CN116219272A - A kind of high magnetic induction grain-oriented silicon steel and preparation method thereof - Google Patents
A kind of high magnetic induction grain-oriented silicon steel and preparation method thereof Download PDFInfo
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Abstract
本申请涉及一种高磁感取向硅钢，所述取向硅钢的钢水成分以质量分数计包括：C：0.02％～0.08％；Si：3.0％～3.5％；Mn：0.02％～0.18％；S：0.005％～0.020％；Al：0.020％～0.042％；N：0.015％～0.040％；Sn：0.08％～0.3％；Cu：0.1％～0.9％。该高磁感取向硅钢通过形成取向硅钢中重要的抑制剂AlN、MnS、Cu2S，改善磁性；通过C元素使热轧和常化时钢中含有一定量的奥氏体，从而获得大量细小的AlN和Cu2S；通过Si提高电阻率，大幅度降低铁损；通过Sn元素增强抑制剂对晶界的钉扎作用，改善磁性。
This application relates to a high magnetic induction oriented silicon steel. The molten steel composition of the oriented silicon steel includes: C: 0.02%-0.08%; Si: 3.0%-3.5%; Mn: 0.02%-0.18%; S: 0.005% to 0.020%; Al: 0.020% to 0.042%; N: 0.015% to 0.040%; Sn: 0.08% to 0.3%; Cu: 0.1% to 0.9%. The high magnetic induction oriented silicon steel improves the magnetic properties by forming the important inhibitors AlN, MnS and Cu 2 S in the oriented silicon steel; through the C element, the steel contains a certain amount of austenite during hot rolling and normalization, so as to obtain a large amount of fine AlN and Cu 2 S; the resistivity is increased by Si, and the iron loss is greatly reduced; the pinning effect of the inhibitor on the grain boundary is enhanced by the Sn element, and the magnetic properties are improved.
Description
Technical Field
The application relates to the field of oriented silicon steel, in particular to high-magnetic induction oriented silicon steel and a preparation method thereof.
Background
The oriented silicon steel is an electrical material with Si content of about 3%, has strong {110} <001> texture, has high magnetic induction and low iron loss, is an important soft magnetic material widely applied in the electronic power industry, and is mainly used for large transformers, reactors and magnetic amplifiers.
Future development of oriented silicon steel requires further improvement of magnetic properties to significantly reduce loss in energy transmission, which requires reduction of thickness of silicon steel sheet, improvement of magnetic induction and reduction of iron loss, but as the thickness of silicon steel sheet is further reduced, the influence of surface on secondary recrystallization is also gradually enhanced, resulting in reduction of secondary grain orientation accuracy and deterioration of magnetic properties. Therefore, the thin gauge oriented silicon steel needs to have higher suppression power than the thick gauge oriented silicon steel, that is, needs to have higher suppression power than conventional AlN, mnS, etc. inhibitors.
Disclosure of Invention
The application provides high-magnetic-induction oriented silicon steel and a preparation method thereof, which are used for solving the problem of insufficient magnetic performance of the existing high-magnetic-induction oriented silicon steel.
In a first aspect, the present application provides a high magnetic induction oriented silicon steel, the molten steel component of the oriented silicon steel includes, in mass fraction: c:0.02% -0.08%; si:3.0 to 3.5 percent; mn:0.02% -0.18%; s: 0.005-0.020%; al:0.020% -0.042%; n:0.015 to 0.040 percent; sn:0.08 to 0.3 percent; cu:0.1 to 0.9 percent.
Further, the molten steel component of the oriented silicon steel comprises the following components in percentage by mass: c:0.02% -0.08%; si:3.0 to 3.3 percent; mn:0.04 to 0.90 percent; s:0.01 to 0.015 percent; al:0.020 to 0.030 percent; n:0.015 to 0.025 percent; sn:0.08 to 0.2 percent; cu:0.1 to 0.9 percent.
