WO2021238895A1 - 一种低成本极低铝的无取向电工钢板及其制造方法 - Google Patents

一种低成本极低铝的无取向电工钢板及其制造方法 Download PDF

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WO2021238895A1
WO2021238895A1 PCT/CN2021/095717 CN2021095717W WO2021238895A1 WO 2021238895 A1 WO2021238895 A1 WO 2021238895A1 CN 2021095717 W CN2021095717 W CN 2021095717W WO 2021238895 A1 WO2021238895 A1 WO 2021238895A1
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oriented electrical
electrical steel
steel sheet
manufacturing
rolling
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PCT/CN2021/095717
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English (en)
French (fr)
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张峰
沈侃毅
宗震宇
李国保
房现石
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宝山钢铁股份有限公司
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Priority to MX2022014497A priority Critical patent/MX2022014497A/es
Priority to EP21813476.5A priority patent/EP4137603A4/en
Priority to KR1020227040497A priority patent/KR20220162179A/ko
Priority to JP2022571881A priority patent/JP2023526128A/ja
Priority to US17/927,165 priority patent/US20230203613A1/en
Publication of WO2021238895A1 publication Critical patent/WO2021238895A1/zh

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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
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
    • C21D8/1222—Hot rolling
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    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0006—Adding metallic additives
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    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
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    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
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    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
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    • C21D6/00—Heat treatment of ferrous alloys
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    • 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
    • C21D8/1205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular fabrication or treatment of ingot or slab
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    • 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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    • 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
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1244—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest
    • C21D8/1272—Final recrystallisation annealing
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    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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    • 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
    • C22C33/06—Making ferrous alloys by melting using master alloys
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/16—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2201/00—Treatment for obtaining particular effects

Definitions

  • the invention relates to a steel plate and a manufacturing method thereof, in particular to a non-oriented electrical steel plate and a manufacturing method thereof.
  • Non-oriented electrical steel sheet has a non-unique grain direction inside, and is a functional material with excellent electromagnetic properties.
  • non-oriented electrical steel sheets have been continuously developing in two directions: one is high-efficiency, high-grade steel with high manufacturing costs and complex production processes, but excellent electromagnetic and mechanical properties; second, low manufacturing costs and production processes Simple, medium and low grade steel with excellent electromagnetic and mechanical properties.
  • the number of medium and low grade non-oriented electrical steel sheets accounted for 70% or more of all non-oriented electrical steel sheets. Therefore, it is of great practical significance to study how to produce low- and medium-grade non-oriented electrical steel plates more economically and conveniently, and to further improve its cost performance.
  • the low and medium grades of non-oriented electrical steel plates most of them are used in small and medium-sized motors, EI cores, small generators, etc. Therefore, the user market is constantly demanding to reduce the iron loss of the steel plate, and the magnetic induction of the steel plate The demand for increasing the power is more urgent, and the purpose is to more effectively reduce the copper loss of the iron core.
  • the publication number is CN101992210A
  • the publication date is March 30, 2011, and the Chinese patent document titled "A method for producing cold-rolled non-oriented silicon steel and aluminum-free steel grades” discloses a method for producing cold-rolled non-oriented silicon steel and non-aluminum steel.
  • the method of aluminum steel grades pointed out that by controlling the content of residual elements that are easy to form nitrides and Al ⁇ 0.0010%, hot rolling adopts low-temperature heating and temperature-controlled rolling, and cold-rolled products are once or twice cold-rolled with intermediate annealing.
  • the specific control method is to control the residual aluminum content brought in during the alloying process including deoxidized aluminum, auxiliary materials and refractory materials, control Al ⁇ 0.0010%, and use Si deoxidation in the refining deoxidation process; control the smelting nitrogen content and the easy formation of nitrides
  • hot rolling adopts low temperature heating and finishing rolling to implement temperature-controlled rolling, that is, rolling in the ferrite single-phase zone, and control the two-phase precipitation state;
  • the heating temperature of hot-rolled billets is 1000 ⁇ 1150°C, the opening temperature is ⁇ 950°C, the final rolling temperature is ⁇ 840°C, and the coiling temperature is ⁇ 690°C;
  • the cold rolling adopts primary or secondary cold rolling with intermediate annealing.
  • Non-oriented electrical steel sheet and manufacturing method thereof Its components are calculated by weight percentage: C: 0.03 ⁇ 0.15%, Si ⁇ 0.15%, Mn: 1.0-1.8%, P ⁇ 0.025%, S ⁇ 0.015%, Ti: 0.08 ⁇ 0.18%, Nb: 0.02 ⁇ 0.07 %, Al: 0.02 ⁇ 0.10%, N ⁇ 0.010%, the rest is iron and residual content.
  • the hot-rolling raw material composition design requires that the chemical composition of the cast slab meets the requirements, C ⁇ 0.005%, Si: 0.1 ⁇ 1.0%, Mn ⁇ 0.35%, P ⁇ 0.08%, S ⁇ 0.01%, N ⁇ 0.008%, O ⁇ 0.015%, the rest is Fe and unavoidable impurities; casting billet hot charging, hot rolling, critical deformation cold rolling, user stress relief annealing to obtain a semi-process non-oriented electrical steel with excellent magnetic properties.
  • the heating temperature of the cast slab is 900 ⁇ 1150°C
  • the final rolling temperature is required to be 10 ⁇ 50°C lower than the Ar3 transformation point
  • the thickness of the hot-rolled plate is 2.0 ⁇ 2.5mm
  • the intermediate annealing temperature is 600 ⁇ 850°C
  • the time is 1 ⁇ 2min
  • the intermediate annealing atmosphere is H 2 , N 2 mixed gas
  • the proportion of H 2 is 10-40%
  • no humidification and decarburization are required
  • the recrystallization rate after intermediate annealing is ⁇ 40%
  • the critical deformation cold rolling means that the steel strip after intermediate annealing is cold-rolled to 0.5mm with a critical deformation reduction rate of 0.5-15%, and the hardness of the steel plate after critical deformation cold rolling is 130-180HV;
  • User stress relief annealing refers to the user's stress relief annealing for cold-rolled and punched sheets after critical deformation and lamination at a temperature of 700 to 850°C for 1 to 2 hours.
  • the annealing atmosphere is required to be a mixture of H 2 and N 2 gas.
  • the proportion of H 2 is 10-40%, and the cooling method is slow cooling, requiring cooling to 450°C at a cooling rate of 10-100°C/h, and then cooling with the furnace to obtain the final desired product.
  • the cast slab does not contain Al, Sn, Sb, Cu, Cr, Ni, B, rare earth and other alloying elements, and the production cost is greatly reduced. Using a larger critical reduction, and optimizing the annealing process, the product produced has better magnetic properties.
  • One of the objectives of the present invention is to provide a low-cost and extremely low-aluminum non-oriented electrical steel sheet.
  • the non-oriented electrical steel sheet optimizes the chemical composition of the steel, with the help of the steel containing extremely low aluminum content, and the steel and slag containing an appropriate amount of oxidation. Due to its unique technical characteristics, the quality of special alloys for RH refining, deoxidation and alloying has been lowered to greatly reduce the cost of steel manufacturing and effectively control the cost of alloys.
  • the iron loss P 15/50 of the non-oriented electrical steel sheet is reduced by 0.2 to 0.8 W/kg on average, and the magnetic induction B 50 is increased by 0.01 to 0.04 T on average.
  • the iron loss of the non-oriented electrical steel sheet of the specific grade of the present invention is reduced by 0.2 to 0.8 W/kg on average, and the magnetic induction B 50 is increased by 0.01 to 0.04 T on average.
