WO2021027797A1 - 一种高磁感取向硅钢及其制造方法 - Google Patents

一种高磁感取向硅钢及其制造方法 Download PDF

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WO2021027797A1
WO2021027797A1 PCT/CN2020/108333 CN2020108333W WO2021027797A1 WO 2021027797 A1 WO2021027797 A1 WO 2021027797A1 CN 2020108333 W CN2020108333 W CN 2020108333W WO 2021027797 A1 WO2021027797 A1 WO 2021027797A1
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Prior art keywords
annealing
silicon steel
oriented silicon
temperature
manufacturing
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PCT/CN2020/108333
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English (en)
French (fr)
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章华兵
李国保
沈侃毅
刘宝军
侯长俊
张鑫强
陈建兵
吴美洪
马长松
刘德胜
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宝山钢铁股份有限公司
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Priority to US17/631,693 priority Critical patent/US20220275470A1/en
Priority to AU2020328712A priority patent/AU2020328712B2/en
Priority to EP20851796.1A priority patent/EP3992324A4/en
Priority to CA3146020A priority patent/CA3146020C/en
Priority to JP2022505654A priority patent/JP7454646B2/ja
Publication of WO2021027797A1 publication Critical patent/WO2021027797A1/zh

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    • 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
    • H01F1/18—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 with insulating coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0206—Manufacturing of magnetic cores by mechanical means
    • H01F41/0233—Manufacturing of magnetic circuits made from 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
    • C21D2201/05—Grain orientation
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties
    • C22C2202/02—Magnetic

Definitions

  • the invention relates to a steel type and a manufacturing method thereof, in particular to a oriented silicon steel and a manufacturing method thereof.
  • Oriented silicon steel is an indispensable soft magnetic material in the power and defense industries. It is composed of grains with a so-called Goss texture.
  • the Gauss texture is expressed as ⁇ 110 ⁇ 001> by Miller index.
  • the ⁇ 110 ⁇ crystal plane is parallel to the rolling plane, and the ⁇ 001> crystal orientation of the crystal grains is parallel to the rolling direction, so that it has the best easy magnetization performance under a directional magnetic field, and makes full use of the magnetocrystalline anisotropy to achieve polycrystalline materials Best magnetic performance.
  • Oriented silicon steel is used to make the core in power transformers or transmission transformers. Under the working conditions of directional magnetic field, its extremely high magnetic induction and extremely low iron loss can significantly save materials and electricity.
  • Oriented silicon steel usually uses iron loss P 17/50 and magnetic induction B 8 to characterize the level of magnetic performance, where P17/50 represents the iron loss of the sample in Kg when the maximum magnetic induction intensity is 1.7T and the frequency is 50 Hz; B 8 represents Corresponds to the magnetic induction intensity when the magnetic field intensity is 800A/m.
  • oriented silicon steel can be divided into two categories: ordinary oriented silicon steel (B 8 ⁇ 1.88T) and high magnetic induction oriented silicon steel (B 8 ⁇ 1.88T).
  • the traditional high magnetic induction oriented silicon steel is a high-temperature slab heating process, and its disadvantage is that in order to fully dissolve the inhibitor, the heating temperature of the slab usually needs to reach 1400 °C, which is the limit level of the traditional heating furnace .
  • the utilization rate of the heating furnace is low, the service life is short, the silicon segregates at the grain boundary, the hot edge crack is serious, the yield is low, the energy consumption is high, and the manufacturing cost is high.
  • the slab heating temperature range there are two main improvement paths: one is the medium-temperature slab heating process, the slab heating temperature is 1250 ⁇ 1320 °C, using AlN and Cu 2 S as inhibitors; the other This is a low-temperature slab heating process.
  • the slab heating temperature is between 1100 and 1250°C.
  • the inhibitor is introduced by nitriding.
  • the low-temperature slab heating process can be used to produce high magnetic induction oriented silicon steel at a lower cost.
  • the main difficulty of the low-temperature slab heating process is the selection and morphology control of inhibitors.
  • the low-temperature slab heating process has obvious advantages in manufacturing costs and yield, compared with the high-temperature slab heating process, the inhibitor is unstable factors
  • Significant increase, for example, the coarse precipitates formed during the casting process, such as TiN-cored MnS+AlN composite precipitates, are difficult to solid-dissolve in the subsequent annealing, and the inhibitory effect is reduced, resulting in increased difficulty in controlling the primary grain size
  • Large there may also be problems such as uneven distribution of nitriding amount, which leads to uneven distribution of inhibitors AlN, (Al,Si)N, (Al,Si,Mn), etc.
  • the typical magnetic induction B 8 of high magnetic induction oriented silicon steel in the low-temperature slab heating process is between 1.88 ⁇ 1.92T, which is lower than the magnetic induction of similar high-temperature process products, and the occurrence rate of defects such as oxide film is relatively high. high.
  • Some improvements in low-temperature slab heating technology focus on further upgrading product grades, such as thinning strip thickness, increasing silicon content, nicking magnetic domain refinement, rapid induction heating, etc. In order to obtain high quality, these technologies will increase investment or Manufacturing cost; other improved processes focus on reducing the content of inhibitor elements from the source of steelmaking and optimizing the heat treatment process to further reduce manufacturing costs, such as:
  • the publication number is CN1708594, the publication date is December 14, 2005, and the Chinese patent document entitled “Method for manufacturing grain-oriented electrical steel sheet and grain-oriented electrical steel sheet” discloses a technical solution which can be regarded as "inhibitor-free Method” high magnetic induction oriented silicon steel manufacturing method.
  • the slab composition contains C: 0.08% or less, Si: 2.0 to 8.0%, Mn: 0.005% to 3.0% in mass%, Al is 100 ppm or less, and N, S and Se are below 50 ppm, and the balance is Fe and unavoidable impurities.
  • This technical solution does not carry out nitriding operation during the annealing process of cold-rolled sheet, and can reduce the heating temperature of the slab to below 1250°C. Also, because of the low content of C, N, S, Se, and Al, it can effectively reduce the high-temperature annealing process. cost.
  • the above-mentioned manufacturing method has simple processes and reduced manufacturing costs, the product grade is not high and there is a problem of unstable magnetic properties.
  • the magnetic induction B 8 in all the examples is lower than 1.91T. In order to solve the problem of unstable magnetic properties of the inhibitor-free process, additional improved processes need to be added, which inevitably increases manufacturing costs.
  • the publication number is CN101573458, the publication date is November 4, 2009, and the Chinese patent document titled “Method for Producing Grain Oriented Electrical Steel Sheets With Excellent Magnetic Properties With High Productivity” discloses a technical solution, which can be called It is a "low-temperature slab semi-solid solution nitriding method" high magnetic induction oriented silicon steel manufacturing method.
  • the slab component contains C: 0.04 to 0.07% by mass%, Si: 2.0 to 4.0%, P: 0.02 to 0.075%, Cr: 0.05 to 0.35%, acid soluble Al: 0.020 to 0.040%, Mn: less than 0.20%, N: less than 0.0055%, S: less than 0.0055%, and the balance is Fe and inevitable impurities.
  • This technical solution heats the slab to a temperature at which the precipitates in the slab partially dissolve, and requires that the amount of N dissolved in the slab heating process is between 0.0010% and 0.0040%, followed by hot rolling, hot-rolled sheet annealing, and cold rolling.
  • the slab heating temperature is also required to be 1050 to 1250°C.
  • the difficulty lies in how to achieve a high level of matching between the driving force and the restraining force of secondary recrystallization stably.
  • reducing the content of inhibitor elements will reduce the inhibitory force necessary for primary recrystallization and secondary recrystallization, which leads to increased and non-uniform primary crystal grain diameters and an increase in the secondary recrystallization temperature.
  • the driving force for secondary recrystallization will be reduced, and secondary crystal nuclei will be reduced; if the primary grain diameter is not uniform, the non-Gaussian grains will undergo secondary recrystallization;
  • the increase in the secondary recrystallization temperature means that the heating time before the secondary recrystallization increases, which increases the risk of the inhibitor being coarsened or oxidized, which will cause the magnetic properties of the finished product to degrade or even be scrapped. It is precisely the problem that the magnetic properties are difficult to control stably, and some existing technologies reduce the manufacturing cost by changing the shape of the inclusions precipitated in the slab, such as:
  • the slab heating temperature is 1200 to 1330°C; if the cold-rolled sheet is subjected to nitriding treatment, the heating temperature of the sheet temperature can be further reduced to 1050 to 1150°C.
  • One of the objectives of the present invention is to provide a high magnetic induction oriented silicon steel.
  • the amount of the secondary inhibitor is ensured, and the precipitation form of the primary inhibitor is more finely dispersed, so that the primary grain diameter is more Uniformity, thereby achieving a high level of matching between the primary grain diameter in the secondary recrystallization process and the inhibitor, so that the final product of high magnetic induction oriented silicon steel has a sharp Gauss texture and excellent magnetic properties, which can further reduce manufacturing costs .
