钢板的磁感，并导致钢的制造成本大大增加。因此，在本发明所述的无取向电工钢板中，在控制单一化学元素质量百分含量的同时，还可以优选地控制Si 2/Mn：0.017～0.17％。
进一步地，在本发明所述的无取向电工钢板中，在其他不可避免的杂质中：S≤0.0040％、O≤0.003％、N≤0.003％，P≤0.2％、Nb≤0.001％、V≤0.001％、Ti≤0.001％。
在上述技术方案中，S、O、N、P、Nb、V和Ti均是本发明所述的无取向电工钢板中不可避免的杂质元素，在技术条件允许情况下，为了获得性能更好且质量更优的钢材，应尽可能降低无取向电工钢板中杂质元素的含量。
S：在本发明所述的无取向电工钢板中，S是杂质元素，钢中S元素含量不宜过高，当钢中S元素含量高于0.004％时，会导致钢中的硫化物数量快速增多且尺寸细小，从而恶化成品钢板的电磁性能。因此，在本发明所述的无取向电工钢板中，有必要严格控制S的质量百分比为S≤0.0040％。
O：在本发明所述的无取向电工钢板中，钢中O元素含量同样不宜过高，当钢中O元素含量高于0.003％时，会使氧的Al、Si、Ca等有害夹杂物大大增加，强烈阻碍成品钢板的晶粒长大，恶化成品钢板的电磁性能。基于此，在本发明所述的无取向电工钢板中，控制O元素的质量百分比为O≤0.003％。
N：在本发明所述的无取向电工钢板中，N是杂质元素，钢中N元素含量不宜过高，当钢中N元素含量超过0.003％时，会使N的Nb、V、Ti、Al夹杂物显著增加，从而导致夹杂物数量大大增加，强烈阻碍成品钢板的晶粒长大，恶化成品钢板的电磁性能。基于此，在本发明所述的无取向电工钢板中，控制N元素的质量百分含量为N≤0.003％。
P：在本发明所述的无取向电工钢板中，钢中P元素含量不宜过高，当钢中P元素含量超过0.2％时，会显著降低冷轧轧制过程稳定性，导致冷轧钢板出现边裂、断带等异常情况。基于此，在本发明所述的无取向电工钢板中，控制P元素的质量百分含量为P≤0.2％。
Nb：在本发明所述的无取向电工钢板中，钢中Nb元素含量不宜过高，当钢中Nb元素的含量超过0.001％时，会使Nb的C、N等有害析出物大大增加，阻碍晶粒长大，恶化钢的磁性。基于此，在本发明所述的无取向电工钢板中，控制Nb元素的质量百分含量为Nb≤0.001％。
V：在本发明所述的无取向电工钢板中，钢中V元素含量不宜过高，当钢中V元素的含量超过0.001％时，会使V的C、N等有害析出物大大增加，阻碍晶粒长大，恶化钢的磁性。基于此，在本发明所述的无取向电工钢板，控制V元素的质量百分含量为V≤0.001％。
Ti：在本发明所述的无取向电工钢板中，钢中Ti元素含量不宜过高，当钢中Ti元素的含量超过0.001％时，会使Ti的C、N等有害析出物大大增加，阻碍晶粒长大，恶化钢的磁性。基于此，在本发明所述的无取向电工钢板，控制Ti元素的质量百分含量为Ti≤0.001％。
进一步地，在本发明所述的无取向电工钢板中，还满足：Nb+V+Ti≤0.0025％。其中，式中的Nb、V和Ti均代入各元素对应的质量百分含量。