Further, the molten steel component of the oriented silicon steel further comprises at least one of the following components: cr:0.01 to 0.2 percent; sb:0.01 to 0.08 percent; mo:0.01 to 0.08 percent; bi:0.01 to 0.08 percent; as:0.01% -0.05%; p:0.05 to 0.3 percent.
In a second aspect, the present application provides a method for preparing high magnetic induction oriented silicon steel, which is used for preparing the high magnetic induction oriented silicon steel according to any one of the embodiments of the first aspect, the method includes:
pouring molten steel into a tundish after being calmed, and carrying out thin strip continuous casting to obtain a thin strip blank;
carrying out hot rolling, cooling and curling on the Bao Daipi to obtain a hot rolled plate;
carrying out normalizing treatment, acid washing and cold rolling on the hot rolled plate to obtain a cold rolled plate;
and carrying out decarburization annealing, high-temperature annealing and insulating layer coating on the cold-rolled sheet to obtain the high-magnetic induction oriented silicon steel.
Further, the reaction parameters of the continuous strip casting include: the pulling speed is 70-100m/min, and the temperature for guiding out the thin strip blank is 1300-1400 ℃; and/or
The thickness of the thin strip blank is 2-3mm.
Further, the reaction parameters of the hot rolling include: the hot rolling temperature is 1050-1150 ℃, the rolling reduction is 25-67%, and the final rolling temperature is 900-1000 ℃; and/or
The thickness of the hot rolled plate is 1-1.5mm.
Further, the normalizing treatment is divided into a first segment normalizing treatment and a second segment normalizing treatment;
the first-stage normalized reaction parameters include: the temperature is 1050-1150 ℃ and the time is 0.5-5min;
the second-stage normalized reaction parameters include: the temperature is 850-1000 deg.C, and the time is 0-1min.
Further, the reaction parameters of the pickling include: the pickling solution is HCl with the volume concentration of 3-7%, the temperature of the pickling solution is 70-90 ℃, and the pickling time is 0.5-1.5min; and/or
The reaction parameters of the cold rolling include: the total rolling reduction is 80% -95%; and/or
The thickness of the cold-rolled sheet is 0.10-0.20mm.
Further, the reaction parameters of the decarburization annealing include: the temperature rising rate is 20-50 ℃/s, the decarburization temperature is 780-880 ℃, and the heat preservation time is 1-4min; and/or
The decarburization annealing atmosphere is H with volume fraction of 60-75% 2 And 25-40% by volume of N 2 The dew point temperature of the decarburization annealing atmosphere is 40-60 ℃.
Further, the high temperature annealing includes: coating MgO release agent on the cold-rolled sheet after decarburization annealing, then preserving heat for 1-2 hours at 600-800 ℃, then heating to 960 ℃ at a heating rate of 15-40 ℃/h, then preserving heat for 10-40 hours at 10-20 ℃/h to 1200 ℃, then cooling to 600 ℃ at 50-60 ℃/h, and then cooling to below 200 ℃ along with a furnace; wherein,,
the atmosphere before heating to 1100 ℃ is 25-40% N by volume 2 And 60-75% by volume of H 2 The atmosphere after the temperature is raised to 1100 ℃ and the heat preservation is finished to 1200 ℃ is full H 2 Atmosphere, after the end of the heat preservation at 1200 ℃ until the temperature is cooled to 600 ℃, the atmosphere is H with the volume fraction of 75-85 percent 2 And 15-25% by volume of N 2 The atmosphere after cooling to 600 ℃ to below 200 ℃ was pure nitrogen.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
according to the high-magnetic induction oriented silicon steel provided by the embodiment of the application, a certain amount of austenite is contained in the steel during hot rolling and normalizing through the element C, so that a large amount of fine AlN and Cu are obtained 2 S, S; the resistivity is improved through Si, so that the iron loss is greatly reduced; al and N form an important inhibitor AlN in the oriented silicon steel,meanwhile, al can improve the resistivity of the steel; the resistivity of the oriented silicon steel is improved through Mn, and meanwhile, an important inhibitor MnS in the oriented silicon steel is formed with S element, so that the magnetism is improved; the pinning effect of the Sn element enhancement inhibitor on the grain boundary is utilized to inhibit the normal growth of primary recrystallized grains and improve the magnetism; formation of Cu by Cu element and S element 2 S inhibitor can inhibit the normal growth of primary recrystallized grains, obtain high-proportion Goss texture and improve magnetic performance. Therefore, the high-magnetic-induction oriented silicon steel improves the stability of the inhibitor in the decarburization and high-temperature annealing process by enhancing the inhibition force of the inhibitor, thereby improving the magnetic performance.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
Fig. 1 is a schematic flow chart of a method for preparing high magnetic induction oriented silicon steel according to an embodiment of the present application.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
Unless specifically indicated otherwise, the various raw materials, reagents, instruments, equipment, and the like used in this application are commercially available or may be prepared by existing methods.