  • the present invention proposes a high magnetic induction oriented silicon steel, the mass percentage of chemical elements is:
  • the balance is Fe and other unavoidable impurities.
  • the inventors of the present case conducted an energy spectrum analysis of the coarse MnS+AlN composite inclusions precipitated in the prior art and found that the size of the MnS+AlN composite inclusions is 0.5-3.0 ⁇ m. However, the size of the AlN precipitated alone is usually less than 400nm. This shows that MnS+AlN composite inclusions will significantly increase the difficulty of adjusting the inhibitor morphology, which is not conducive to obtaining excellent magnetic properties.
  • the inventor of the present case optimized the design of the steel composition and improved the precipitation conditions of AlN by controlling the content of Als, N, and Nb elements, so that AlN preferentially adheres to Nb(C,N) instead of MnS to precipitate, reducing MnS+
  • the precipitation amount of AlN composite precipitates promotes the fine dispersion precipitation of AlN as a primary inhibitor, which improves the magnetic properties, so that oriented silicon steel with magnetic induction B 8 >1.93T can be obtained, and the S content in the slab is reduced and once suppressed
  • the improvement of the agent morphology can significantly reduce the manufacturing cost of the inhibitor morphology adjustment and subsequent processes such as high temperature purification annealing.
  • inhibitors use fine precipitates with good thermal stability.
  • inhibitors include manganese sulfide (MnS), copper sulfide (Cu 2 S), aluminum nitride (AlN), some segregated elements
  • MnS manganese sulfide
  • Cu 2 S copper sulfide
  • AlN aluminum nitride
  • Sn and P can also be used as auxiliary inhibitors.
  • MnS manganese sulfide
  • Cu 2 S copper sulfide
  • AlN aluminum nitride
  • Sn and P can also be used as auxiliary inhibitors.
  • the effect of MnS with a high solid solution temperature should be weakened as much as possible.
  • the size of AlN precipitates is smaller and the suppression effect is better. Therefore, AlN is used as the main inhibitor.
  • Inhibitors can be subdivided into primary inhibitors and secondary inhibitors according to the source of acquisition: the primary inhibitors come from the existing precipitates in the slab, which are formed during the steelmaking and casting process, and are part of the slab heating process. Solid solution and precipitation during the rolling process, and adjust the precipitate morphology through hot-rolled sheet annealing, which has an important impact on the primary recrystallization and therefore also affects the magnetic properties of the final product; the secondary inhibitor mainly comes from the decarburization annealing Through the nitriding treatment, the nitrogen is combined with the original aluminum in the steel to form fine and dispersed AlN, (Al,Si)N, (Al,Si,Mn)N and other particles.
  • the secondary inhibitor and the primary inhibitor jointly promote the secondary recrystallization.
  • the driving force determined by the primary grain diameter matches the inhibitory force determined by the inhibitor, the secondary recrystallization Gaussian texture Fengrui, the final product has excellent magnetic properties.
  • Si is the basic element of the oriented silicon steel, which can increase the resistivity and reduce the iron loss.
  • the mass percentage of Si is less than 2.0%, the resistivity decreases, which cannot effectively reduce the eddy current loss of the oriented silicon steel; but if the mass percentage of Si is higher than 4.0%, the brittleness of the steel plate increases due to the tendency of Si to segregate along the grain boundary, which makes The poor rollability will also make the recrystallization structure and inhibitor unstable, resulting in imperfect secondary recrystallization.
  • the mass percentage of Si defined in the high magnetic induction oriented silicon steel of the present invention is 2.0-4.0%.
  • the content of C In the high magnetic induction oriented silicon steel of the present invention, the content of C must match the content of Si, so as to ensure that an appropriate proportion of ⁇ phase is obtained during the hot rolling process. If the mass percentage of C is less than 0.03%, the ⁇ ratio of the hot rolling process is low, which is not conducive to the use of phase change rolling to form a uniform and fine hot-rolled texture; but if the mass percentage of C is higher than 0.07%, coarseness will appear These coarse carbides are difficult to remove in the decarburization process, thus reducing the decarburization efficiency and increasing the decarburization cost. Based on this, the mass percentage of C in the high magnetic induction oriented silicon steel of the present invention is limited to 0.03% to 0.07%.
  • the mass percentage of Als is limited to 0.015 to 0.035%, because Als can form a secondary inhibitor in the subsequent nitriding treatment, and it can be formed by the joint action of the primary inhibitor Sufficient pinning strength promotes secondary recrystallization. Taking into account that when the mass percentage of Als is less than 0.015%, the pinning strength of the inhibitor will be insufficient, and some non-favorable textures will also undergo secondary recrystallization, the magnetic properties will deteriorate, and even secondary recrystallization will not occur; The mass percentage of Als is higher than 0.035%, the nitride of Als will be coarsened, and the inhibitor effect will also decrease. Based on this, in the technical solution of the present invention, the mass percentage of Als is limited to 0.015 to 0.035%.
  • controlling the mass percentage of N at 0.0030 to 0.0100% can form a suitable amount of primary inhibitor AlN, so that the pinning strength of the primary inhibitor matches the decarburization annealing temperature , And then obtain a fine and uniform primary grain diameter.
  • the amount of N added to the steel is for the main purpose of stably controlling the primary grain size.
  • N forms nitrides in the form of AlN, which is an element that forms a primary inhibitor.
  • the mass percentage of N is less than 0.0030%, the amount of primary inhibitor is insufficient, which is not conducive to the formation of fine and uniform primary grain diameters; but when the mass percentage of N exceeds 0.0100%, the cold-rolled steel sheet is prone to bubble defects and increases the refining Steel load. Based on this, in the technical solution of the present invention, the mass percentage of N is limited to 0.003 to 0.010%.
  • Nb is an effective grain refining and microalloying element, which can promote the formation of fine and uniform primary grain diameters, and the formed Nb(C,N) can also be As an auxiliary inhibitor, it reduces the difficulty of adjusting the form of the primary inhibitor.
  • the mass percentage of Nb is less than 0.0010%, the above effect cannot be effectively exerted; but if the mass percentage of Nb exceeds 0.0500%, it has a strong preventive effect on recrystallization, and the secondary recrystallization is not perfect. Therefore, in the present invention In the high magnetic induction oriented silicon steel, the mass percentage of Nb is limited to 0.0010 to 0.0500%.
  • the high magnetic induction oriented silicon steel of the present invention also has at least one of the following chemical elements: Mn: 0.05 to 0.20%, P: 0.01 to 0.08%, Cr: 0.05 to 0.40% , Sn: 0.03 to 0.30%, Cu: 0.01 to 0.40%.
  • Mn is added because, similar to Si, Mn can increase resistivity and reduce eddy current loss. In addition, Mn can also expand the ⁇ phase region, and has the effect of improving hot rolling ductility and microstructure, thereby improving hot rolling rollability.
  • the mass percentage of Mn added is less than 0.05%, the above effect cannot be effectively exerted; and if the mass percentage of Mn added is higher than 0.20%, a mixed dual phase structure of ⁇ and ⁇ is prone to appear, causing phase transformation during annealing Stress and produce ⁇ phase, causing instability of secondary recrystallization. Based on the above reasons, in some preferred embodiments, the mass percentage of Mn added can be preferably set to 0.05% to 0.20%.
  • P is added because: P is a grain boundary segregation element and acts as an auxiliary inhibitor. In the process of secondary recrystallization, P still has the effect of grain boundary segregation even at a high temperature of about 1000 °C, which can delay the premature oxidation and decomposition of AlN, which is beneficial to secondary recrystallization.
  • the mass percentage of P added is less than 0.01%, the above effects cannot be effectively performed; P can also significantly increase the resistivity and reduce the eddy current loss, but if the mass percentage of P added is higher than 0.08%, not only will the nitriding efficiency be reduced , It will also make cold rollability worse. Based on the above reasons, in some preferred embodiments, the mass percentage of added P can be preferably set to 0.01-0.08%.
  • the addition of Cr can increase the resistivity, and also help improve the mechanical properties, and by promoting the oxidation of the steel plate, it can significantly improve the quality of the bottom layer.
  • the mass percentage of Cr added can be higher than 0.05%, but considering that when Cr is added higher than 0.40%, a dense oxide layer will be formed during the decarburization process, which will affect decarburization and Nitriding efficiency. Based on the above reasons, in some preferred embodiments, the mass percentage of Cr added may be preferably set to 0.05 to 0.40%.
  • Sn is added because: Sn is a grain boundary segregation element and acts as an auxiliary inhibitor, which can compensate for the coarsening of AlN precipitates due to increased Si content or thinning of strip thickness. The resulting decrease in restraining force and the expansion of the process window are conducive to the stable magnetic properties of the finished product. Taking into account that the addition amount of Sn by mass percentage is less than 0.03%, the above effects cannot be effectively obtained; while the addition amount of Sn by mass percentage is higher than 0.30%, which will not only affect the decarburization efficiency, but also cause poor bottom layer quality and poor magnetic properties. Will be improved and manufacturing costs will increase. Therefore, in some preferred embodiments, the mass percentage of Sn may preferably be limited to 0.03 to 0.30%.