在上述技术方案中，在其他不可避免的杂质中，可以控制Nb、V和Ti元素满足Nb+V+Ti≤0.0025％。这是因为：Nb、V和Ti元素均是强烈的C、O、N化物形成元素，其会与C、O、N元素结合，生成尺寸细小、数量众多的有害夹杂物。因此，从生产控制的便利性角度出发，在本发明中希望Nb、V和Ti元素总量越低越好，并优选控制Nb+V+Ti≤0.0025％。
进一步地，在本发明所述的无取向电工钢板中，夹杂物指数R满足0.11≤R≤0.71，其中R＝Ca/(O+1/2S)。式中，Ca、O和S均分别代入各元素 对应的化学元素的质量百分含量。
进一步地，在本发明所述的无取向电工钢板中，Ca的含量为0.0005％～0.0025％。
进一步地，在本发明所述的无取向电工钢板中，其表面无瓦楞状缺陷。
本发明所述的无取向电工钢板没有瓦棱状缺陷，也没有内、外氧化层缺陷，质量十分优异。
进一步地，本发明所述的无取向电工钢板的铁损P 10/50≤3.2W/kg，磁感B 50≥1.72T。
相应地，本发明的另一目的在于提供一种免常化中间退火的无取向电工钢板的制造方法，该制造方法生产工艺简便，采用该制造方法制得的无取向电工钢板，具有高磁感和低铁损的特性，其铁损P 10/50≤3.2W/kg，磁感B 50≥1.72T。
为了实现上述目的，本发明提出了上述的无取向电工钢板的制造方法，包括步骤：
(1)冶炼和连铸，其中在该步骤不采用电磁搅拌；
(2)热轧，包括：粗轧、精轧、卷取和保温的步骤；其中控制粗轧之后、精轧之前的中间坯温度≥950℃；
(3)冷轧，上述热轧步骤后不进行常化中间退火或罩式炉中间退火而直接进行冷轧；
(4)连续退火。
在本发明上述的制造方法中，在步骤(1)中，冶炼和连铸的具体工艺流程可以包括：高炉铁水→铁水预处理→转炉冶炼→RH精炼(钢液真空循环脱气法)→连续浇铸。在上述步骤中，高炉铁水经过铁水预处理步骤“三脱”之后(脱硫、脱硅、脱磷)，可以与适量废钢按照比例搭配入炉，然后经顶底复吹转炉冶炼之后，在RH精炼过程中依序进行深脱碳、脱氧、合金化的步骤以调整钢液化学成分，最后，将RH精炼之后的钢液转运以进行连续浇铸，在不采用炼钢电磁搅拌的条件下，可以得到厚度为170～250mm、宽度为800～1400mm的连铸坯。本申请提供的技术方案在不采用电磁搅拌的前提下，不仅获得了与采用电磁搅拌相当的等轴晶率、柱状晶率比例，有效的解决了现有技术中不采用电磁搅拌的成品钢板表面瓦棱状缺陷问题，还降低了设备投资和生产成本，使平均每吨钢制造成本可节约数十元至数百元。
在本发明所述的步骤(1)中，基于钢中有害夹杂物的控制和电磁性能的改善需求，在RH精炼过程中采用加入Ca合金的方式进行钙处理，并控制钢中Ca元素的含量。合适的钙处理效果可以有效地抑制钢中微细的硫化类夹杂物生成，改善钢中大颗粒的氧化类夹杂物的组成和分布，进而可以确保连铸浇铸步骤的顺畅、稳定，得到的钢板电磁性能优良。
研究表明，导致连铸浇铸步骤出现液面波动、水口堵塞等异常的根本原因是，钢液中存在着一定数量的大颗粒氧化类夹杂物，且以呈链条状、枝晶状的Al 2O 3类夹杂物为主。这类氧化物夹杂物致密、坚硬，熔点高、粘度大，在钢液浇铸过程中，随着钢液温度的降低、钢液粘度的增大，越来越不容易上浮、去除，而是悬浮、停留在钢液中，在钢液浇铸过程中，这部分氧化类夹杂物会与浸入式水口壁相碰撞，从而导致水口壁内径逐渐缩小，进而造成钢液浇铸时的液面波动，或者钢液浇铸的不顺畅，严重时，会导致钢材表面质量缺陷，以及连铸浇铸生产中断等问题。为了确保连铸浇铸顺畅，就必须确保钙处理之后的钢液中有合适的氧化类夹杂物。如果氧化类夹杂物主要呈现为尺寸大、熔点高、形状不规则的Al 2O 3、SiO 2、MgO的链条状和枝晶状共存的形式，则危害极大。