  • Excellent economy also has the characteristics of high magnetic induction and low iron loss.
  • the reference value of the above electromagnetic performance is an ordinary non-oriented electrical steel sheet in the current user market.
  • the iron loss P 15/50 is generally 5.5 ⁇ 6.5W/kg, and the magnetic induction B 50 is generally 1.74 ⁇ 1.76T; in the electromagnetic performance of the conventional B50A800 brand, the iron loss P 15/50 is generally 5.0 ⁇ 5.5W/kg, magnetic induction B 50 is generally 1.71 ⁇ 1.73T; in the electromagnetic performance of conventional B50A600 grades, iron loss P 15/50 is generally 3.9 ⁇ 4.5W/kg, magnetic induction B 50 is generally 1.68 ⁇ 1.71T .
  • the present invention provides a low-cost and extremely low-aluminum non-oriented electrical steel sheet, which contains the following chemical elements in the following mass percentages:
  • the mass percentage of each chemical element is:
  • C In the non-oriented electrical steel sheet according to the present invention, carbon is one of the strong aging forming elements. When the content of C element in the steel is higher than 0.003%, it is easy to combine with Nb, V, Ti, etc., forming a large number of fine inclusions, resulting in a significant increase in the loss of the finished steel sheet. Therefore, the mass percentage of C in the non-oriented electrical steel sheet of the present invention is controlled to be C ⁇ 0.003%. In the non-oriented electrical steel sheet of the present invention, the C element content is controlled as low as possible. Specifically, the mass percentage of C is controlled to be 0 ⁇ C ⁇ 0.003%.
  • the element Si can significantly increase the resistivity of the material.
  • the Si element content in the steel is less than 0.1%, the iron loss of the finished steel sheet cannot be effectively reduced; and if the Si element content in the steel is higher than 1.2%, the magnetic induction of the finished steel sheet will be significantly deteriorated. Therefore, the mass percentage of Si in the non-oriented electrical steel sheet of the present invention is controlled to be between 0.1% and 1.2%.
  • the Mn element can be combined with the S element to form MnS, thereby effectively improving the magnetic properties of the finished steel sheet.
  • the steel needs to add more than 0.1% Mn, but it should be noted that the Mn element content should not be too high. If the Mn element content in the steel is higher than 0.4%, it will significantly damage the finished steel plate. Recrystallization texture. Therefore, the mass percentage of Mn in the non-oriented electrical steel sheet of the present invention is controlled to be between 0.1% and 0.4%.
  • the element P can significantly increase the strength of the material.
  • the P element content in the steel is less than 0.01%, it cannot effectively improve the strength of the finished steel sheet. If the P element content in the steel is higher than 0.2%, it will significantly reduce the cold-rollability. Therefore, the mass percentage of P in the non-oriented electrical steel sheet of the present invention is controlled to be between 0.01% and 0.2%.
  • the S element content should not be too high.
  • the S element content in the steel is higher than 0.003%, it will significantly increase the number of inclusions such as MnS, Cu 2 S, and hinder the growth of grains. Great, deteriorating the magnetic properties of the finished steel sheet. Therefore, the mass percentage of S in the non-oriented electrical steel sheet of the present invention is controlled to be 0 ⁇ S ⁇ 0.003%.
  • the mass percentage of S in the non-oriented electrical steel sheet of the present invention is controlled to be 0 ⁇ S ⁇ 0.003%.
  • the content of Al element in the steel should not be too high.
  • the mass percentage of Al in the non-oriented electrical steel sheet of the present invention is controlled to be Al ⁇ 0.001%.
  • the mass percentage of Al is controlled to be 0 ⁇ Al ⁇ 0.001%.
  • the mass percentage of Al can be controlled to be Al ⁇ 0.0005%.
  • the mass percentage of O in the non-oriented electrical steel sheet of the present invention is controlled to be between 0.003% and 0.01%.
  • the mass percentage of O can be controlled between 0.045% and 0.007%.
  • the N element content in the steel should not be too high.
  • the N element content in the steel exceeds 0.003%, the Nb, V, Ti, and Al inclusions of N will increase significantly. It hinders the growth of crystal grains and degrades the magnetic properties of the finished steel sheet. Therefore, in the non-oriented electrical steel sheet of the present invention, the mass percentage of N is controlled to be N ⁇ 0.003%.
  • the mass percentage of N is controlled to be 0 ⁇ C ⁇ 0.003%.
  • Sn is a grain boundary segregation element.
  • the appropriate amount of beneficial element Sn added to the steel can play a role in improving the segregation of grain boundaries and improving the beneficial microstructure during the hot rolling process.
  • the mass percentage of Sn in the non-oriented electrical steel sheet of the present invention is controlled to be between 0.005% and 0.05%.
  • the mass percentage of Sn can be controlled between 0.005% and 0.02%.
  • the Si element and P element are also controlled to satisfy Si 2 /P: 0.89 to 26.04, where Si and P both represent corresponding The number before the percent sign of the element's mass percentage.
  • Si and P both represent corresponding The number before the percent sign of the element's mass percentage.
  • the properties of Si element and P element are similar, which can significantly increase the resistivity of the material and reduce the iron loss of the finished steel sheet, but at the same time it will degrade the magnetic induction of the finished steel sheet.
  • the P element has a very good and significant effect, but it will degrade the cold-rollability under conditions of high Si content. Therefore, the electromagnetic and mechanical properties of the finished steel sheet are comprehensively considered, and in the non-oriented electrical steel sheet of the present invention, the Si 2 /P is controlled to be between 0.89 and 26.04.
  • Si 2 /P in order to obtain a better implementation effect, Si 2 /P can be controlled between 0.89 and 16.67.
  • the inevitable impurities in the steel include Nb, V, Ti, Ca, Mg, and REM.
  • REM is a rare earth element, which can also be referred to as RE for short.
  • Al is less than or equal to 0.0005%.
  • Si 2 / P 0.89-16.67.
  • the iron loss P 15/50 is reduced by 0.2 to 0.8 W/kg on average, and the magnetic induction B 50 is increased by 0.01 to 0.04 on average.
  • the thickness thereof is 0.5 ⁇ 0.1 mm.
  • another object of the present invention is to provide a method for manufacturing a low-cost, very low-aluminum non-oriented electrical steel sheet.
  • the manufacturing method has simple production process and low manufacturing cost.
  • the non-oriented electrical steel sheet produced by the manufacturing method and Compared with conventional products of the same brand, the iron loss P 15/50 is reduced by 0.2 ⁇ 0.8W/kg on average, and the magnetic induction B 50 is increased by 0.01 ⁇ 0.04T on average. It has the characteristics of high magnetic induction and low iron loss.
  • the present invention proposes the above-mentioned manufacturing method of non-oriented electrical steel sheet, which includes the steps:
  • Hot rolling After coiling, the hot-rolled sheet is not subjected to normalization treatment or bell furnace annealing, but uses the residual heat of the hot-rolled steel coil for soaking and insulation;
  • the hot rolling process mainly includes: slab heating, rough rolling, finishing rolling and coiling processes.
  • the normalization treatment or bell furnace annealing refers to a process in which the hot-rolled coil is subjected to intermediate annealing after hot rolling and before cold rolling, with the purpose of improving the electromagnetic properties of the finished product.
  • the hot-rolled sheet is not subjected to normalization treatment or bell furnace annealing after coiling, but uses the residual heat of the hot-rolled steel coil for soaking and holding, which can effectively promote the trace amount
  • the element Sn is segregated to improve the recrystallization structure of the hot-rolled steel sheet and promote the growth of the grain size, which can replace or supplement the effect of normalized annealing or bell furnace annealing.