  • Cu is added because: Cu, similar to Mn, can expand the ⁇ phase region and help to obtain fine AlN precipitates. In addition to expanding the ⁇ phase region, Cu preferentially combines with S to form Cu 2 S than Mn, which has the effect of inhibiting the formation of MnS at a high solid solution temperature. Considering that the mass percentage of Cu added is less than 0.01%, the above-mentioned effects cannot be exerted; but if the mass percentage of Cu added is higher than 0.40%, the manufacturing cost will increase and the magnetic properties will not be improved. Therefore, in some preferred embodiments, the mass percentage of Cu may preferably be set to 0.01 to 0.40%.
  • S is an element that forms precipitates such as MnS, Cu 2 S, etc.
  • appropriate precipitates such as MnS, Cu 2 S are beneficial to suppress the change of the initial grain diameter.
  • the S content is controlled within 0.0050 ⁇ 0.0120%.
  • the inventor of the present case has found through a large number of experimental studies that by reducing the S content in the slab, the effect of suppressing the variation of the primary crystal grain diameter is better, the magnetic properties are improved, and the manufacturing cost can be further reduced. Therefore, preferably, The mass percentage of S is limited to S ⁇ 0.0050%.
  • V and Ti are commonly used steel microalloying elements. V forms VN after nitriding and affects secondary recrystallization, which is not conducive to magnetic properties. However, Ti preferentially precipitates TiN, while MnS will precipitate with TiN, and then AlN will precipitate with MnS, which will easily form coarse MnS+AlN composite inclusions, which is also not conducive to magnetic properties. In addition, reducing the content of Ti and V can also reduce the harmful inclusions of TiN and VN in the finished product. Therefore, in the technical solution of the present invention, the mass percentage of Ti is limited to Ti ⁇ 0.0050%, and the mass percentage of V is limited to: V ⁇ 0.0050%;
  • another object of the present invention is to provide a method for manufacturing the above-mentioned high magnetic induction oriented silicon steel, by which a high magnetic induction oriented silicon steel with excellent magnetic properties can be obtained, and the manufacturing method is low in manufacturing cost.
  • the present invention proposes a method for manufacturing high magnetic induction oriented silicon steel, which includes the steps:
  • steelmaking can be carried out by, for example, a converter or an electric furnace.
  • the molten steel is subjected to secondary refining and continuous casting to obtain a slab, and the obtained slab is heated, as the inhibitor form in the slab is improved , And there is no need to consider the solid solution problem of MnS or Cu 2 S. Therefore, the heating temperature and heating time of the slab heating only need to ensure smooth hot rolling without special consideration of the solid solution amount of the inhibitor.
  • the size of AlN as the primary inhibitor is smaller, and the pinning effect of the inhibitor is better. Therefore, the primary grain diameter is more uniform, which is beneficial to achieve The initial grain diameter is matched with the high level of the inhibitor to improve the magnetic properties of the final product.
  • the slab heating temperature is 1050 to 1250°C, and the slab heating time is less than 300 min.
  • the slab heating temperature is 1050 to 1150°C, and the slab heating time is less than 200 minutes, thereby effectively reducing the manufacturing cost of the slab heating.
  • step (4) the cold rolling reduction rate is ⁇ 85%.
  • the decarburization annealing temperature is 800-900° C., and the time is 90-170 s.
  • step (6) the content of infiltrated nitrogen is 50-260 ppm.
  • the high-temperature annealing temperature is 1050-1250°C
  • the high-temperature annealing time is 15-40h.
  • the above scheme takes into account that if the high temperature annealing temperature is lower than 1050°C, the annealing time needs to be extended, which will reduce the production efficiency and increase the manufacturing cost, which is not conducive to reducing the manufacturing cost; but if the high temperature annealing temperature is higher than 1250°C, the steel coil defects will increase , The magnetic performance will not be improved, and the equipment life will be reduced.
  • the high temperature annealing temperature can preferably be controlled at 1050 to 1200°C.
  • the annealing time is 15-20h.
  • step (3) there is a hot-rolled sheet annealing step between step (3) and step (4), wherein the hot-rolled sheet annealing temperature is 850 to 1150°C, and the hot-rolled sheet The annealing time of the board is 30-200s.
  • a hot-rolled sheet annealing step can be set between step (3) and step (4).
  • the hot-rolled sheet annealing step may not be provided. step.
  • the annealing temperature of the hot-rolled sheet is lower than 850°C, it cannot adjust the structure of the hot-rolled sheet, nor can it effectively adjust the shape of the AlN inhibitor; but if the annealing temperature of the hot-rolled sheet is higher than 1150°C, the hot-rolled sheet The grains after annealing are coarsened, which is not conducive to the first recrystallization.
  • the annealing time of the hot-rolled sheet is less than 30s, it will not be able to effectively adjust the AlN inhibitor morphology and the structure of the hot-rolled sheet due to the short annealing time, and the effect of improving the magnetic properties will not be achieved; but if the annealing time of the hot-rolled sheet is high In 200s, the production efficiency is reduced, and the magnetic performance will not improve. Similarly, since this case reduces the number of coarse MnS+AlN composite inclusions in the hot coil, it can reduce the difficulty of adjusting the morphology of the AlN inhibitor in the hot-rolled sheet annealing process.
  • the annealing temperature of the hot-rolled sheet may preferably be 850 to 1100° C., and the annealing time of the hot-rolled sheet may be preferably 30-160 s.
  • the high magnetic induction oriented silicon steel and the manufacturing method thereof have the following advantages and beneficial effects:
  • the high magnetic induction oriented silicon steel of the present invention through the design of the chemical composition of the silicon steel, not only ensures the amount of the secondary inhibitor, but also makes the precipitation form of the primary inhibitor smaller and dispersed, so that the primary grain diameter is more uniform, and the secondary
  • the primary grain diameter in the recrystallization process matches the high level of the inhibitor, so that the final high magnetic induction oriented silicon steel has a sharp Gauss texture and excellent magnetic properties, which can further reduce manufacturing costs.
  • the manufacturing method of the present invention also has the above-mentioned advantages and beneficial effects.
  • Figure 1 shows the morphology of the coarse MnS+AlN composite inclusions obtained by the prior art.
  • Figure 1 shows the morphology of the coarse MnS+AlN composite inclusions obtained by the prior art.
  • the size of the precipitated coarse MnS+AlN composite inclusions is 0.5-3.0 ⁇ m, and according to the results of the energy spectrum analysis method, the position 1 marked in the figure is mainly Mn, S, Ti element, and the positions 2, 3, 4, 5, 6, 7, 8, 9, and 10 indicated in the figure are Al and N elements. Since the size of the separated AlN is usually less than 400nm, it indicates that the coarse MnS+AlN composite inclusions will significantly increase the difficulty of adjusting the inhibitor morphology, which is not conducive to obtaining excellent magnetic properties.
  • the inventor of the present case believes that the precipitation conditions of AlN can be improved by controlling the content of elements such as Als, N, S, Ti, V and Nb, so that AlN preferentially depends on Nb(C,N) instead of MnS to precipitate, thereby reducing coarseness
  • the precipitation amount of MnS+AlN composite inclusions promotes the fine dispersion and precipitation of the primary inhibitor AlN, which improves the magnetic properties, and can obtain oriented silicon steel with magnetic induction B 8 >1.93T, and due to the reduction of the S content in the slab and the primary suppression
  • the improvement of the agent morphology can significantly reduce the manufacturing cost of the inhibitor morphology adjustment and high temperature purification annealing process.
  • the average primary grain diameter and the standard deviation of the average primary grain diameter are obtained by the following methods: after obtaining the primary grain size metallographic photo; by area method analysis, the average primary grain diameter and the standard deviation of the average primary grain diameter are obtained.
  • P 17/50 and B 8 are obtained by using Epstein square circle to measure the magnetic properties of electrical steel sheet (strip) specified in the national standard GB/T 3655.
  • Hot-rolled annealing annealing temperature of hot-rolled sheet is 1120°C, annealing time is 170s, and then cooling;
  • the decarburization temperature is 810 ⁇ 880°C
  • the decarburization time is 90 ⁇ 170s
  • the content of [C] in the steel plate is reduced to less than 30ppm
  • Nitriding treatment the infiltration nitrogen content is between 131 ⁇ 210ppm;
  • Coating MgO coating coating MgO coating on the steel plate
  • Insulating coating and flattening annealing After uncoiling, coating insulating coating and hot-stretching flattening annealing to obtain high magnetic induction oriented silicon steel.
  • Table 1 lists the mass percentage ratios of the chemical elements of the high magnetic induction oriented silicon steels of Examples A1-A11 and the comparative silicon steels of Comparative Examples B1-B7.