除此之外，钙处理之后，还容易生成部分CaS类有棱角的、高熔点的硫化类夹杂物，它们可以单独存在，也可以和上述氧化类夹杂物共存，同样会造成连铸浇铸浸入式水口的堵塞。因此，为了钢液中的氧化类夹杂物控制效果，定义Ca元素的杂物指数为R＝Ca/(O+1/2S)，并优选控制指数R值满足0.11≤R≤0.71。
从实际控制效果出发，考虑到了Ca元素与S元素的相互作用，根据二者的结合效果，将S元素的折算系数定义为1/2。当指数R值低于0.11时，则说明钢中Ca元素的加入量不足，在弱钙处理条件下，Ca元素无法对这些呈链状、枝晶状的Al 2O 3、SiO 2、MgO复合氧化类夹杂物有效变性，达到减小其尺寸，降低其熔点的效果；当指数R值高于0.71时，说明钢中Ca元素的加入量太高，在强钙处理条件下，钢液中的氧化类夹杂物会以CaO·Al 2O 3和2CaO·Al 2O 3为主，加之过量的Ca元素会与S元素结合，生成为数众多的硫化类夹杂物CaS，同样也不能从根本上解决连铸浇铸步骤中浸入式水口的堵塞问题。因此，在本发明中，可以优选地控制氧化类夹杂物指数R满足0.11≤R≤0.71。
需要说明的是，在本发明所述的步骤(2)中，由步骤(1)制得的连铸坯经过加热炉加热进入热轧步骤之后，首先需要进行粗轧。其中，粗轧环节可以通过适当减少轧制道次，和提高粗轧道次压下率的方法，以破碎粗大、发达的柱状晶并形成细小的等轴晶。例如，一般来说轧制过程会采用6个或更多道次，而本申请可以采用2～4个道次，为轧制到相同的厚度，道次之间的压下率需相应提高。同时，上述轧制过程还能减小连铸坯从出加热炉到精轧步骤之前的温降，以确保在相同的连铸坯出炉温度条件下，获得尽可能高的精轧入口温度。在本发明的工艺条件下，要求确保控制粗轧之后、精轧之前的中间坯温度≥950℃，例如为950～1020℃。当然，在一些优选的实施方式中，为了获得更优的效果，也可以控制粗轧之后、精轧之前的中间坯温度≥980℃。
相应地，由于精轧入口温度提高的缘故，在随后的精轧轧制过程中，热轧钢板中奥氏体向铁素体的相变会提前到大压下率的前机架发生，进一步促进柱状晶的破碎，并在随后的高温条件下，改善热轧钢板显微组织中的晶粒均匀性，从而可以消除成品钢板的瓦棱状缺陷。此时，为了尽可能的改善成品钢板的电磁性能，热轧带钢完成精轧、卷取之后，需要采用保温装置对其进行保温、保护。
研究表明，利用热轧钢卷自身热量，采用时间换温度的方式(即温度低时延长保温时间；温度高时缩短保温时间)，仍然能够促进热轧钢板生成尺寸为10～80μm的晶粒，进而可以获得与经过常化或者罩式炉中间退火相媲美的再结晶显微组织和平均晶粒尺寸。考虑到保温时间的有效性，在本发明所述制造方法的步骤(2)中，可以优选地控制保温步骤中热轧钢卷的保温时间为1h～120h。当然在某些优选的实施方案中，为了进一步提高生产效率，也可以控制热轧钢卷的保温时间为1h～48h。