In a first aspect, embodiments of the present application provide a high magnetic induction oriented silicon steel, wherein a molten steel component of the oriented silicon steel includes, in mass fraction: c:0.02% -0.08%; si:3.0 to 3.5 percent; mn:0.02% -0.18%; s: 0.005-0.020%; al:0.020% -0.042%; n:0.015 to 0.040 percent; sn:0.08 to 0.3 percent; cu:0.1 to 0.9 percent.
According to the high-magnetic induction oriented silicon steel provided by the embodiment of the application, a certain amount of austenite is contained in the steel during hot rolling and normalizing through the element C, so that a large amount of fine AlN and Cu are obtained 2 S, S; the resistivity is improved through Si, so that the iron loss is greatly reduced; al and N form an important inhibitor AlN in the oriented silicon steel, and meanwhile, the Al can improve the resistivity of the steel; the resistivity of the oriented silicon steel is improved through Mn, and meanwhile, an important inhibitor MnS in the oriented silicon steel is formed with S element, so that the magnetism is improved; the pinning effect of the Sn element enhancement inhibitor on the grain boundary is utilized to inhibit the normal growth of primary recrystallized grains and improve the magnetism; formation of Cu by Cu element and S element 2 S inhibitor can inhibit the normal growth of primary recrystallized grains, obtain high-proportion Goss texture and improve magnetic performance. Therefore, the high-magnetic-induction oriented silicon steel improves the stability of the inhibitor in the decarburization and high-temperature annealing process by enhancing the inhibition force of the inhibitor, thereby improving the magnetic performance.
C is an austenite stabilizing element, and in this application, the amount of C is added to the molten steel in order to ensure that the steel contains a certain amount of austenite during hot rolling and normalizing. Ensuring a certain amount of austenite phase in the steel during hot rolling and normalizing, which is beneficial to obtaining a large amount of fine AlN and Cu 2 S, S. However, too high a C content makes decarburization difficult. Therefore, the C content is defined to be 0.02% to 0.08%.
Si can improve resistivity, greatly reduce iron loss, promote graphitization of carbon in steel by adding Si, reduce bonding and aging phenomena among steel plates, but the content of Si can reduce saturation induction intensity, and meanwhile, the increase of the content of Si can lead to uneven structure of a hot rolled plate and increase brittleness of steel. Therefore, the content of Si element in the present application is defined to be 3.0% to 3.5%.
Al and N form an important inhibitor AlN in the oriented silicon steel, and a large amount of AlN precipitates during normalization, and meanwhile, the resistivity of the Al can be improved. Too low contents of Al and N elements may result in too low contents of inhibitors, and incomplete secondary recrystallization. Too high an Al content tends to deteriorate the quality of the underlayer, and if too high an N content results in surface defects of the product. Therefore, the contents of the Al element and the N element are defined as Al:0.020% -0.042%; n:0.015 to 0.040 percent.