  • Table 2 lists the average primary grain diameter and the coefficient of variation of primary grain diameter involved in A1-A11 and Comparative Examples B1-B7, and the magnetic properties P 17/50 and B 8 of the finished product.
  • the examples A1-A11 of this case are due to the slab composition Als, N, S, V, Ti and Nb, and the average primary grain diameter and primary grain size.
  • the steel plate whose grain diameter variation coefficient meets the requirements has generally good magnetic properties, with higher magnetic induction B 8 and lower iron loss P 17/50 .
  • Hot-rolled annealing annealing temperature of hot-rolled sheet is 1120°C, annealing time is 190s, and then cooling;
  • Nitriding treatment the infiltration nitrogen content is between 138 ⁇ 173ppm;
  • Coating MgO coating coating MgO coating on the steel plate
  • Insulating coating and flattening annealing After uncoiling, coating the insulating coating and hot-stretching flattening annealing to obtain the oriented silicon steel product.
  • Example A12 in Table 3 "Table 1-A1", which means that Example A12 is smelted with the same chemical elements in the table as Example A1.
  • Table 1-A1 the slab composition of Example A12 in Table 3 "Table 1-A1”
  • Example A12 is smelted with the same chemical elements in the table as Example A1.
  • Other examples and comparisons The proportions of the slab composition can be deduced by analogy and will not be repeated here.
  • Hot-rolled annealing annealing temperature of hot-rolled sheet is 1100°C, annealing time is 150s, and then cooling;
  • decarburization temperature is 840°C
  • decarburization time is 150s
  • the content of [C] in the steel plate is reduced to less than 30ppm
  • Nitriding treatment the infiltration nitrogen content is between 146 ⁇ 186ppm;
  • Coating MgO coating coating MgO coating on the steel plate
  • High temperature annealing perform high temperature purification annealing for 20 hours under the conditions of an atmosphere of 100% H 2 and a temperature of 1200°C;
  • Insulating coating and flattening annealing After uncoiling, coating the insulating coating and hot-stretching flattening annealing to obtain the oriented silicon steel product.
  • Hot-rolled annealing annealing the hot-rolled sheet according to the annealing temperature and time shown in Table 5, followed by cooling;
  • decarburization temperature is 830°C
  • decarburization time is 155s
  • the content of [C] in the steel plate is reduced to less than 30ppm
  • Nitriding treatment the infiltration nitrogen content is between 133 ⁇ 182ppm;
  • Coating MgO coating coating MgO coating on the steel plate
  • High-temperature annealing perform high-temperature purification annealing for 20 hours under the conditions of an atmosphere of 100% H 2 and a temperature of 1210°C;
  • Insulating coating and flattening annealing After uncoiling, coating the insulating coating and hot-stretching flattening annealing to obtain the oriented silicon steel product.
  • the high magnetic induction oriented silicon steel of Examples A19-A22 can obtain excellent magnetic properties even if the heating temperature of the hot-rolled sheet is reduced or the heating time of the hot-rolled sheet is shortened, while the comparative silicon steel of Comparative Examples B18-B21 When the annealing temperature of the hot-rolled sheet is reduced or the annealing time of the hot-rolled sheet is shortened, the magnetic properties are also degraded to varying degrees.
  • Hot-rolled annealing annealing temperature of hot-rolled sheet is 1100°C, annealing time is 160s, and then cooling;
  • the decarburization temperature is 835°C
  • the decarburization time is 155s
  • the [C] content in the steel plate is reduced to less than 30ppm
  • Nitriding treatment the infiltration nitrogen content is between 134 ⁇ 196ppm;
  • Coating MgO coating coating MgO coating on the steel plate
  • Insulating coating and flattening annealing After uncoiling, coating the insulating coating and hot-stretching flattening annealing to obtain the oriented silicon steel product.
  • the high magnetic induction oriented silicon steel of Examples A23-A30 even if the high temperature purification annealing temperature is reduced or the high temperature purification annealing time is shortened, the residual S content in the finished product is less than 10 ppm, and there is no significant difference in magnetic properties.