为了避免由于高温和保温时间过常造成热轧钢卷表面产生内、外氧化层，进而劣化成品钢板表面状态、降低其电磁性能，保温时需要采用保护气氛，例如100％纯氮气氛。经过该保温步骤处理之后的热轧钢卷，无需再进行常化或者罩式炉中间退火处理，可以直接进行酸洗、冷轧和连续退火处理。最终获得了一种无瓦棱状缺陷的，电磁性能优良的无取向电工钢板，其铁损P 10/50≤3.2W/kg，且磁感B 50≥1.72T。也就是说，本申请在不进行常化或者罩式炉退火的前提下，达到与采用常化或罩式炉退火相当甚至更优的性能，一方面节省设备投资、降低生产成本，另一方面使生产效率明显 提高。
进一步地，在本发明所述的制造方法中，在步骤(2)中，粗轧之后、精轧之前的中间坯温度≥980℃。
进一步地，在本发明所述的制造方法中，在步骤(2)中，在保温步骤，热轧钢卷的保温时间为1h～120h，保护气氛为纯氮气氛。
进一步地，在本发明所述的制造方法中，在步骤(2)中热轧钢卷的保温时间为1h～48h。
本发明所述的免常化中间退火的无取向电工钢板及其制造方法相较于现有技术具有如下所述的优点以及有益效果：
本发明所述的免常化中间退火的无取向电工钢板的制造方法通过提供一种全新的化学成分设计体系，及其相应的有害杂质控制要求，通过减少热轧粗轧道次和提高粗轧道次压下率，以提高粗轧之后、精轧之前的中间坯温度，并在热轧终轧、卷取之后，采用保温装置对热轧钢卷在保护气氛下进行保温处理，以获得一种表面质量良好，电磁性能优良的无取向电工钢板。
该发明能够在不采用炼钢电磁搅拌和常化中间退火的条件下，进一步减轻炼钢、热轧等生产工序的负担，降低炼钢环节有害元素和夹杂物的控制难度，降低热轧环节再结晶显微组织的控制难度，明显改善钢的制造成本，减少生产工序流程。借助该制造方法生产的成品钢板，在没有炼钢电磁搅拌，免常化中间退火或免罩式炉退火的条件下，具有极高的磁感、极低的铁损，钢板表面没有瓦棱状缺陷。
本发明所述的免常化中间退火的无取向电工钢板的生产成本较低，表面质量良好，且具有高磁感和低铁损的特性，其铁损P 10/50≤3.2W/kg，磁感B 50≥1.72T，可以用于制作中小型电机、压缩机、EI铁芯、大型发电机、新能源汽车驱动电机等设备，具有十分良好的推广前景和应用价值。
附图说明
图1示意性地显示了本发明所述的无取向电工钢板中的夹杂物指数R与铁损P 15/50的关系。
图2示意性地显示了Si的质量百分含量分别为1.0％、1.8％、2.6％时，Nb+V+Ti的质量百分含量与无取向电工钢板的磁感B 50的关系。
图3示意性地显示了本发明所述的无取向电工钢板中的钙合金加入量M Ca与夹杂物指数R的关系。
图4为实施例2的无取向电工钢板的显微组织图。
图5为对比例3的对比钢板的显微组织图。
具体实施方式
下面将结合具体的实施例和说明书附图对本发明所述的无取向电工钢板及其制造方法做进一步的解释和说明，然而该解释和说明并不对本发明的技术方案构成不当限定。
实施例1-10和对比例1-3
表1-1和表1-2列出了实施例1-10的无取向电工钢板和对比例1-3的对比钢中各化学元素质量百分比。
表1-1.(质量百分含量，％，余量为Fe和除S、O、N、P、Nb、V和Ti以外的其他不可避免的杂质)
Figure PCTCN2022083918-appb-000001
表1-2.