  • this operation can also effectively simplify the process, reduce production burden and manufacturing difficulty, and reduce production costs.
  • step (1) during the deoxidation and alloying of RH refining, ferrophosphorus, ferrosilicon, and ferromanganese are sequentially added.
  • step (1) during the deoxidation and alloying of the RH refining, ferrophosphorus, ferrosilicon, and ferromanganese are sequentially added. That is, at the end of RH refining, ferrophosphorus, ferrosilicon, and ferromanganese are added to the molten steel to remove free oxygen in the steel, and element components are added in accordance with the requirements of the present invention.
  • the Al, Ti, Nb, V, Ca, Mg, REM, etc. in the ferrophosphorus and ferrosilicon will rapidly undergo oxidation and reduction reactions, and successively generate large oxides and particles.
  • ferrophosphorus, ferrosilicon and ferromanganese refer to alloys containing P, Si, and Mn, and the percentage of the composition is not limited, as long as the composition of the steel plate formed after the addition meets the above content requirements.
  • the amount of ferrosilicon added needs to be considered in two aspects: on the one hand, adding ferrosilicon according to the chemical composition P to ensure that Si 2 /P is controlled between 0.89 and 26.04; on the other hand, it needs to be based on the chemical composition.
  • the component O is added to ferrosilicon to ensure that the O content in the steel is adjusted by Si deoxidation under the condition of extremely low aluminum content, so as to prevent the O content from being too low or too high.
  • step (3) the opening-rolling temperature is controlled to be 1050-1150°C, the final rolling temperature is 650-950°C, the coiling temperature is 650-850°C, and soaking And the holding temperature is 650 ⁇ 850°C, and the holding time is at least 10s.
  • controlling the soaking and holding temperature to be 650-850°C can effectively promote the segregation of trace element Sn, so as to improve the recrystallization structure of the hot-rolled steel sheet and promote the growth of grain size.
  • the further heat preservation time is 10s-60h, and further, the heat preservation time can be controlled within 24h, for example, 2h-24h.
  • step (3) rough rolling and finishing rolling are completed in 2 to 8 passes.
  • One pass is rolling once, and 2-8 passes are rolling 2-8 times.
  • the annealing temperature is 650-950°C
  • the annealing atmosphere is a mixed gas of H 2 and N 2
  • the volume ratio of H 2 is 20%-60 %.
  • Nitrogen contains a small amount of oxygen, which is easy to cause oxidation and blackening of the surface of the steel plate.
  • the main purpose of adding hydrogen is to avoid oxidation of the surface of the steel strip.
  • the above-mentioned hydrogen volume ratio is effective, and the cost can be controlled within a reasonable range.
  • the low-cost and extremely low-aluminum non-oriented electrical steel sheet and the manufacturing method thereof according to the present invention have the following advantages and beneficial effects:
  • the low-cost and extremely low-aluminum non-oriented electrical steel sheet of the present invention reduces the RH refining and deoxidizing technology by optimizing the design of the chemical composition of the steel, with the help of the extremely low aluminum content in the steel and the proper amount of oxidizing properties in the steel and slag. , Alloying special alloy quality, in order to greatly reduce the cost of steel manufacturing, and effectively control the cost of alloys.
  • the iron loss P 15/50 of this non-oriented electrical steel plate is reduced by 0.2 ⁇ 0.8W/kg on average, and the magnetic induction B 50 is increased by 0.01 ⁇ 0.04T on average. , It also has the characteristics of high magnetic induction and low iron loss.
  • the manufacturing method of the present invention has simple production process and low manufacturing cost. It controls the process conditions, especially the hot rolling process, to control the hot-rolled sheet not to undergo normalization treatment or bell furnace annealing after coiling. It uses the residual heat of the hot-rolled steel coil for soaking and heat preservation, which can segregate the trace element Sn in the steel, which can improve the recrystallization structure of the hot-rolled steel sheet and promote the growth of the grain size.
  • Figure 1 schematically shows the relationship between the oxygen content in the non-oriented electrical steel sheet of the present invention and the iron loss P 15/50 of the finished steel sheet.
  • FIG. 2 is a microstructure diagram of the hot rolled steel sheet of Example 2.
  • FIG. 2 is a microstructure diagram of the hot rolled steel sheet of Example 2.
  • FIG. 3 is a microstructure diagram of the hot rolled steel sheet of Comparative Example 2.
  • Example 4 is a microstructure diagram of the finished non-oriented electrical steel sheet of Example 3.
  • FIG. 5 is a microstructure diagram of the finished steel plate of Comparative Example 3.
  • FIG. 5 is a microstructure diagram of the finished steel plate of Comparative Example 3.
  • Table 1 lists the mass percentages of various chemical elements in the non-oriented electrical steel sheets of Examples 1-6. It should be noted that the inevitable impurities in steel grades mainly include: Nb, V, Ti, Ca, Mg and REM.
  • non-oriented electrical steel sheets of Examples 1-6 of the present invention are all prepared by the following steps:
  • Hot rolling control the opening temperature of 1050 ⁇ 1150°C, the final rolling temperature of 650 ⁇ 950°C, the coiling temperature of 650 ⁇ 850°C, the soaking and holding temperature of 650 ⁇ 850°C, and the holding time of at least 10s , Rough rolling and finishing rolling are completed in 2-8 passes, and the target thickness of hot rolling is 1.2-2.8mm.
  • the hot-rolled sheet is not subjected to normalization treatment or bell furnace annealing after coiling, but uses the residual heat of the hot-rolled steel coil for soaking and insulation. After the hot rolling is completed, pickling the hot-rolled steel coil;
  • the annealing temperature is controlled to be 650-950°C
  • the annealing time is ⁇ 180s
  • the annealing atmosphere is a mixed gas of H 2 and N 2
  • the volume ratio of H 2 is 20% to 60%.
  • Table 2-1 and Table 2-2 list the specific process parameters of the manufacturing method of the non-oriented electrical steel sheet of Example 1-6.
  • the rough rolling and finishing rolling passes in Table 2-2 represent the rolling times of rough rolling and finishing rolling, for example, 4+7 in Example 1 means that the rough rolling is completed in 4 passes, and the finishing rolling is divided into 7 passes. Time to complete.
  • Example 1 Al ⁇ 0.1%, Ti ⁇ 0.03%, P ⁇ 0.05%
  • Example 2 Al ⁇ 0.10%, Ti ⁇ 0.03%, P ⁇ 0.05%
  • Example 3 Al ⁇ 0.10%, Ti ⁇ 0.03%, P ⁇ 0.05%
  • Example 4 Al ⁇ 0.10%, Ti ⁇ 0.03%, P ⁇ 0.05%
  • Example 5 Al ⁇ 0.10%, Ti ⁇ 0.03%, P ⁇ 0.05%
  • Example 6 Al ⁇ 0.10%, Ti ⁇ 0.03%, P ⁇ 0.05%
  • Table 3 lists the mass percentages of various chemical elements in the non-oriented electrical steel sheets of Comparative Examples 1-6.
  • Table 4 lists the specific process parameters of the manufacturing method of the non-oriented electrical steel sheet of Comparative Examples 1-6.
  • Example 1 corresponds to the national standard B50A1300 steel of Comparative Example 1
  • Example 2 corresponds to the national standard B50A800 steel of Comparative Example 2
  • Example 3 corresponds to the national standard B50A470 steel of Comparative Example 3
  • Example 4 It corresponds to the national standard B50A1300 steel of Comparative Example 4, the example 5 corresponds to the national standard B50A800 steel of Comparative Example 5, and the example 6 corresponds to the national standard B50A470 steel of Comparative Example 6.