  • the comparative silicon steels of comparative examples B22-B33 when the high-temperature purification annealing temperature is reduced or the purification annealing time is shortened, the magnetic properties are deteriorated to different degrees, and the residual S content in the finished product is relatively high.
  • Decarburization annealing Use the process parameters shown in Table 7 for decarburization annealing to reduce the content of [C] in the steel plate to less than 30 ppm;
  • Nitriding treatment the infiltration nitrogen content is between 131 ⁇ 192ppm;
  • Coating MgO coating coating MgO coating on the steel plate
  • High temperature annealing high temperature purification annealing for 20 hours under the conditions of an atmosphere of 100% H 2 and a temperature of 1200°C;
  • Insulation coating and flattening annealing After uncoiling, coating the insulating coating and hot-stretching flattening annealing to obtain the oriented silicon steel product.
  • the coefficient of variation of the primary crystal grain diameter average primary crystal grain diameter/standard deviation of the primary crystal grain diameter.
  • the high magnetic induction oriented silicon steel of the present invention not only ensures the amount of the secondary inhibitor, but also makes the precipitation form of the primary inhibitor smaller and dispersed, so that the primary grain The diameter is more uniform, and the average primary grain diameter in the secondary recrystallization process is matched with the high level of the inhibitor, so that the finished product of high magnetic induction oriented silicon steel has sharp Gauss texture and excellent magnetic properties. Further reduce manufacturing costs.
  • the manufacturing method of the present invention also has the above-mentioned advantages and beneficial effects.

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Abstract

一种高磁感取向硅钢，其化学元素质量百分比为：Si：2.0～4.0％；C：0.03～0.07％；Als：0.015～0.035％；N：0.003～0.010％；Nb：0.0010～0.0500％；余量为Fe和其他不可避免的杂质。该高磁感取向硅钢的制造方法包括步骤：(1)冶炼和铸造；(2)板坯加热；(3)热轧；(4)冷轧；(5)脱碳退火；(6)渗氮处理；(7)涂覆MgO涂层；(8)高温退火；(9)绝缘涂层；其中，制造方法使得高磁感取向硅钢平均初次晶粒直径为14～22μm，初次晶粒直径变动系数大于1.8，初次晶粒直径变动系数＝平均初次晶粒直径/初次晶粒直径的标准偏差。

Description

一种高磁感取向硅钢及其制造方法 技术领域
本发明涉及一种钢种及其制造方法，尤其涉及一种取向硅钢及其制造方法。
背景技术
取向硅钢是电力和国防工业不可或缺的软磁材料，由具有被称为高斯(Goss)织构的晶粒组成，其高斯织构用Miller指数表示为{110}<001>，晶粒的{110}晶面平行于轧制平面，晶粒的<001>晶向平行于轧制方向，从而在定向磁场下具有最佳的易磁化性能，充分利用磁晶各向异性实现多晶体材料的最佳磁性能。采取取向硅钢制成动力变压器或传输变压器中的铁心，在定向磁场的工况下，其极高的磁感和极低的铁损可显著节省材料和电能。取向硅钢通常采用铁损P 17/50和磁感B 8来表征磁性能水平，其中 P17/50表示在最大磁感应强度为1.7T、频率为50Hz时，单位Kg试样的铁损；B 8表示对应于磁场强度为800A/m时的磁感应强度。
按照磁感B 8进行区分，取向硅钢可分为普通取向硅钢(B 8＜1.88T)和高磁感取向硅钢(B 8≥1.88T)两大类。其中，传统的高磁感取向硅钢为高温板坯加热工艺，其不足之处在于：为了使抑制剂充分固溶，板坯的加热温度通常需达到1400℃，而这是传统加热炉的极限水平。此外，由于板坯加热温度高，导致加热炉利用率低、寿命短，硅在晶界偏析、热卷边裂严重、成材率低、能源消耗大、制造成本高。
鉴于存在上述问题，因而，越来越多的研究致力于如何降低取向硅钢加热温度。目前，按照板坯加热温度范围来区分，其主要改进路径有两种：一种是中温板坯加热工艺，板坯加热温度在1250～1320℃，采用AlN和Cu 2S作为抑制剂；另一种是低温板坯加热工艺，板坯加热温度在1100～1250℃，在后工序采用渗氮方法导入抑制剂。其中，低温板坯加热工艺，由于可以实现较低成本地生产制造高磁感取向硅钢，因而，其应用较多。
而低温板坯加热工艺的主要难点在于抑制剂的选择与形态控制，尽管低温板坯加热工艺具有明显的制造成本与成材率优势，但与高温板坯加热工艺相比，抑制剂的不稳定因素显著增多，例如，在浇铸过程中形成的粗大析出物，例如TiN为核心的MnS+AlN复合析出物在后续退火中难以固溶，抑制剂的抑制效果降低，导致初次晶粒直径的控制难度增大，还可能存在渗氮量分布不均匀等问题，这导致在高温退火过程中通过氮扩散形成的抑制剂AlN、(Al,Si)N、(Al,Si,Mn)等分布不均匀，反映在产品质量上表现为沿板宽和卷长方向的磁性能不均匀。与高温生产工艺相比，低温板坯加热工艺要求抑制剂形成元素如成分Als等元素的控制范围达ppm级，并对脱碳退火后的初次晶粒直径和渗氮量提出苛刻要求，对制造工艺与技术装备要求高。由于技术难度显著增加，通常低温板坯加热工艺的高磁感取向硅钢典型磁感B 8介于1.88～1.92T，低于同类高温工艺产品的磁感，且氧化膜等缺陷发生率也相对较高。
低温板坯加热的一些改进工艺聚焦进一步提升产品等级，如减薄带钢厚度、提高硅含量、刻痕细化磁畴、快速感应加热等，为了获得高品质，这些技术会一定程度增加投资或制造成本；另一些改进工艺则专注于从炼钢源头降低抑制剂元素含量并优化热处理工艺，以进一步降低制造成本，如：
公开号为CN1708594，公开日为2005年12月14日，名称为“方向性电磁钢板的制造方法以及方向性电磁钢板”的中国专利文献公开了一种技术方案，其可以被认为“无抑制剂法”的高磁感取向硅钢制造方法。在该专利文献所公开的技术方案中，板坯成分包含质量％计的C：0.08％以下，Si：2.0～8.0％，Mn：0.005％～3.0％，使Al在100ppm以下，并且使N、S和Se分别在50ppm以下，余量为Fe及不可避免的杂质。该技术方案在冷轧板退火过程中未进行渗氮操作，并可以使板坯加热温度降低至1250℃以下，还因为C、N、S、Se、Al含量低，可以有效降低高温退火工序制造成本。虽然上述的制造方法工序简单、制造成本下降，但产品等级不高且存在磁性能不稳定的问题，所有实施例中的磁感B 8均低于1.91T。而为了解决无抑制剂法工艺磁性能不稳定的问题，需要额外添加改进工艺，势必不可避免地又增加了制造成本。
公开号为CN101573458，公开日为2009年11月4日，名称为“高生产率地生产具有优异磁特性的晶粒定向电工钢板的方法”的中国专利文献公开了一种技术方案，其可以被称为“低温板坯半固溶渗氮法”高磁感取向硅钢制造方 法。在该专利文献所公开的技术方案中，板坯成分包含质量％计的C：0.04～0.07％，Si：2.0～4.0％，P：0.02～0.075％，Cr：0.05～0.35％，酸可溶Al：0.020～0.040％，Mn：低于0.20％，N：低于0.0055％，S：低于0.0055％，余量为Fe及不可避免的杂质。该技术方案将板坯加热至板坯中的析出物部分溶解的温度，要求板坯加热过程溶解的N量介于0.0010～0.0040％，随后经热轧、热轧板退火、冷轧，在氨气、氢气和氮气的混合气氛中同时脱碳和氮化退火，再进行高温退火得到成品。该技术方案将板坯中N和S的含量控制在低水平，控制有效抑制剂的量和形态，使平均初次晶粒直径为18～30μm，在获得优异磁性能的同时可以大幅缩短高温退火时间。由于S含量较低，因此可以减轻高温退火过程中的脱S负荷，但考虑到该技术方案中包含冷轧板的渗氮退火处理，实际上很难大幅缩短高温退火过程中的净化退火时间。此外，为了控制板坯加热过程溶解的N量，还要求板坯加热温度为1050～1250℃。