Figure PCTCN2022083918-appb-000002
Figure PCTCN2022083918-appb-000003
注：Si+Al表示Si和Al元素的化学元素质量百分含量之和；Si 2/Mn中的Si和Mn分别代入Si元素和Mn元素的质量百分含量；Nb+V+Ti表示Nb、V和Ti元素的化学元素质量百分比之和；R＝Ca/(O+1/2S)，式中Ca、O和S分别表示各自化学元素的质量百分含量。
本发明所述实施例1-10的无取向电工钢板和对比例1-3的对比钢均采用以下步骤制得：
(1)按照表1-1和表1-2所列举的各化学成分配比冶炼并连铸：高炉铁水经过铁水预处理“三脱”之后，与适量废钢按照比例进行搭配入炉，经顶底复吹转炉冶炼，依次在RH精炼过程中进行深脱碳、脱氧、合金化以调整钢液化学成分：调整钢中的Si、Mn含量满足发明设计要求，限制钢液Nb、V、Ti等有害元素含量满足要求。在对钢液进行钙处理时，按照本发明经验公式加入 适量的钙合金，一方面要合理控制钢液中的钙含量；另一方面，要控制钢液中的氧化类夹杂物指数R。最后，将RH精炼之后的钢液转运以进行连续浇铸步骤，在不采用炼钢电磁搅拌的条件下，得到厚度为170～250mm、宽度为800～1400mm的连铸坯。
(2)热轧，包括：粗轧、精轧、卷取和保温的步骤；调整粗轧道次及道次间压下率，以控制粗轧之后、精轧之前的中间坯温度≥950℃，优选可以控制中间坯温度≥980℃；然后对中间坯进行精轧、卷取之后，借助保温装置对热轧钢卷在保护气氛下进行保温处理。其中，在保温步骤中，热轧钢卷的保温时间可以控制为1h～120h，优选地可以控制在在1h～48h之间，保护气氛为纯氮气氛。
(3)冷轧，在上述热轧步骤后不进行常化中间退火或罩式炉中间退火而直接进行冷轧，冷轧之前需要进行酸洗。
(4)连续退火。
需要注意的是，在本发明中，实施例1-10的无取向电工钢板的化学成分及其相关工艺参数均满足本发明设计规范控制要求。
而对比例1-3的对比钢的化学成分均存在未能满足本发明设计的要求的参数，其工艺步骤虽然采用上述工艺步骤，但是具体的工艺操作或工艺参数均存在不满足本发明设计规范要求的内容。
表2列出了实施例1-10的无取向电工钢板和对比例1-3的对比钢的制造方法的具体工艺参数。
表2.
Figure PCTCN2022083918-appb-000004
Figure PCTCN2022083918-appb-000005
注：上表中，“电磁搅拌”列中的“√”表示制造过程中采用了电磁搅拌工艺，“×”表示制造过程中未采用电磁搅拌工艺；“常化中间退火或罩式炉中间退火处理”列中的“√”表示制造过程中采用了常化中间退火或罩式炉中间退火处理工艺，“×”表示制造过程中未采用常化中间退火或罩式炉中间退火处理工艺。
需要注意的是，在进行上述工艺操作过程中，本发明针对步骤(1)的冶炼和连铸操作后得到的实施例和对比例的连铸坯进行了检测和分析，并对最终步骤(4)的连续退火后所得的各实施例和对比例的成品钢板同样也进行了观察和检测，相关观察和检测结果列于下述表3之中。表3中的3个指标与采用电磁搅拌能达到的连铸坯等轴晶率为30～100％、再结晶发生率为100％、平均晶粒尺寸为50～75μm是相当的。
表3.
Figure PCTCN2022083918-appb-000006
相应地，对最终得到的实施例1-10的无取向电工钢板和对比例1-3的对比钢进行取样，对各实施例和对比例钢板的样品进行观察，并进行相关各项性能进行测试，将观察及相关性能测试得到的结果列于表4中，相关性能的具体测试手段如下所述：
铁损性能测试：基于国家标准GB/T 3655-2008，采用爱波斯坦方圈法进 行铁损性能测试，测试温度为20℃恒温测试，试样尺寸为30mm×300mm，目标质量为0.5kg，测试参数为P 15/50。
磁感性能测试：基于国家标准GB/T 3655-2008，采用爱波斯坦方圈法进行铁损性能测试，测试温度为20℃恒温测试，试样尺寸为30mm×300mm，目标质量为0.5kg，测试参数为B 50。
表4列出了实施例1-10的无取向电工钢板和对比例1-3的对比钢的观察及相关性能测试结果。
表4.