  • Table 5 lists the performance test results of the non-oriented electrical steel plates of Examples 1-6 and the steel plates of Comparative Examples 1-6.
  • the iron loss performance test Based on the national standard GB/T 3655-2008, the Epstein square ring method is used for the iron loss performance test, the test temperature is 20 °C constant temperature test, the sample size is 30mm ⁇ 300mm, and the target mass is 0.5 kg, the test parameter is P 15/50 .
  • Magnetic induction performance test Based on the national standard GB/T 3655-2008, the Epstein square ring method is used for iron loss performance test, 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 B 50 .
  • the comparative example 1-6 steel plate prepared under conventional process conditions and the non-oriented electrical steel plate of Example 1-6 have significant differences in iron loss P 15/50 and magnetic induction B 50 properties.
  • the electromagnetic performance test density is 7.85 g/cm 3
  • the iron loss P 15/50 of Example 1 is 0.4 W/kg lower than that of Comparative Example 1, and the magnetic induction B 50 is increased by 0.04 T.
  • the Al content in Comparative Example 1 is as high as 0.01%, which has exceeded the upper limit of 0.001% in the right of the invention, and the temperature of the steel coil after hot rolling is only 547°C during soaking and holding.
  • the soaking and holding temperature is 583°C, which does not meet the control range of 650-850°C, and the soaking and holding time is 0, which is lower than the design requirements of the present invention. 10s; when the electromagnetic performance test density is 7.80g/cm 3 , the iron loss P 15/50 of Example 5 is reduced by 0.7 W/kg compared with Comparative Example 5, and the magnetic induction B 50 is increased by 0.03T.
  • the O content in the comparative example 6 is only 0.0019%, which is lower than the lower limit of the present invention 0.003%
  • the soaking and holding time is 0, which is less than the lower limit of the design requirement of the present invention by 10s.
  • the non-oriented electrical steel sheet of each embodiment of the present invention has excellent performance through reasonable chemical composition design and process design. Compared with the conventional products of the same grade, the iron loss P 15/50 of this non-oriented electrical steel plate is reduced by 0.2 ⁇ 0.8W/kg on average, and the magnetic induction B 50 is increased by 0.01 ⁇ 0.04T on average. , It also has the characteristics of high magnetic induction and low iron loss.
  • Figure 1 schematically shows the relationship between the oxygen content in the non-oriented electrical steel sheet of the present invention and the iron loss P 15/50 of the finished steel sheet.
  • Figure 1 schematically shows the relationship between the oxygen content and the iron loss P 15/50 of the finished steel plate.
  • the steel plate shown in Figure 1 is manufactured with the steel grade of the national standard B50A1300 as the standard.
  • the other components of the steel plate in 1 are all within the range defined by the composition of the present invention, and the manufacturing method thereof is also within the scope required by the present invention.
  • the mass percentage of each chemical element in the steel plate in Figure 1 satisfies: C ⁇ 0.003%, Si: 0.1% ⁇ 1.2%, Mn: 0.1% ⁇ 0.4%, P: 0.01% ⁇ 0.2%, S ⁇ 0.003%, Al ⁇ 0.001%, N ⁇ 0.003%, Sn: 0.005%-0.05%, the balance is Fe and other inevitable impurities; and satisfies Si 2 / P: 0.89-26.04, in which the oxygen content is shown in Figure 1.
  • the manufacturing method of the steel plate adopts steps including: (1) smelting; (2) continuous casting; (3) hot rolling: after coiling, the hot-rolled sheet is not subjected to normalization treatment or bell furnace annealing, but hot-rolled The residual heat of the steel coil is soaked and kept warm; (4) one cold rolling; (5) continuous annealing.
  • the iron loss of the finished steel sheet is closely related to the oxygen content in the steel.
  • the oxygen content is less than 30ppm
  • the iron loss of the steel plate will exceed 6.0W/kg, and the lower the oxygen content, the higher the iron loss of the steel plate; and when the oxygen content is between 30-100ppm, the iron loss of the steel plate is generally lower , And the control effect can be stabilized at 5.5W/kg or below; and after the oxygen content is higher than 100ppm, as the oxygen content continues to increase, the iron loss of the steel plate increases monotonously and rapidly, and when the oxygen content reaches 130ppm, the iron loss of the steel plate The loss can even reach 8.5W/kg, which is much higher than the iron loss of the steel plate corresponding to low oxygen content.
  • FIG. 2 is a microstructure diagram of the hot rolled steel sheet of Example 2.
  • FIG. 2 is a microstructure diagram of the hot rolled steel sheet of Example 2.
  • FIG. 3 is a microstructure diagram of the hot rolled steel sheet of Comparative Example 2.
  • the hot-rolled steel sheet corresponding to Example 2 can achieve complete recrystallization, with uniform and coarse grain size, and the average grain size can reach 80 ⁇ m, while the corresponding hot-rolled steel sheet corresponding to Comparative Example 2 does not Complete recrystallization is achieved. Recrystallization is achieved only at a position close to about 5% of the upper and lower surfaces of the hot-rolled steel sheet.
  • the middle position of the steel sheet is a fibrous incomplete recrystallization structure, in which the grain size that can be recrystallized is relatively small, and the average is insufficient 50 ⁇ m.
  • Example 4 is a microstructure diagram of the finished non-oriented electrical steel sheet of Example 3.
  • FIG. 5 is a microstructure diagram of the finished steel plate of Comparative Example 3.
  • FIG. 5 is a microstructure diagram of the finished steel plate of Comparative Example 3.
  • Example 3 the microstructure of the finished steel strip is dominated by coarse equiaxed grains.
  • the long and short axis sizes between the grains are close, and the shape is regular and average.
  • the crystal size is 75 ⁇ m.
  • Comparative Example 3 of the same grade there is a phenomenon that the crystal grains cannot grow up effectively.
  • the fine crystal grains show local clusters and segregation.
  • the remaining equiaxed grains that can be recrystallized normally show The crystal grain size is small and the distribution is uneven.