Mn can improve the resistivity of the oriented silicon steel, and forms an important inhibitor MnS in the oriented silicon steel with S element, so that the primary recrystallization structure of the oriented silicon steel is perfected, the (111) surface texture is reduced, and the magnetism is improved. However, if the manganese-sulfur ratio is kept too low, the oriented silicon steel is liable to be thermally brittle during hot rolling, and generally needs to be more than 3. Therefore, the contents of Mn element and S element are defined as Mn:0.02% -0.18%; s: 0.005-0.020%.
Sn element can be subjected to segregation at the interfaces of crystal grains and precipitated phases in the high-magnetic-induction oriented silicon steel matrix, the pinning effect of the inhibitor on the crystal boundaries is enhanced, the normal growth of primary recrystallized crystal grains is inhibited, and the magnetism can be effectively improved. Since the rapid solidification process is adopted, the addition amount of Sn element can be increased appropriately to enhance the grain boundary inhibition capability. However, sn addition deteriorates the quality of the bottom layer of the glass film on the surface of the steel strip. Therefore, the content of Sn element is defined as Sn in the present application: 0.08 to 0.3 percent.
Cu is an element for enlarging an austenite phase region, and forms Cu with S element 2 S inhibitor can inhibit the normal growth of primary recrystallized grains, obtain high-proportion Goss texture and improve magnetic performance. Meanwhile, the problem that Sn is added to deteriorate the quality of the bottom layer of the glass film on the surface of the steel belt can be greatly solved. Therefore, the content of Cu element is defined as Cu:0.1 to 0.9 percent.
The molten steel component of the oriented silicon steel in the application comprises C, si, mn, S, al, N, sn, cu, and the rest is Fe and unavoidable acrobatics.
As an implementation mode of the embodiment of the invention, the molten steel component of the oriented silicon steel comprises the following components in percentage by mass: c:0.02% -0.08%; si:3.0 to 3.3 percent; mn:0.04 to 0.90 percent; s:0.01 to 0.015 percent; al:0.020 to 0.030 percent; n:0.015 to 0.025 percent; sn:0.08 to 0.2 percent; cu:0.1 to 0.9 percent.
As an implementation mode of the embodiment of the invention, the molten steel component of the oriented silicon steel further comprises at least one of the following components: cr:0.01 to 0.2 percent; sb:0.01 to 0.08 percent; mo:0.01 to 0.08 percent; bi:0.01 to 0.08 percent; as:0.01% -0.05%; p:0.05 to 0.3 percent.
In a second aspect, the present application provides a method for preparing high magnetic induction oriented silicon steel, which is used for preparing the high magnetic induction oriented silicon steel according to any one of the embodiments of the first aspect, as shown in fig. 1, and the preparation method includes:
pouring molten steel into a tundish after being calmed, and carrying out thin strip continuous casting to obtain a thin strip blank;
carrying out hot rolling, cooling and curling on the Bao Daipi to obtain a hot rolled plate;
carrying out normalizing treatment, acid washing and cold rolling on the hot rolled plate to obtain a cold rolled plate;
and carrying out decarburization annealing, high-temperature annealing and insulating layer coating on the cold-rolled sheet to obtain the high-magnetic induction oriented silicon steel.
In the application, the characteristic of rapid solidification of the strip continuous casting process is utilized, so that the solidification structure of the strip blank is homogeneous and fine, the inhibitor forming element and the segregation facilitating element are in a solid solution state, and the fine and dispersed inhibitor is separated out in the subsequent normalizing and annealing stages, so that the defect of uneven distribution of the inhibitor caused by nitriding in the prior art is overcome. In addition, the surface effect is enhanced due to the thickness reduction, and the curing effect of the inhibitor is remarkable. Compared with the low-temperature high-magnetic induction oriented silicon steel, the production cost is greatly reduced due to the shortened working procedure and the reduced energy consumption, the strict requirements of steel components are reduced, and the magnetic performance of the product is improved.