提升取向硅钢的产品等级和降低制造成本往往难以兼得。上述的专利文献中，难点在于如何稳定实现二次再结晶的驱动力与抑制力高水平匹配。通常，降低抑制剂元素含量，会降低初次再结晶和二次再结晶所必须的抑制力，这导致初次晶粒直径增大且不均匀，二次再结晶温度提高。如果平均初次晶粒直径过大，会降低二次再结晶的驱动力，二次晶核会减少；如果初次晶粒直径不均匀，非高斯位向的晶粒会发生二次再结晶；如果二次再结晶温度提高，意味着二次再结晶前的升温时间增加，增加了抑制剂粗化或被氧化的风险，这些都会导致成品磁性能降级甚至报废。正是存在磁性能难以稳定控制的问题，还有一些现有技术通过采取改变板坯中析出的夹杂物形态来降低制造成本，如：
公开号为CN103805918A，公开日为2014年5月21日，名称为“一种高磁感取向硅钢及其生产方法”的中国专利文献公开了一种高磁感取向硅钢及其生产方法。在该专利文献所公开的技术方案中，板坯成分包含质量％计的C：0.035～0.120％，Si：2.5～4.5％，Mn：0.05～0.20％，S：0.005～0.050％，Als：0.015～0.035％，N：0.003～0.010％，Sn：0.03～0.30％，Cu：0.01～0.50％，通过控制微量元素，使V：低于0.0100％，Ti：低于0.0100％，Sb+Bi+Nb+Mo：0.0025～0.0250％，且(Sb/121.8+Bi/209.0+Nb/92.9+Mo/95.9)/(Ti/47.9+V/50.9)＝0.1～15，使板坯中尺寸粗大的析出物数量大幅度减少，可以降低板坯加热温度100～150℃。如果冷轧板不进行渗氮处理，板坯加热温度为1200～1330℃； 如果冷轧板进行渗氮处理，板温加热温度可进一步降低至1050～1150℃。
发明内容
本发明的目的之一在于提供一种高磁感取向硅钢，通过对硅钢化学成分的设计，既保证了二次抑制剂量，又使一次抑制剂析出形态更为细小弥散，使初次晶粒直径更加均匀，进而实现二次再结晶过程中的初次晶粒直径与抑制剂的高水平匹配，使得最终获得的高磁感取向硅钢的成品高斯织构锋锐、磁性能优异，还可进一步降低制造成本。
为了实现上述目的，本发明提出了一种高磁感取向硅钢，其化学元素质量百分比为：
Si：2.0～4.0％；
C：0.03～0.07％；
Als：0.015～0.035％；
N：0.003～0.010％；
Nb：0.0010～0.0500％；
余量为Fe和其他不可避免的杂质。
本案发明人通过对现有技术中析出的粗大MnS+AlN复合夹杂物进行能谱分析发现，MnS+AlN复合夹杂物的尺寸为0.5～3.0μm，然而，单独析出的AlN尺寸通常小于400nm，由此说明，MnS+AlN复合夹杂物会显著增加抑制剂形态的调整难度，不利于获得优异的磁性能。
基于该发现，本案发明人通过对钢成分进行优化设计，通过控制Als、N、Nb元素含量从而改善AlN的析出条件，使AlN优先依附Nb(C,N)而非MnS析出，减少了MnS+AlN的复合析出物析出数量，促使作为一次抑制剂的AlN细小弥散析出，使磁性能得到改善，从而可以获得磁感B 8＞1.93T的取向硅钢，并由于板坯中S含量降低和一次抑制剂形态改善，从而可以明显降低抑制剂形态调整和后续的例如高温净化退火等工序的制造成本。
需要说明的是，抑制剂利用具有良好热稳定性的微细析出物，本技术领域当中，抑制剂包括硫化锰(MnS)、硫化铜(Cu 2S)、氮化铝(AlN)，一些偏析元素例如Sn、P也可以被用于辅助抑制剂。在选择抑制剂时，要尽可能弱化固溶温度高的MnS的作用。此外，相比MnS和Cu 2S，由于AlN析出物的 尺寸更为细小，抑制效果更好，因此，采用AlN作为主要抑制剂。根据获取来源可以将抑制剂细分为一次抑制剂和二次抑制剂：一次抑制剂来源于板坯中已有的析出物，这些析出物在炼钢浇铸过程中形成，在板坯加热过程部分固溶并在轧制过程中析出，并通过热轧板退火调整析出物形态，对初次再结晶有着重要影响从而也会影响最终产品的磁性能；而二次抑制剂主要来源于脱碳退火后通过渗氮处理，使氮与钢中原有的铝结合，形成细小弥散的AlN、(Al,Si)N、(Al,Si,Mn)N等质点。在高温退火过程中，二次抑制剂与一次抑制剂共同促进二次再结晶，当由初次晶粒直径决定的驱动力与由抑制剂决定的抑制力相匹配时，二次再结晶高斯织构锋锐，最终产品的磁性能优异。
此外，本发明所述的高磁感取向硅钢的各化学元素的设计原理具体如下所述：
Si：在本发明所述的高磁感取向硅钢中，Si是取向硅钢的基础元素，其可以提高电阻率并降低铁损。当Si的质量百分比低于2.0％，电阻率下降，不能有效降低取向硅钢的涡流损耗；但若Si的质量百分比高于4.0％，由于Si有沿晶界偏聚的倾向导致钢板脆性增加，使可轧性变差，还会使再结晶组织和抑制剂变得不稳定，造成二次再结晶不完善。基于此，在本发明所述的高磁感取向硅钢中限定的Si的质量百分比在2.0-4.0％。
C：在本发明所述的高磁感取向硅钢中，C含量要与Si含量匹配，从而确保热轧过程获得适当比例的γ相。若C的质量百分比低于0.03％，热轧过程的γ相比例低，不利于利用相变轧制形成均一精细的热轧织构；但若C的质量百分比高于0.07％，则会出现粗大的碳化物质点，这些粗大的碳化物很难在脱碳工序被去除，因而降低脱碳效率进而增加脱碳成本。基于此，在本发明所述的高磁感取向硅钢中C的质量百分比被限定在0.03％～0.07％。
Als：对本发明所述的高磁感取向硅钢中，将Als的质量百分比限定在0.015～0.035％，是因为：Als在后续渗氮处理中可以形成二次抑制剂，与一次抑制剂共同作用形成足够的钉扎强度促进二次再结晶。考虑到当Als的质量百分比低于0.015％时，会导致抑制剂的钉扎强度不够，一些非有利织构也会发生二次再结晶，磁性能劣化，甚至不能发生二次再结晶；而若Als的质量百分比高于0.035％，Als的氮化物会粗化，抑制剂效果也会下降。基于此，在本发明所述的技术方案中，Als的质量百分比被限定为0.015～0.035％。
N：在本发明所述的高磁感取向硅钢中，控制N的质量百分比在0.0030～0.0100％，可以形成合适数量的一次抑制剂AlN，使得一次抑制剂的钉扎强度和脱碳退火温度匹配，进而获得细小均匀的初次晶粒直径。钢中添加的N量以稳定控制初次晶粒直径为主要目的，N形成AlN等形式的氮化物，是形成一次抑制剂的元素。若N的质量百分比低于0.0030％，则一次抑制剂量不足，不利于形成细小均匀的初次晶粒直径；但当N的质量百分比超过0.0100％，则冷轧钢板容易出现气泡类缺陷，并增加炼钢负荷。基于此，在本发明所述的技术方案中，N的质量百分比被限定为0.003～0.010％。
Nb：在本发明所述的高磁感取向硅钢中，Nb是有效的细化晶粒微合金化元素，可以促进形成细小均匀的初次晶粒直径，同时形成的Nb(C,N)还可以作为辅助抑制剂，降低了对一次抑制剂形态的调整难度。当Nb的质量百分比低于0.0010％，则不能有效地发挥上述作用；但若Nb的质量百分比超过0.0500％，则对再结晶有强烈的阻止作用，二次再结晶不完善，因此，在本发明所述的高磁感取向硅钢中，Nb的质量百分比被限定为0.0010～0.0500％。
进一步地，在本发明所述的高磁感取向硅钢中，其还具有下述各化学元素的至少其中之一：Mn：0.05～0.20％，P：0.01～0.08％，Cr：0.05～0.40％，Sn：0.03～0.30％，Cu：0.01～0.40％。
Mn：在一些优选的实施方式中，添加Mn是因为：Mn与Si类似可以提高电阻率降低涡流损耗。此外，Mn还可以扩大γ相区，具有改善热轧塑性和组织的效果进而提高热轧可轧性。但若添加的Mn的质量百分比低于0.05％，则不能有效地发挥上述作用；而若添加的Mn的质量百分比高于0.20％，则易出现α和γ混合双相组织，退火时造成相变应力并产生γ相，造成二次再结晶不稳定。基于上述理由，在一些优选的实施方式中，添加Mn的质量百分比可以优选地设置为0.05％～0.20％。
P：在一些优选的实施方式中，添加P是因为：P为晶界偏析元素，有辅助抑制剂的作用。P在二次再结晶过程中，即使在约1000℃的高温下仍有晶界偏析的作用，可以延缓AlN过早氧化分解，有利于二次再结晶。但若P添加的质量百分比低于0.01％，则不能有效地发挥上述作用；P还可以明显提高电阻率，降低涡流损耗，但若P的添加质量百分比高于0.08％，不但会降低渗氮效率，还会使冷轧可轧性变差。基于上述理由，在一些优选的实施方式中，添 加P的质量百分比可以优选地设置为0.01～0.08％。
Cr：在一些优选的实施方式中，添加Cr可以提高电阻率，又有利于改善力学性能，并通过促进钢板氧化，可明显改善底层质量。为了使Cr的作用充分发挥出来，添加Cr的质量百分比可以高于0.05％，但考虑到当添加Cr高于0.40％，则会在脱碳过程中形成致密的氧化物层，会影响脱碳和渗氮效率。基于上述理由，在一些优选的实施方式中，添加Cr的质量百分比可以优选地设置为0.05～0.40％。
Sn：在一些优选的实施方式中，添加Sn是因为：Sn是晶界偏析元素，有辅助抑制剂的作用，可以弥补因Si含量提高或带钢厚度减薄等情况下，AlN析出物粗化导致的抑制力下降的问题，扩大工艺窗口，有利于成品磁性能稳定。考虑到Sn的质量百分比添加量低于0.03％，则不能有效获得上述效果；而Sn的质量百分比添加量高于0.30％，不但会影响脱碳效率，还会造成底层质量不良，磁性能也不会得到改善，制造成本增加。因而，在一些优选的实施方式中，Sn的质量百分比可以优选地被限定为0.03～0.30％。
Cu：在一些优选的实施方式中，添加Cu是因为：Cu与Mn类似可以扩大γ相区，有助于获得细小AlN析出物。Cu除扩大γ相区外，比Mn优先与S结合形成Cu 2S，具有抑制高固溶温度MnS形成的作用。考虑到添加Cu的质量百分比低于0.01％，不能发挥其上述作用；但若添加Cu的质量百分比高于0.40％，则制造成本增加，磁性能也不会得到改善。因此，在一些优选的实施方式中，Cu的质量百分比可以优选地被设置为0.01～0.40％。
进一步地，在本发明所述的高磁感取向硅钢中，在其它不可避免的杂质中，S≤0.0050％，V≤0.0050％，Ti≤0.0050％。
S：在本发明所述的技术方案中，考虑到S是形成MnS、Cu 2S等析出物的元素，通常认为，合适的MnS、Cu 2S等析出物有利于抑制初次晶粒直径变动，并将S含量控制在0.0050～0.0120％。然而，本案发明人通过大量试验研究发现，通过降低板坯中的S含量，抑制初次晶粒直径变动的效果更好，磁性能改善，而且还可以进一步降低制造成本，因此，优选地，可以将S的质量百分比限定在S≤0.0050％。