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Abstract

本发明公开了一种低成本极低铝的无取向电工钢板，其含有质量百分比如下的下述化学元素：C≤0.003％、Si：0.1％～1.2％、Mn：0.1％～0.4％、P：0.01％～0.2％、S≤0.003％、Al≤0.001％、O：0.003％～0.01％、N≤0.003％、Sn：0.005％～0.05％，且满足Si2/P：0.89～26.04。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；(2)连铸；(3)热轧：其中热轧板在卷取后不进行常化处理或罩式炉退火，而是利用热轧钢卷的自身余热进行均热和保温；(4)一次冷轧；(5)连续退火。本发明所述的无取向电工钢板采用合理的化学成分和工艺设计，不仅有优良的经济性，还具有高磁感和低铁损的特性。

Description

一种低成本极低铝的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
无取向电工钢板内部晶粒方向不唯一，是具有优良电磁性能的一种功能材料。长期以来，无取向电工钢板都在沿着两个方向不断发展：一是制造成本昂贵、生产工艺复杂，但电磁性能、机械性能优良的高效、高牌号钢种；二是制造成本低廉、生产工艺简便，具有优良电磁性能、机械性能的中低牌号钢种。
据统计，由于使用场合不同的缘故，中低牌号无取向电工钢板的数量，占到了全部无取向电工钢板的70％或以上。因此，研究如何更加经济、便捷的生产中低牌号无取向电工钢板，进一步提高其性价比具有十分重要的现实意义。同时，考虑到中低牌号无取向电工钢板，绝大多数都应用于中小型电机、EI铁芯、小型发电机等方面，因此，用户市场在不断要求降低钢板铁损的同时，对钢板磁感的提高需求更为迫切，目的就是为了更加有效地降低铁芯铜损。
此外，研究表明，在无取向电工钢板的电磁性能指标中，铁损、磁感两者之间相互制约，很难同时实现低铁损、高磁感，除非采用增加热轧钢板常化处理或罩式炉退火处理等，但这无形之中会大大增加成品钢板的制造成本。
近年来，围绕在不进行热轧板常化处理或罩式炉退火处理的前提下，如何有效地改善无取向电工钢板的电磁性能，同时降低其制造成本，大量的科技工作者做了很多有益的尝试。
公开号为CN101992210A，公开日为2011年3月30日，名称为“一种生产冷轧无取向硅钢无铝钢种的方法”的中国专利文献，公开了一种涉及生产冷轧无取向硅钢无铝钢种的方法，指出通过控制Al≤0.0010％及易形成氮化物的残余元素含量，热轧采取低温加热及控温轧制，冷轧材一次或带有中间退火的二次冷轧轧制，实行湿氢脱碳、再结晶温度退火等综合性能控制措施，从而 在现有设备条件下，以较低的生产成本，实现了批量生产高效无铝冷轧无取向硅钢，其电磁新更能均优于同牌号常规工艺生产的冷轧无取向硅钢，铁损平均降低了0.4W/kg左右，磁感平均提高了0.2T。其具体控制方法为，控制包含脱氧铝、辅材和耐火材料合金化过程中带入的残铝含量，控制Al≤0.0010％，精炼脱氧工艺采用Si脱氧；控制冶炼氮含量及其易形成氮化物的残余元素含量，控制N、Ti、Nb、V含量分别≤0.0020％；热轧采取低温加热及精轧实行控温轧制，即铁素体单相区轧制，并控制二相析出状态；热轧钢坯加热温度为1000～1150℃，开轧温度≥950℃，终轧温度≥840℃，卷取温度≥690℃；冷轧采用一次或者带有中间退火的二次冷轧法轧制为成品厚度；退火采用罩式炉火连续退火炉进行湿氢脱碳、再结晶温度退火。无取向电工钢板及其制造方法。其组分按重量百分比计为：C：0.03～0.15％，Si≤0.15％，Mn：1.0-1.8％，P≤0.025％，S≤0.015％，Ti：0.08～0.18％，Nb：0.02～0.07％，Al：0.02～0.10％，N≤0.010％，其余为铁及残余含量。
公开号为CN101306434A，公开日为2008年11月19日，名称为“一种低碳低硅无铝半工艺无取向电工钢的制备方法”的中国专利文献，公开了一种低碳低硅无铝半工艺无取向电工钢的制备方法。其工艺步骤为：热轧原料成分设计要求其铸坯化学成分满足，C≤0.005％，Si：0.1～1.0％，Mn≤0.35％，P≤0.08％，S≤0.01％，N≤0.008％，O≤0.015％，其余为Fe和不可避免的杂质；铸坯热装、热轧，临界变形冷轧，用户消除应力退火后得到磁性优良的半工艺无取向电工钢。其特征在于，所述的铸坯加热温度为900～1150℃，要求终轧温度低于Ar3相变点10～50℃，热轧板厚度为2.0～2.5mm；所述的中间退火温度为600～850℃，时间为1～2min，中间退火气氛为H 2、N 2混合气体，H 2的比例为10～40％，且不需要加湿脱碳，并保证中间退火后再结晶率≥40％；所述的临界变形冷轧是指，中间退火后的钢带经过压下率为0.5～15％的临界变形冷轧至0.5mm，临界变形冷轧后钢板硬度为130～180HV；所述的用户消除应力退火是指，临界变形后的冷轧冲片、叠片后经温度为700～850℃、时间为1～2h的用户消除应力退火，要求退火气氛为H 2、N 2混合气体，H 2的比例为10～40％，冷却方式为缓冷，要求以冷却速度10～100℃/h冷却至450℃，然后随炉冷却，得到最终需要的产品。其优点在于，最终产品磁性能优良，P 15/50＝3.35～5.05W/kg、B 5000＝1.69～1.76T。铸坯中不含Al、Sn、Sb、Cu、Cr、 Ni、B、稀土等合金元素，生产成本大幅度降低。采用了较大的临界压下量，且优化了退火工艺，生产出的成品磁性能更优。
发明内容
本发明的目的之一在于提供一种低成本极低铝的无取向电工钢板，该无取向电工钢板通过优化钢的化学成分，借助钢中含有极低铝含量，以及钢、渣含有适量的氧化性技术特点，调低了RH精炼脱氧、合金化专用合金品质，以大幅降低钢的制造成本，有效控制了合金成本。该无取向电工钢板与常规同牌号产品相比，其铁损P 15/50平均降低0.2～0.8W/kg，磁感B 50平均升高0.01～0.04T。也就是说，本发明的特定牌号的无取向电工钢板与现有常规的同牌号产品相比，铁损平均降低0.2～0.8W/kg，磁感B 50平均升高0.01～0.04T，不仅有优良的经济性，还具有高磁感和低铁损的特性。其中，上述电磁性能的参考值为现有用户市场上，普通的无取向电工钢板。B50A1300牌号的电磁性能中，铁损P 15/50一般在5.5～6.5W/kg、磁感B 50一般在1.74～1.76T；常规B50A800牌号的电磁性能中，铁损P 15/50一般在5.0～5.5W/kg、磁感B 50一般在1.71～1.73T；常规B50A600牌号的电磁性能中，铁损P 15/50一般在3.9～4.5W/kg、磁感B 50一般在1.68～1.71T。
为了实现上述目的，本发明提供了一种低成本极低铝的无取向电工钢板，其含有质量百分比如下的下述化学元素：
C≤0.003％、Si：0.1％～1.2％、Mn：0.1％～0.4％、P：0.01％～0.2％、S≤0.003％、Al≤0.001％、O：0.003％～0.01％、N≤0.003％、Sn：0.005％～0.05％，且满足Si 2/P：0.89～26.04。
进一步地，在本发明所述的无取向电工钢板中，其各化学元素质量百分比为：