In the application, inert gas is used for protecting the whole process from casting to rolling, so that oxidation loss is reduced, and the yield is improved. In the present application, after the insulating coating is applied, the magnetic domains of the oriented silicon steel may be selectively refined by one of a laser irradiation method, a plasma spraying method, a shot blasting method, and the like.
As an implementation manner of the embodiment of the present invention, the reaction parameters of the continuous strip casting include: the pulling speed is 70-100m/min, and the temperature for guiding out the thin strip blank is 1300-1400 ℃; and/or
The thickness of the thin strip blank is 2-3mm.
In some embodiments, the draw speed may be 70m/min, 75m/min, 80m/min, 85m/min, 90m/min, 95m/min, 100m/min, etc., and the exit temperature of the thin strip may be 1300 ℃, 1310 ℃, 1320 ℃, 1330 ℃, 1340 ℃, 1350 ℃, 1360 ℃, 1370 ℃, 1380 ℃, 1390 ℃, 1400 ℃, etc.
As an implementation of the embodiment of the present invention, the reaction parameters of the hot rolling include: the hot rolling temperature is 1050-1150 ℃, the rolling reduction is 25-67%, and the final rolling temperature is 900-1000 ℃; and/or
The thickness of the hot rolled plate is 1-1.5mm.
In some embodiments, the hot rolling temperature may be 1050 ℃, 1060 ℃, 1070 ℃, 1080 ℃, 1090 ℃, 1100 ℃, 1110 ℃, 1120 ℃, 1130 ℃, 1140 ℃, 1150 ℃, etc., the reduction may be 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 67%, etc., and the finishing temperature may be 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, 950 ℃, 960 ℃, 970 ℃, 980 ℃, 990 ℃, 1000 ℃, etc.
As an implementation of the embodiment of the present invention, the normalization process is divided into a first stage normalization and a second stage normalization;
the first-stage normalized reaction parameters include: the temperature is 1050-1150 ℃ and the time is 0.5-5min;
the second-stage normalized reaction parameters include: the temperature is 850-1000 deg.C, and the time is 0-1min.
As an implementation mode of the embodiment of the invention, the reaction parameters of the acid washing include: the pickling solution is HCl with the volume concentration of 3-7%, the temperature of the pickling solution is 70-90 ℃, and the pickling time is 0.5-1.5min; and/or
The reaction parameters of the cold rolling include: the total rolling reduction is 80% -95%; and/or
The thickness of the cold-rolled sheet is 0.10-0.20mm.
As an embodiment of the present embodiment, the reaction parameters of the decarburization annealing include: the temperature rising rate is 20-50 ℃/s, the decarburization temperature is 780-880 ℃, and the heat preservation time is 1-4min; and/or
The decarburization annealing atmosphere is H with volume fraction of 60-75% 2 And 25-40% by volume of N 2 The dew point temperature of the decarburization annealing atmosphere is 40-60 ℃.
In some embodiments, the heating rate may be 20 ℃/s, 25 ℃/s, 30 ℃/s, 35 ℃/s, 40 ℃/s, 45 ℃/s, 50 ℃/s, etc., the decarburization temperature may be 780 ℃, 790 ℃, 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, etc., and the holding time may be 1min, 2min, 3min, 4min, etc.