Figure PCTCN2022083918-appb-000007
注：上表中，“瓦棱状缺陷”列中的“√”表示钢板存在瓦棱状缺陷，“×”表示钢板不存在瓦棱状缺陷。
结合表1、表2、表3和表4可以看出，在符合本发明设计要求的实施例1至实施例10中，各实施例的化学成分体系设计，Nb、V、Ti等有害元素的控制效果，以及钙处理工艺控制要求等，均满足本发明设计控制要求。并且，钢液在连续浇铸成连铸坯之后，在热轧步骤优化了粗轧道次数量、道次间压下率，以提高精轧入口的中间坯温度，并在热轧卷取之后对热轧钢卷进行保温、保护处理，最终，在没有炼钢电磁搅拌和热轧常化或者罩式炉中间退火的条件下，获得了表面状态良好的成品钢板。经检验，实施例1-10最终所得的成品钢板表面没有瓦棱状缺陷，成品钢板铁损P 10/50≤3.2W/kg，磁感B 50≥1.72T。
相比之下，在对比例1中，对比例1的对比钢材在化学成分设计过程中，Nb、V、Ti三者总量之和达到了0.0028％，也没有采用钙处理，因而导致钢中 的夹杂物指数R只有0.04，不满足发明提供的0.11的下限要求；在没有采用电磁搅拌的条件下，连铸坯中的等轴晶率为0；在没有采用常化中间退火的条件下，热轧钢板的再结晶发生率只有40％，平均晶粒尺寸也只有47μm，相应的，成品钢板表面存在严重的瓦棱状缺陷，对比例1成品钢板的铁损P 10/50为4.2W/kg、磁感B 50为1.67T，其钢板的质量和性能明显劣于实施例1-10的钢材。
相应地，在对比例2、对比例3中，同样存在化学成分设计体系不满足本发明设计要求，或者其它涉及本发明设计控制要求的关键参数不满足控制要求，最终导致了成品钢板的电磁性能不符，或者表面存在瓦棱状缺陷。
图1示意性地显示了本发明所述的无取向电工钢板中的夹杂物指数R与铁损P 15/50的关系。
如图1所示，在本发明所述的无取向电工钢板中，随着夹杂物指数R值的升高，铁损P 15/50快速降低，并在R值大于或等于0.11时，铁损P 15/50可以达到3.2W/kg或以下。然后，随着R值的继续升高，在达到0.71之前，铁损P 15/50基本保持稳定、可控，而在R值高于0.71之后，则铁损P 15/50会超出3.2W/kg，并开始大幅、持续劣化。
图2示意性地显示了本发明所述的无取向电工钢板中的Si的质量百分含量分别为1.0％、1.8％、2.6％时，Nb+V+Ti的质量百分含量与磁感B 50的关系。
如图2所示，在本发明所述的无取向电工钢板中，钢中Nb、V和Ti元素三者的化学元素质量百分比之和Nb+V+Ti与钢板的磁感基本呈线性变化关系。在图2中，随着横坐标Nb+V+Ti含量的增加，纵坐标上钢板的磁感直线降低，而在钢中Nb、V和Ti元素三者的化学元素质量百分比之和达到0.0025％或以上时，钢板的磁感会低于1.73T，甚至更低。
图3示意性地显示了本发明所述的无取向电工钢板中的钙合金加入量M Ca与夹杂物指数R的关系。
如图3所示，在本发明所述的无取向电工钢板中，随着钙铁合金加入量M Ca的增加，夹杂物指数R值相应的增加。两者之间需要保持合理的匹配关系，以满足连铸可浇性的需要。当钙铁合金加入量M Ca较低时，R值会低于0.11；反之，当钙铁合金加入量M Ca较高时，R值会高于0.71。两种情况下，都不利于保持连铸浇铸的稳定性，会造成连铸水口堵塞，钢液面产生波动等异常情况。
图4为实施例2的无取向电工钢板的显微组织图。