C≤0.003％、Si：0.1％～1.2％、Mn：0.1％～0.4％、P：0.01％～0.2％、S≤0.003％、Al≤0.001％、O：0.003％～0.01％、N≤0.003％、Sn：0.005％～0.05％，余量为Fe及其他不可避免的杂质；且满足Si 2/P：0.89～26.04。
在本发明所述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，碳是强时效形成元素之一。当钢中C元素含量高于0.003％时，容易与Nb、V、Ti等结合，形成大量的微细夹 杂物，从而导致成品钢板的损耗显著增加。因此在本发明所述的无取向电工钢板中控制C的质量百分比为C≤0.003％。本发明的无取向电工钢板中，C元素含量控制的越低越好，具体地，控制C的质量百分比为0＜C≤0.003％。
Si：在本发明所述的无取向电工钢板中，Si元素能显著增加材料的电阻率。但需要注意的是，若钢中Si元素含量低于0.1％时，则不能有效降低成品钢板铁损；而若钢中Si元素含量高于1.2％时，则会显著劣化成品钢板磁感。因此，在本发明所述的无取向电工钢板中控制Si的质量百分比在0.1％～1.2％之间。
Mn：在本发明所述的无取向电工钢板中，Mn元素可以与S元素结合形成MnS，从而有效改善成品钢板的磁性。为了保证Mn元素能有效起到作用，钢中需要添加0.1％以上的Mn，但需要注意的是，Mn元素含量也不宜过高，若钢中Mn元素含量高于0.4％，会显著破坏成品钢板再结晶织构。因此，在本发明所述的无取向电工钢板中控制Mn的质量百分比在0.1％～0.4％之间。
P：在本发明所述的无取向电工钢板中，P元素能显著提高材料的强度。当钢中P元素含量低于0.01％时，不能起到有效改善成品钢板强度的作用，而若钢中P元素含量高于0.2％时，则会显著降低冷轧可轧性。因此，在本发明所述的无取向电工钢板中控制P的质量百分比在0.01％～0.2％之间。
S：在本发明所述的无取向电工钢板中，S元素含量不宜过高，当钢中S元素含量高于0.003％时，会显著增加MnS、Cu 2S等夹杂物数量，阻碍晶粒长大，劣化成品钢板的磁性。因此，在本发明所述的无取向电工钢板中控制S的质量百分比为0＜S≤0.003％。本发明的无取向电工钢板中，S元素含量控制的越低越好，具体地，控制S的质量百分比为0＜S≤0.003％。
Al：在本发明所述的无取向电工钢板中，钢中Al元素含量不宜过高，当钢中Al含量高于0.001％时，会生成大量的AlN有害夹杂物，显著劣化成品钢板的磁性。因此，在本发明所述的无取向电工钢板中控制Al的质量百分比为Al≤0.001％。本发明的无取向电工钢板中，Al元素含量控制的越低越好，具体地，控制Al的质量百分比为0＜Al≤0.001％。
在一些优选的实施方式中，Al的质量百分比可以控制为Al≤0.0005％。
O：在本发明所述的无取向电工钢板中，当钢中O元素含量低于0.003％时，不利于Al、Ti含量控制，而若钢中O元素含量高于0.01％时，则会生成 大量的氧化物夹杂物，劣化成品钢板的磁性。因此，在本发明所述的无取向电工钢板中控制O的质量百分比在0.003％～0.01％之间。
在一些优选的实施方式中，O的质量百分比可以控制在0.045％～0.007％之间。
N：在本发明所述的无取向电工钢板中，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，阻碍晶粒长大，劣化成品钢板的磁性。因此，在本发明所述的无取向电工钢板中控制N的质量百分比为N≤0.003％。本发明的无取向电工钢板中，N元素含量控制的越低越好，具体地，控制N的质量百分比为0＜C≤0.003％。
Sn：在本发明所述的无取向电工钢板中，Sn是晶界偏聚元素。钢中添加的适量有益元素Sn，可以在热轧轧制过程中，可以起到改善晶界偏聚和改善微观的有利织构的作用。当钢中Sn元素含量低于0.005％时，不能有效获得偏聚效果，而若钢中Sn元素含量超过0.05％时，则会导致晶粒细化，劣化成品钢板的磁性。因此，在本发明所述的无取向电工钢板中控制Sn的质量百分比在0.005％～0.05％之间。
在一些优选的实施方式中，Sn的质量百分比可以控制在0.005％～0.02％之间。
此外，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，还控制Si元素和P元素满足Si 2/P：0.89～26.04，其中，式中Si和P均表示相应元素的质量百分比百分号前的数字。需要说明的是，Si元素和P元素的性质相近，都能显著提高材料的电阻率和降低成品钢板的铁损，但同时会劣化成品钢板的磁感。而在改善成品钢板的机械轻度方面，P元素具有十分优良的显著作用，但会劣化高Si含量条件时的冷轧可轧性。因此，针对成品钢板的电磁性能、机械性能进行综合考虑，在本发明所述的无取向电工钢板中控制Si 2/P在0.89～26.04之间。
在一些优选的实施方式中，为了得到更优的实施效果，Si 2/P可以控制在0.89～16.67之间。
另外，在本发明所述的无取向电工钢板中，需要说明的是，钢中的不可避免的杂质包括Nb、V、Ti、Ca、Mg和REM。其中REM为稀土元素，也可以简称为RE。
进一步地，在本发明所述的无取向电工钢板中，其中Al≤0.0005％。
进一步地，在本发明所述的无取向电工钢板中，其中O：0.045％～0.007％。
进一步地，在本发明所述的无取向电工钢板中，其中Sn：0.005％～0.02％。
进一步地，在本发明所述的无取向电工钢板中，其中Si 2/P：0.89～16.67。
进一步地，在本发明所述的无取向电工钢板中，其与常规同牌号产品相比，其铁损P 15/50平均降低0.2～0.8W/kg，磁感B 50平均升高0.01～0.04T。进一步地，在本发明所述的无取向电工钢板中，其厚度为0.5±0.1mm。
相应地，本发明的另一目的在于提供一种低成本极低铝的无取向电工钢板的制造方法，该制造方法生产工艺简便、制造成本低廉，采用该制造方法制得的无取向电工钢板与常规同牌号产品相比，其铁损P 15/50平均降低0.2～0.8W/kg，磁感B 50平均升高0.01～0.04T，具有高磁感和低铁损的特性。
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；
(2)连铸；
(3)热轧：其中热轧板在卷取后不进行常化处理或罩式炉退火，而是利用热轧钢卷的自身余热进行均热和保温；
(4)一次冷轧；
(5)连续退火。
在本发明所述的制造方法中，热轧工序主要包括：板坯加热、粗轧、精轧和卷取工序。所说的常化处理或罩式炉退火是指在热轧之后、冷轧之前，对热轧卷进行中间退火的一种工艺，目的是改善成品电磁性能。而本发明在所述步骤(3)中，热轧板在卷取后不进行常化处理或罩式炉退火，而是利用热轧钢卷的自身余热进行均热和保温，可以有效促进微量元素Sn偏聚，改善热轧钢板再结晶组织和促进晶粒尺寸长大，从而可以实现代替或者补充常化退火或者罩式炉退火效果。此外，这一操作还可以有效简便工艺，减轻生产负担和制造难度，降低成产成本。
进一步地，在本发明所述的制造方法中，在步骤(1)中，在RH精炼的脱氧、合金化时，依次加入磷铁、硅铁和锰铁。
在本发明所述的无取向电工钢板的制造方法中，在所述步骤(1)中，在 RH精炼的脱氧、合金化时，依次加入磷铁、硅铁和锰铁。即在RH精炼末期，向钢液中加入磷铁、硅铁和锰铁，以去除钢中的自由氧，并按照本发明要求配加元素成分。这样，钢液在有氧的状态下，磷铁、硅铁中的Al、Ti、Nb、V、Ca、Mg、REM等，会迅速发生氧化、还原反应，并陆续生成了大颗粒氧化物和上浮进入顶渣中，这样就不会劣化钢质洁净度。因此，经过大量的试验研究，已有效降低对磷铁、硅铁的部分有害元素控制要求，从而可以大大降低炼钢环节的生产制造成本。其中磷铁、硅铁和锰铁是指含有P、Si、Mn的合金，其成分百分比不限制，只要能够在加入后形成的钢板的成分符合上述含量要求即可。