V和Ti：V和Ti是常用的钢微合金化元素。V在渗氮处理后形成VN影响二次再结晶，不利于磁性能。而Ti由于其优先析出TiN，而MnS会依附TiN 析出，随后AlN又会依附MnS析出，从而容易形成粗大的MnS+AlN复合夹杂物，也不利于磁性能。此外，降低Ti、V的含量，还可以降低成品中TiN以及VN的有害夹杂物。因此，在本发明所述的技术方案中，Ti的质量百分比被限定为Ti≤0.0050％，V的质量百分比被限定为：V≤0.0050％；
进一步地，在本发明所述的高磁感取向硅钢中，其铁损P 17/50≤0.28+2.5×板厚[mm]W/kg，磁感B 8≥1.93T。
相应地，本发明的另一目的在于提供一种上述的高磁感取向硅钢的制造方法，通过该制造方法可以获得磁性能优异的高磁感取向硅钢，且该制造方法制造成本低。
为了实现上述目的，本发明提出了一种高磁感取向硅钢的制造方法，其包括步骤：
(1)冶炼和铸造；
(2)板坯加热；
(3)热轧；
(4)冷轧；
(5)脱碳退火；
(6)渗氮处理；
(7)涂覆MgO涂层；
(8)高温退火；
(9)绝缘涂层和平整退火；
其中，所述制造方法使得高磁感取向硅钢平均初次晶粒直径为14～22μm，初次晶粒直径变动系数大于1.8，其中初次晶粒直径变动系数＝平均初次晶粒直径/初次晶粒直径的标准偏差。
在本发明所述的制造方法中，可以例如通过转炉或电炉进行炼钢，钢水经二次精炼和连铸后获得板坯，将获得的板坯进行加热，由于板坯中抑制剂形态得到改善，且无需考虑MnS或Cu 2S的固溶问题，因此，板坯加热的加热温度和加热时间只要保证能够顺利热轧即可，而无需特别考虑抑制剂的固溶量。
需要说明的是，在本发明所述的技术方案中，作为一次抑制剂的AlN的尺寸更为细小，抑制剂的钉扎效果更好，因此，初次晶粒直径更为均匀，这有利于实现初次晶粒直径与抑制剂的高水平匹配，使最终成品磁性能得到改善。
进一步地，在本发明所述的制造方法中，在步骤(2)中，板坯加热温度为1050～1250℃，板坯加热时间低于300min。
在一些优选的实施方式中，板坯加热温度为1050～1150℃，板坯加热时间低于200min，从而有效降低板坯加热的制造成本。
进一步地，在本发明所述的制造方法中，在步骤(4)中，冷轧压下率≥85％。
进一步地，在本发明所述的制造方法中，在步骤(5)中，脱碳退火温度为800～900℃，时间为90～170s。
进一步地，在本发明所述的制造方法中，在步骤(6)中，渗入氮含量为50～260ppm。
进一步地，在本发明所述的制造方法中，在步骤(8)中，高温退火温度为1050～1250℃，高温退火时间为15～40h。
上述方案，是考虑到若高温退火温度低于1050℃，需要延长退火时间，会生产效率降低，制造成本增加，不利于降低制造成本；但若高温退火温度高于1250℃，则钢卷缺陷增多，磁性能也不会得到改善，还会降低设备寿命。
由于本案的制造方法所获得的初次晶粒直径更加均匀，可以降低二次再结晶的温度，并由于S含量控制在低水平，因而，优选地可以将高温退火温度控制在1050～1200℃，高温退火时间为15～20h。
进一步地，在本发明任意一项所述的制造方法中，在步骤(3)和步骤(4)之间还具有热轧板退火步骤，其中热轧板退火温度为850～1150℃，热轧板退火时间为30～200s。
上述方案中，在步骤(3)和步骤(4)之间可以设置热轧板退火步骤，当然在一些实施方式中，若对磁性能要求不高的情况下，也可以不设置热轧板退火步骤。
考虑到热轧板退火温度低于850℃，则无法起到调整热轧板组织的作用，也不能有效调整AlN抑制剂的形态；但若热轧板退火温度高于1150℃，则热轧板退火后的晶粒粗大化，不利于初次再结晶。此外，热轧板退火时间低于30s，则会由于退火时间过短不能有效调整AlN抑制剂形态和热轧板组织，也就达不到改善磁性能的效果；但若热轧板退火时间高于200s，生产效率降低，且磁性能也不会改善。同样地，由于本案减少了热卷中粗大MnS+AlN复合夹杂物数 量，因而，可以降低热轧板退火工序调整AlN抑制剂形态的难度。
在一些优选的实施方式中，热轧板退火温度可以优选在850～1100℃，热轧板退火时间优选在30～160s。
本发明所述的高磁感取向硅钢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：
本发明所述的高磁感取向硅钢通过对硅钢化学成分的设计，既保证了二次抑制剂量，又使一次抑制剂析出形态更为细小弥散，使初次晶粒直径更加均匀，进而实现二次再结晶过程中的初次晶粒直径与抑制剂的高水平匹配，进而使得最终获得的高磁感取向硅钢的成品高斯织构锋锐、磁性能优异，还可进一步降低制造成本。
此外，本发明所述的制造方法也同样具有上述的优点以及有益效果。
附图说明
图1显示了采用现有技术获得的粗大的MnS+AlN复合夹杂物的形貌。
具体实施方式
下面将结合说明书附图和具体的实施例对本发明所述的高磁感取向硅钢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。
图1显示了采用现有技术获得的粗大的MnS+AlN复合夹杂物的形貌。
如图1所示，在现有技术中，析出的粗大MnS+AlN复合夹杂物的尺寸在0.5～3.0μm，并且根据能谱分析法结果，图中标示的位置1处主要为Mn、S、Ti元素，而图中标示的位置2、3、4、5、6、7、8、9、10处为Al、N元素。由于通常单独析出的AlN尺寸小于400nm，说明粗大MnS+AlN复合夹杂物会显著增加抑制剂形态的调整难度，不利于获得优异的磁性能。
基于上述发现，本案发明人认为可以通过控制例如Als、N、S、Ti、V和Nb元素含量来改善AlN的析出条件，使AlN优先依附Nb(C,N)而非MnS析出，从而减少粗大的MnS+AlN复合夹杂物的析出数量，促使一次抑制剂AlN细小弥散析出，使磁性能得到改善，可以获得磁感B 8＞1.93T的取向硅钢，并由于板坯中S含量降低和一次抑制剂形态改善，可以明显降低抑制剂形态调整 和高温净化退火工序的制造成本。
测试方法
1、平均初次晶粒直径和初次晶粒直径的标准偏差
平均初次晶粒直径和平均初次晶粒直径的标准偏差通过以下方法获得：在获得初次晶粒尺寸金相照片后；通过面积法分析获得平均初次晶粒直径及平均初次晶粒直径的标准偏差。
2、P 17/50和B 8
采用国标标准GB/T 3655中规定的用爱泼斯坦方圈测量电工钢片(带)磁性能的方法获得P 17/50和B 8。
实施例A1-A11以及对比例B1-B7
按照下列步骤制造实施例A1-A11的高磁感取向硅钢以及对比例B1-B7的对比硅钢：
(1)冶炼和铸造：按照表1所示成分采用转炉或电炉冶炼，连铸成板坯；
(2)板坯加热：板坯在1150℃以下加热200min；
(3)热轧至2.3mm的热轧板；
(4)热轧退火：热轧板退火温度1120℃，退火时间170s，随后冷却；
(5)冷轧：冷轧到成品厚度0.29mm，冷轧压下率为87.4％；
(6)脱碳退火：脱碳温度为810～880℃，脱碳时间为90～170s，将钢板中的[C]含量降到30ppm以下；
(7)渗氮处理：渗入氮含量介于131～210ppm；
(8)涂覆MgO涂层：在钢板上涂覆MgO涂层；
(9)高温退火：在气氛为100％H 2、温度为1200℃的条件下进行25小时的高温净化退火；
(10)绝缘涂层和平整退火：开卷后涂敷绝缘涂层以及热拉伸平整退火后得到高磁感取向硅钢。
表1列出了实施例A1-A11的高磁感取向硅钢以及对比例B1-B7的对比硅钢的各化学元素的质量百分配比。
表1.(wt％，余量为Fe和除S、V、Ti以外的其他杂质)
Figure PCTCN2020108333-appb-000001
Figure PCTCN2020108333-appb-000002
表2列出了A1-A11以及对比例B1-B7中所涉及的平均初次晶粒直径及初次晶粒直径变动系数和成品磁性能P 17/50、B 8。
表2.
Figure PCTCN2020108333-appb-000003
Figure PCTCN2020108333-appb-000004
结合表1和表2可以看出，本案的实施例A1-A11，尤其是一些优选的实施例由于板坯成分Als、N、S、V、Ti和Nb，及平均初次晶粒直径和初次晶粒直径变动系数满足要求的钢板，磁性能普遍很好，具有更高的磁感B 8和更低的铁损P 17/50。
实施例A12-A14以及对比例B8-B13
实施例A12-A14的高磁感取向硅钢以及对比例B8-B13的对比硅钢具体制造步骤如下：
(1)冶炼和铸造：按照表3所示成分采用转炉或电炉冶炼，连铸成板坯；
(2)板坯加热：板坯在1150℃以下加热210min；
(3)热轧至2.6mm的热轧板；
(4)热轧退火：热轧板退火温度1120℃，退火时间190s，随后冷却；
(5)冷轧：冷轧到成品厚度0.27mm，冷轧压下率为89.6％；
(6)脱碳退火：按表3所示的脱碳温度和脱碳时间进行，将钢板中的[C]含量降到30ppm以下；
(7)渗氮处理：渗入氮含量介于138～173ppm；
(8)涂覆MgO涂层：在钢板上涂覆MgO涂层；
(9)高温退火：在气氛为100％H 2、温度为1200℃的条件下进行25小时的高温净化退火；
(10)绝缘涂层和平整退火：开卷后涂敷绝缘涂层以及热拉伸平整退火后得到取向硅钢成品。
需要说明的是，例如，实施例A12在表3中的板坯成分“表1-A1”，其表示实施例A12采用表中与实施例A1相同的各化学元素成分冶炼，其他实施例以及对比例的板坯成分以此类推，不再赘述。
表3
Figure PCTCN2020108333-appb-000005
Figure PCTCN2020108333-appb-000006
由表3可以看出，通过调整脱碳温度和脱碳时间，使平均初次晶粒直径和初次晶粒直径变动系数满足要求的实施例A12-A14的高磁感取向硅钢，可以获得的磁性能更为优异，具有更高的磁感B 8和更低的铁损P 17/50。
实施例A15-A18以及对比例B14-B17
实施例A15-A18的高磁感取向硅钢以及对比例B14-B17的对比硅钢具体制造步骤如下：
(1)冶炼和铸造：按照表4所示成分采用转炉或电炉冶炼，连铸成板坯；
(2)板坯加热：按照表4所示的参数加热板坯；
(3)热轧至2.4mm的热轧板；
(4)热轧退火：热轧板退火温度1100℃，退火时间150s，随后冷却；
(5)冷轧：冷轧到成品厚度0.29mm，冷轧压下率为87.9％；
(6)脱碳退火：脱碳温度为840℃，脱碳时间为150s，将钢板中的[C]含量降到30ppm以下；
(7)渗氮处理：渗入氮含量介于146～186ppm；
(8)涂覆MgO涂层：在钢板上涂覆MgO涂层；
(9)高温退火：在气氛为100％H 2、温度为1200℃的条件下进行20小时的高温净化退火；
(10)绝缘涂层和平整退火：开卷后涂敷绝缘涂层以及热拉伸平整退火后得到取向硅钢成品。
表4.