如图4所示，在该实施方式中，本发明所述的实施例2的无取向电工钢板的显微组织已经完全实现了再结晶，再结晶晶粒均为等轴晶，且晶粒尺寸粗大、均匀。
图5为对比例3的对比钢板的显微组织图。
如图5所示，就对比例3的对比钢材而言，对比例3对比钢材的显微组织尚未完全实现再结晶，中间存在较多的纤维状未完全再结晶组织，而已经实现再结晶的晶粒等轴晶比例低，且晶粒尺寸不均匀。
需要注意的是，本案中各技术特征的组合方式并不限本案权利要求中所记载的组合方式或是具体实施例所记载的组合方式，本案记载的所有技术特征可以以任何方式进行自由组合或结合，除非相互之间产生矛盾。
还需要注意的是，以上所列举的实施例仅为本发明的具体实施例。显然本发明不局限于以上实施例，随之做出的类似变化或变形是本领域技术人员能从本发明公开的内容直接得出或者很容易便联想到的，均应属于本发明的保护范围。

Claims (12)

  1. 一种无取向电工钢板，其特征在于，其各化学元素质量百分含量为：
    0＜C≤0.004％、Si：1.0～2.6％、Mn：0.2～1.0％、Al：0.2～1.6％、Ca：0.0003％～0.0035％，余量为Fe和其他不可避免的杂质。
  2. 如权利要求1所述的无取向电工钢板，其特征在于，各化学元素质量百分含量还满足下述各项的至少其中之一：
    Si+Al：1.4～3.2％；
    Si 2/Mn：0.017～0.17％。
  3. 如权利要求1所述的无取向电工钢板，其特征在于，所述其他不可避免的杂质满足S≤0.0040％、O≤0.003％、N≤0.003％，P≤0.2％、Nb≤0.001％、V≤0.001％、Ti≤0.001％。
  4. 如权利要求3所述的无取向电工钢板，其特征在于，化学元素质量百分含量还满足Nb+V+Ti≤0.0025％。
  5. 如权利要求3所述的无取向电工钢板，其特征在于，所述无取向电工钢板的夹杂物指数R满足0.11≤R≤0.71，其中R＝Ca/(O+1/2S)，Ca、O、S为相应元素在所述无取向电工钢板中的质量百分含量。
  6. 如权利要求1所述的无取向电工钢板，其特征在于，Ca的质量百分含量为0.0005％～0.0025％。
  7. 如权利要求1所述的无取向电工钢板，其特征在于，所述无取向电工钢板的表面无瓦楞状缺陷。
  8. 如权利要求1所述的无取向电工钢板，其特征在于，其铁损P 10/50≤3.2W/kg，磁感B 50≥1.72T。
  9. 一种如权利要求1～8中任意一项所述的无取向电工钢板的制造方法，其特征在于，包括步骤：
    (1)冶炼和连铸，在该步骤不采用电磁搅拌；
    (2)热轧，包括粗轧、精轧、卷取和保温的步骤；其中，控制粗轧之后、精轧之前的中间坯的温度≥950℃；
    (3)冷轧，在上述热轧步骤后不进行常化中间退火或罩式炉中间退火而直接进行冷轧；
    (4)连续退火。
  10. 如权利要求9所述的制造方法，其特征在于，在所述步骤(2)中，控制粗轧之后、精轧之前的中间坯的温度≥980℃。
  11. 如权利要求9所述的制造方法，其特征在于，在所述步骤(2)中，在所述保温步骤中，热轧钢卷的保温时间为1h～120h，并采用纯氮作为保护气氛。
  12. 如权利要求11所述的制造方法，其特征在于，所述保温时间为1h～48h。
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