此外，需要说明的是，硅铁的加入量需要考虑两个方面：一方面，根据化学成分P加入硅铁，以确保Si 2/P控制在0.89～26.04之间，另一方面，需要根据化学成分O加入硅铁，以确保在极低铝含量条件下，依靠Si脱氧调节钢中的O含量，以免O含量出现过低或过高。当硅铁加入量过大时，脱氧能力强，钢中的O含量偏低，生成的大量脱氧产物SiO 2进入渣中，会导致Al、Ti、Nb、V、Ca、Mg、REM等元素还原重新进入钢中；当硅铁加入量过小时，脱氧能力弱，钢中的O含量偏高，并在最终连铸浇铸时，随着钢液温度的不断降低，过饱和而再次生成大量尺寸细小的二次脱氧化物SiO 2，此时，其已无法上浮和去除，残留在钢中，并为后续热轧期间MnS夹杂物析出提供核心。因此，需要根据化学成分O加入硅铁，确保钢中O含量严格控制在0.003％～0.01％之间。上述连铸的缩写是CC，浇铸是指把钢水浇铸成连铸坯。
进一步地，在本发明所述的制造方法中，其中，在所述硅铁中，Al≤0.1％并且/或者Ti≤0.03％。
进一步地，在本发明所述的制造方法中，在步骤(3)中，控制开轧温度为1050～1150℃，终轧温度为650～950℃，卷取温度为650～850℃，均热和保温温度为650～850℃，保温时间至少为10s。
上述方案中，在所述步骤(3)中，控制均热和保温温度为650～850℃，可以有效促进微量元素Sn偏聚，以改善热轧钢板再结晶组织和促进晶粒尺寸长大。控制保温时间至少为10s，在温度条件允许的情况下，可以适当延长以扩大改善效果。例如，进一步保温时间在10s～60h，更进一步地，可将保温时间控制在24h以内，例如在2h～24h。
进一步地，在本发明所述的制造方法中，在步骤(3)中，粗轧和精轧分2～8个道次完成。一个道次就是轧制一次，2～8个道次就是轧制2～8次。
进一步地，在本发明所述的制造方法中，在步骤(5)中，退火温度为650～950℃，退火气氛为H 2和N 2混合气体，其中H 2的体积比例为20％～60％。氮气中会含有少量的氧，易导致钢板表面氧化发黑，添加氢气主要是为了避免带钢表面氧化。上述氢气体积比例效果较好，且能够成本控制在合理范围。
本发明所述的低成本极低铝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：
本发明所述的低成本极低铝的无取向电工钢板通过优化钢的化学成分设计，借助钢中含有极低铝含量，以及钢、渣含有适量的氧化性技术特点，调低了RH精炼脱氧、合金化专用合金品质，以大幅降低钢的制造成本，有效控制了合金成本。该无取向电工钢板与常规同牌号产品相比，其铁损P 15/50平均降低0.2～0.8W/kg，磁感B 50平均升高0.01～0.04T，实现了在具有良好经济性的同时，还具有高磁感和低铁损的特性。
此外，本发明所述的制造方法生产工艺简便、制造成本低廉，其通过对工艺条件尤其是热轧工艺的控制，控制热轧板在卷取后不进行常化处理或罩式炉退火，而是利用热轧钢卷的自身余热进行均热和保温，可以使钢中微量元素Sn偏聚，起到改善热轧钢板再结晶组织和促进晶粒尺寸长大的效果。
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氧含量与成品钢板铁损P 15/50之间的关系。
图2为实施例2的热轧钢板的显微组织图。
图3为对比例2的热轧钢板的显微组织图。
图4为实施例3的成品无取向电工钢板的显微组织图。
图5为对比例3的成品钢板的显微组织图。
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低成本极低铝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1-6和对比例1-6
表1列出了实施例1-6的无取向电工钢板中各化学元素质量百分比。需要说明的是，钢种中不可避免的杂质主要包括：Nb、V、Ti、Ca、Mg和REM。
表1.(％，余量为Fe和其他不可避免的杂质)
Figure PCTCN2021095717-appb-000001
本发明所述实施例1-6的无取向电工钢板均采用以下步骤制得：
(1)冶炼：高炉铁水以及适量废钢经转炉冶炼之后，在RH精炼依次完成脱碳、脱氧、合金化，然后浇铸成合格板坯。在RH精炼的脱氧、合金化时，依次加入磷铁、硅铁和锰铁，其中，在硅铁中，Al≤0.1％，Ti≤0.03％；
(2)连铸；
(3)热轧：控制开轧温度为1050～1150℃，终轧温度为650～950℃，卷取温度为650～850℃，均热和保温温度为650～850℃，保温时间至少为10s，粗轧和精轧分2～8个道次完成，热轧目标厚度为1.2～2.8mm。其中热轧板在卷取后不进行常化处理或罩式炉退火，而是利用热轧钢卷的自身余热进行均热和保温。热轧完成后，对热轧钢卷进行酸洗；
(4)一次冷轧：一次性轧制成目标厚度；
(5)连续退火：控制退火温度为650～950℃，退火时间≤180s，退火气氛为H 2和N 2混合气体，其中H 2的体积比例为20％～60％。
表2-1和表2-2列出了实施例1-6的无取向电工钢板的制造方法的具体工艺参数。其中，表2-2中粗轧和精轧道次分别代表粗轧和精轧的轧制次数，例如实施例1中4+7代表粗轧分4个道次完成，精轧分7个道次完成。
表2-1.
编号 步骤(1)
  硅铁品质
实施例1 Al≤0.1％，Ti≤0.03％，P≤0.05％
实施例2 Al≤0.10％，Ti≤0.03％，P≤0.05％
实施例3 Al≤0.10％，Ti≤0.03％，P≤0.05％
实施例4 Al≤0.10％，Ti≤0.03％，P≤0.05％
实施例5 Al≤0.10％，Ti≤0.03％，P≤0.05％
实施例6 Al≤0.10％，Ti≤0.03％，P≤0.05％
表2-2.
Figure PCTCN2021095717-appb-000002
表3列出了对比例1-6的无取向电工钢板中各化学元素质量百分比。
表3.(％，余量为Fe和其他不可避免的杂质)
Figure PCTCN2021095717-appb-000003
表4列出了对比例1-6的无取向电工钢板的制造方法的具体工艺参数。
表4.
Figure PCTCN2021095717-appb-000004
Figure PCTCN2021095717-appb-000005
需要说明的是，对比例1-6的钢板并不采用本发明的制造工艺，其仅采用常规的工艺条件制得，且对比例1-6的钢板分别与实施例1-6一一对应。其中，实施例1对应的是对比例1的国标B50A1300牌号钢，实施例2对应的是对比例2的国标B50A800牌号钢，实施例3对应的是对比例3的国标B50A470牌号钢；实施例4对应的是对比例4的国标B50A1300牌号钢，实施例5对应的是对比例5的国标B50A800牌号钢，实施例6对应的是对比例6的国标B50A470牌号钢。
将冷轧得到的最终目标厚度0.5±0.1mm的实施例1-6的无取向电工钢板以及对比例1-6的钢板行各项性能测试，所得的测试结果列于表3中。
表5列出了实施例1-6的无取向电工钢板以及对比例1-6钢板的性能测试结果。其中，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5.