Figure PCTCN2020108333-appb-000007
Figure PCTCN2020108333-appb-000008
由表4可以看出，实施例A15-A18的高磁感取向硅钢，即使板坯加热温度降低或板坯加热时间缩短也能获得优异的磁性能，而对比例B14-B17的对比硅钢由于采用的化学元素成分非本案所限定的范围，因而当板坯温度降低或板坯加热时间缩短时，磁性能出现不同程度地劣化。
实施例A19-A22以及对比例B18-B21
实施例A19-A22的高磁感取向硅钢以及对比例B18-B21的对比硅钢具体制造步骤如下：
(1)冶炼和铸造：按照表5所示成分采用转炉或电炉冶炼，连铸成板坯；
(2)板坯加热：板坯在1120℃以下加热210min；
(3)热轧至2.5mm的热轧板；
(4)热轧退火：按照表5所示的退火温度和时间进行热轧板退火，随后冷却；
(5)冷轧：冷轧到成品厚度0.23mm，冷轧压下率为90.8％；
(6)脱碳退火：脱碳温度为830℃，脱碳时间为155s，将钢板中的[C]含量降到30ppm以下；
(7)渗氮处理：渗入氮含量介于133～182ppm；
(8)涂覆MgO涂层：在钢板上涂覆MgO涂层；
(9)高温退火：在气氛为100％H 2、温度为1210℃的条件下进行20小时的高温净化退火；
(10)绝缘涂层和平整退火：开卷后涂敷绝缘涂层以及热拉伸平整退火后得到取向硅钢成品。
表5
Figure PCTCN2020108333-appb-000009
Figure PCTCN2020108333-appb-000010
由表5可以看出，实施例A19-A22的高磁感取向硅钢，即使热轧板加热温度降低或热轧板加热时间缩短也能获得优异的磁性能，而对比例B18-B21的对比硅钢则在热轧板退火温度降低或热轧板退火时间缩短，磁性能也有不同程度地劣化。
实施例A23-A30以及对比例B22-B33
实施例A23-A30的高磁感取向硅钢以及对比例B22-B33的对比硅钢具体制造步骤如下：
(1)冶炼和铸造：按照表6所示成分采用转炉或电炉冶炼，连铸成板坯；
(2)板坯加热：板坯在1120℃以下加热210min；
(3)热轧至2.6mm的热轧板；
(4)热轧退火：热轧板退火温度1100℃，退火时间160s，随后冷却；
(5)冷轧：冷轧到成品厚度0.23mm，冷轧压下率为91.2％；
(6)脱碳退火：脱碳温度为835℃，脱碳时间为155s，将钢板中的[C]含量降到30ppm以下；
(7)渗氮处理：渗入氮含量介于134～196ppm；
(8)涂覆MgO涂层：在钢板上涂覆MgO涂层；
(9)高温退火：在气氛为100％H 2，按表6所示的温度和时间进行高温净化退火；
(10)绝缘涂层和平整退火：开卷后涂敷绝缘涂层以及热拉伸平整退火后得到取向硅钢成品。
表6
Figure PCTCN2020108333-appb-000011
Figure PCTCN2020108333-appb-000012
由表6可以看出，实施例A23-A30的高磁感取向硅钢，即使高温净化退火温度降低或高温净化退火时间缩短，成品中残留的S含量均小于10ppm，且磁性能没有明显差异，而对比例B22-B33的对比硅钢则在高温净化退火温度降低或净化退火时间缩短，磁性能有不同程度地劣化，成品中残留的S含量也相对较高。
实施例A31-A33以及对比例B34-B37
实施例A31-A33的高磁感取向硅钢以及对比例B34-B37的对比硅钢具体制造步骤如下：
(1)冶炼和铸造：按照表7所示成分采用转炉或电炉冶炼，连铸成板坯；
(2)板坯加热：板坯在1100℃以下加热180min；
(3)热轧至2.3mm的热轧板；
(4)冷轧：冷轧到成品厚度0.30mm，冷轧压下率去87.0％；
(5)脱碳退火：采用表7所示工艺参数进行脱碳退火，将钢板中的[C]含量降到30ppm以下；
(6)渗氮处理：渗入氮含量介于131～192ppm；
(7)涂覆MgO涂层：在钢板上涂覆MgO涂层；
(8)高温退火：在气氛为100％H 2、温度为1200℃的条件下进行20小时的高温净化退火；
(9)绝缘涂层和平整退火：开卷后涂敷绝缘涂层以及热拉伸平整退火后得到取向硅钢成品。
表7
Figure PCTCN2020108333-appb-000013
由表7可以看出，实施例A31-A33的高磁感取向硅钢在不进行热轧板退火，通过调整平均初次晶粒直径，也能获得高磁感取向硅钢，而对于对比例B34-B37的对比硅钢在不进行热轧板退火后，由于一次抑制剂的抑制力弱，初次晶粒直径不均匀，磁性能差。
需要说明的是，上述实施例中，初次晶粒直径变动系数＝平均初次晶粒直径/初次晶粒直径的标准偏差。
综上所述可以看出，本发明所述的高磁感取向硅钢通过对硅钢化学成分的设计，既保证了二次抑制剂量，又使一次抑制剂析出形态更为细小弥散，使初次晶粒直径更加均匀，进而实现二次再结晶过程中的平均初次晶粒直径与抑制剂的高水平匹配，进而使得最终获得的高磁感取向硅钢的成品高斯织构锋锐、磁性能优异，还可进一步降低制造成本。
此外，本发明所述的制造方法也同样具有上述的优点以及有益效果。
需要说明的是，本发明的保护范围中现有技术部分并不局限于本申请文件 所给出的实施例，所有不与本发明的方案相矛盾的现有技术，包括但不局限于在先专利文献、在先公开出版物，在先公开使用等等，都可纳入本发明的保护范围。
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 (11)

  1. 一种高磁感取向硅钢，其特征在于，其化学元素质量百分比为：
    Si：2.0～4.0％；
    C：0.03～0.07％；
    Als：0.015～0.035％；
    N：0.003～0.010％；
    Nb：0.0010～0.0500％；
    余量为Fe和其他不可避免的杂质。
  2. 如权利要求1所述的高磁感取向硅钢，其特征在于，其还具有下述各化学元素的至少其中之一：Mn：0.05～0.20％，P：0.01～0.08％，Cr：0.05～0.40％，Sn：0.03～0.30％，Cu：0.01～0.40％。
  3. 如权利要求1所述的高磁感取向硅钢，其特征在于，在其他不可避免的杂质中，S≤0.0050％，V≤0.0050％，Ti≤0.0050％。
  4. 如权利要求1-3中任意一项所述的高磁感取向硅钢，其特征在于，其铁损P 17/50≤(0.28+2.5×t)W/kg，其中t表示板厚，单位参量为mm；磁感B 8≥1.93T。
  5. 如权利要求1-4中任意一项所述的高磁感取向硅钢的制造方法，其特征在于，包括步骤：
    (1)冶炼和铸造；
    (2)板坯加热；
    (3)热轧；
    (4)冷轧；
    (5)脱碳退火；
    (6)渗氮处理；
    (7)涂覆MgO涂层；
    (8)高温退火；
    (9)绝缘涂层；
    其中，所述制造方法使得高磁感取向硅钢平均初次晶粒直径为14～22μm，初次晶粒直径变动系数大于1.8，其中初次晶粒直径变动系数＝ 平均初次晶粒直径/初次晶粒直径的标准偏差。
  6. 如权利要求5所述的制造方法，其特征在于，在所述步骤(2)中，板坯加热温度为1050～1250℃，板坯加热时间低于300min。
  7. 如权利要求5所述的制造方法，其特征在于，在所述步骤(4)中，冷轧压下率≥85％。
  8. 如权利要求5所述的制造方法，其特征在于，在所述步骤(5)中，脱碳退火温度为800～900℃，时间为90～170s。
  9. 如权利要求5所述的制造方法，其特征在于，在所述步骤(6)中，渗入氮含量为50～260ppm。
  10. 如权利要求5所述的制造方法，其特征在于，在所述步骤(8)中，高温退火温度为1050～1250℃，高温退火时间为15～40h。
  11. 如权利要求5-10中任意一项所述的制造方法，其特征在于，在步骤(3)和步骤(4)之间还具有热轧板退火步骤，其中热轧板退火温度为850～1150℃，热轧板退火时间为30～200s。
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