Figure PCTCN2021095717-appb-000006
Figure PCTCN2021095717-appb-000007
由表3可看出，采用常规的工艺条件制得的对比例1-6钢板与实施例1-6的无取向电工钢板在铁损P 15/50和磁感B 50性能上均存在明显差异。电磁性能测试密度为7.85g/cm 3时，实施例1较对比例1铁损P 15/50降低了0.4W/kg，磁感B 50升高了0.04T。这主要是因为，对比例1中的Al含量高达0.01％，已经超出了发明权利项中的上限0.001％，且热轧之后的钢卷在进行均热和保温时，温度仅为547℃，不满足650～850℃控制范围；电磁性能测试密度为7.80g/cm 3时，实施例2较对比例2铁损P 15/50降低了0.6W/kg，磁感B 50升高了0.02T，这主要是因为，对比例2中的Si、P含量设计不匹配，从而导致Si 2/P高达45.56，已经超出上限26.04，且热轧之后的钢卷在进行均热和保温时，温度高达872℃，不满足650～850℃控制范围；电磁性能测试密度为7.70g/cm 3时，实施例3较对比例3铁损P 15/50降低了0.8W/kg，磁感B 50升高了0.01T，这主要是因为，对比例3中的Si含量太低，从而导致Si 2/P只有0.05，不能满足0.89的控制下限，且热轧之后的钢卷在进行均热和保温时，温度仅为349℃，不满足650～850℃控制范围；电磁性能测试密度为7.85g/cm 3时，实施例4较对比例4铁损P 15/50降低了0.8W/kg，磁感B 50升高了0.04T，这主要是因为，对比例4中，采用了含Al钢成分设计，向钢中加入了高达0.4％的Al，导致O含量低于本发明控制下限0.003％，只有0.0022％。同时，在热轧之后的钢卷在进行均热和保温时，均热和保温温度为583℃，不满足650～850℃控制范围，且均热和保温时间为0，低于本发明设计要求10s；电磁性能测试密度为7.80g/cm 3时，实施例5较对比例5铁损P 15/50降低了0.7W/kg，磁感B 50升高了0.03T，这主要是因为，对比例5中的Al含量为0.0022％，超出本发明控制上限0.001％，且O含量高达0.0125％，已超出本发明设计上限0.01％；电磁性能测试密度为7.70g/cm 3时，实施例6较对比例6铁损P 15/50降低了0.8W/kg，磁感B 50升高了0.04T，这主要是因为，对比例6中的O含量只有0.0019％，低于本发明设计下限0.003％，且热轧之后的钢卷在进行均热和保温时，虽然均热和保温高达 900℃，但均热和保温时间为0，低于本发明设计要求下限10s。
由此可见，本发明各实施例的无取向电工钢板通过合理的化学成分设计和工艺设计，具有优异的性能。该无取向电工钢板与常规同牌号产品相比，其铁损P 15/50平均降低0.2～0.8W/kg，磁感B 50平均升高0.01～0.04T，实现了在具有良好经济性的同时，还具有高磁感和低铁损的特性。
图1示意性地显示了本发明所述的无取向电工钢板中氧含量与成品钢板铁损P 15/50之间的关系。
如图1所示，图1示意性地显示了氧含量与成品钢板铁损P 15/50之间的关系，其中图1所示的钢板是以国标B50A1300牌号的钢种为标准制造的，图1中钢板的其它成分均在本发明成分限定的范围内，其制造方法也均在本发明要求的范围内。也即，图1中钢板的各化学元素质量百分比满足：C≤0.003％、Si：0.1％～1.2％、Mn：0.1％～0.4％、P：0.01％～0.2％、S≤0.003％、Al≤0.001％、N≤0.003％、Sn：0.005％～0.05％，余量为Fe及其他不可避免的杂质；且满足Si 2/P：0.89～26.04，其中氧含量如图1中所示。并且，钢板的制造方法采用步骤包括：(1)冶炼；(2)连铸；(3)热轧：热轧板在卷取后不进行常化处理或罩式炉退火，而是利用热轧钢卷的自身余热进行均热和保温；(4)一次冷轧；(5)连续退火。
由图1可知，成品钢板的铁损与钢中的氧含量密切相关。氧含量低于30ppm时，钢板的铁损会超出6.0W/kg，并且氧含量越低，钢板的铁损越高；而在氧含量位于30-100ppm之间时，钢板的铁损总体较低，且控制效果可以稳定在5.5W/kg或以下；而在氧含量高于100ppm之后，随着氧含量的不断升高，钢板铁损单调、快速增加，而在氧含量达到130ppm时，钢板铁损甚至可以达到8.5W/kg，大大高于低氧含量对应的钢板铁损。
图2为实施例2的热轧钢板的显微组织图。
图3为对比例2的热轧钢板的显微组织图。
如图2和图3所示，实施例2对应的热轧钢板能够实现完全再结晶，晶粒尺寸均匀、粗大，平均晶粒尺寸可以达到80μm，而相应的对比例2对应的热轧钢板没有实现完全再结晶，仅靠近热轧钢板上下表面约5％的位置实现了再结晶，钢板中间位置即为纤维状未完全再结晶组织，其中能够实现再结晶的晶粒尺寸相对较小，平均不足50μm。
图4为实施例3的成品无取向电工钢板的显微组织图。
图5为对比例3的成品钢板的显微组织图。
结合图4和图5可以看出，对于实施例3而言，其成品带钢的显微组织以粗大的等轴晶粒为主，晶粒之间的长短轴尺寸接近，形状规则且平均再结晶尺寸为75μm，同牌号的对比例3中，存在晶粒不能有效长大的现象，细小的晶粒表现出局部团簇、偏聚，其余能够正常完成再结晶的等轴晶粒，则表现出晶粒尺寸细小，分布不均匀现象。
需要注意的是，以上所列举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。
此外，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 (13)

  1. 一种低成本极低铝的无取向电工钢板，其特征在于，其含有质量百分比如下的下述化学元素：
    C≤0.003％、Si：0.1％～1.2％、Mn：0.1％～0.4％、P：0.01％～0.2％、S≤0.003％、Al≤0.001％、O：0.003％～0.01％、N≤0.003％、Sn：0.005％～0.05％，且满足Si 2/P：0.89～26.04。
  2. 如权利要求1所述的无取向电工钢板，其特征在于，其各化学元素质量百分比为：
    C≤0.003％、Si：0.1％～1.2％、Mn：0.1％～0.4％、P：0.01％～0.2％、S≤0.003％、Al≤0.001％、O：0.003％～0.01％、N≤0.003％、Sn：0.005％～0.05％，余量为Fe及其他不可避免的杂质；且满足Si 2/P：0.89～26.04。
  3. 如权利要求1或2所述的无取向电工钢板，其特征在于，其中Al≤0.0005％。
  4. 如权利要求1或2所述的无取向电工钢板，其特征在于，其中O：0.045％～0.007％。
  5. 如权利要求1或2所述的无取向电工钢板，其特征在于，其中Sn：0.005％～0.02％。
  6. 如权利要求1或2所述的无取向电工钢板，其特征在于，其中Si 2/P：0.89～16.67。
  7. 如权利要求1或2所述的无取向电工钢板，其特征在于，与常规同牌号产品相比，其铁损P 15/50平均降低0.2～0.8W/kg，磁感B 50平均升高0.01～0.04T。
  8. 一种如权利要求1-7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；
    (2)连铸；
    (3)热轧：其中热轧板在卷取后不进行常化处理或罩式炉退火，而是利用热轧钢卷的自身余热进行均热和保温；
    (4)一次冷轧；
    (5)连续退火。
  9. 如权利要求8所述的制造方法，其特征在于，在步骤(1)中，在RH精炼的脱氧、合金化时，依次加入磷铁、硅铁和锰铁。
  10. 如权利要求9所述的制造方法，其特征在于，其中，在所述硅铁中，Al≤0.1％并且/或者Ti≤0.03％。
  11. 如权利要求8所述的制造方法，其特征在于，在步骤(3)中，控制开轧温度为1050～1150℃，终轧温度为650～950℃，卷取温度为650～850℃，均热和保温温度为650～850℃，保温时间至少为10s。
  12. 如权利要求8或11所述的制造方法，其特征在于，在步骤(3)中，粗轧和精轧分2～8个道次完成。
  13. 如权利要求8所述的制造方法，其特征在于，在步骤(5)中，退火温度为650～950℃，退火气氛为H 2和N 2混合气体，其中H 2的体积比例为20％～60％。
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