As an implementation of the embodiment of the present invention, the high temperature annealing includes: coating MgO release agent on the cold-rolled sheet after decarburization annealing, then preserving heat for 1-2 hours at 600-800 ℃, then heating to 960 ℃ at a heating rate of 15-40 ℃/h, then preserving heat for 10-40 hours at 10-20 ℃/h to 1200 ℃, then cooling to 600 ℃ at 50-60 ℃/h, and then cooling to below 200 ℃ along with a furnace; wherein,,
the atmosphere before heating to 1100 ℃ is 25-40% N by volume 2 And 60-75% by volume of H 2 The atmosphere after the temperature is raised to 1100 ℃ and the heat preservation is finished to 1200 ℃ is full H 2 Atmosphere, after the end of the heat preservation at 1200 ℃ until the temperature is cooled to 600 ℃, the atmosphere is H with the volume fraction of 75-85 percent 2 And 15-25% by volume of N 2 The atmosphere after cooling to 600 ℃ to below 200 ℃ was pure nitrogen.
The present application is further illustrated below in conjunction with specific examples. It should be understood that these examples are illustrative only of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
A high magnetic induction oriented silicon steel and a preparation method thereof specifically comprise the following steps:
(1) The molten steel with qualified component smelting (the molten steel components are shown in table 1) is sedated for 25min, molten steel is poured into a tundish from a ladle through a long nozzle, molten steel in the tundish is poured between two rollers of a double-roller thin-strip continuous casting machine through a submerged nozzle, a thin strip blank with the thickness of 3mm is produced by the double-roller thin-strip continuous casting machine, the pulling speed is 85m/min, and the leading-out temperature of the thin strip blank is 1350 ℃;
(2) Hot rolling the thin strip at 1100 ℃, wherein the total rolling reduction is 50%, the final rolling temperature is about 950 ℃, then cooling with mist water with the cooling speed of 70 ℃/s, and then curling at 520 ℃ to obtain a hot rolled plate with the thickness of 1.5 mm;
(3) Normalizing the hot-rolled plate at 1050 ℃ for 180 seconds, normalizing at 950 ℃ for 40 seconds, pickling in HCl with the volume concentration of 5% at 80 ℃ for 50 seconds, and then cold-rolling and controlling the total deformation to 87%, thereby obtaining a cold-rolled plate with the thickness of 0.2 mm;
(4) Alkali washing and drying the cold-rolled sheet in sodium hydroxide solution, and then increasing the temperature to 870 ℃ at a heating rate of 35 ℃/s for decarburization annealing for 3min, wherein the decarburization annealing atmosphere comprises 70% of H by volume fraction 2 And a volume fraction of N of 30% 2 Composition, dew point temperature 50 ℃;
(5) Coating MgO release agent on the decarburized and annealed cold-rolled sheet, and then carrying out high-temperature annealing in a hood-type annealing furnace, wherein the atmosphere of the hood-type annealing furnace is H with the volume fraction of 75 percent 2 And 25% by volume of N 2 The hood-type annealing furnace is firstly heated to 600 ℃ for 2 hours, then heated to 960 ℃ at the heating rate of 20 ℃/H, then heated to 1100 ℃ at the heating rate of 10 ℃/H, and then the atmosphere is converted into pure H 2 And heating to 1200 ℃ at 10 ℃ per hour, preserving heat for 25 hours, and then converting the atmosphere into H with the volume fraction of 75 percent 2 And 25% by volume of N 2 And cooled to 600 c at 55 c/h, after which the atmosphere was switched to pure nitrogen and taken out with furnace cooling to 180 c.
Example 2
A high magnetic induction oriented silicon steel and a preparation method thereof specifically comprise the following steps:
(1) The molten steel with qualified component smelting (the molten steel components are shown in table 1) is sedated for 25min, molten steel is poured into a tundish from a ladle through a long nozzle, molten steel in the tundish is poured between two rollers of a double-roller thin-strip continuous casting machine through a submerged nozzle, a thin strip billet with the thickness of 2.5mm is produced by the double-roller thin-strip continuous casting machine, the pulling speed is 70m/min, and the export temperature of the thin strip billet is 1300 ℃;
(2) Hot rolling the thin strip at 1050 ℃, wherein the total rolling reduction is 60%, the final rolling temperature is 950 ℃, then cooling with mist water with the cooling speed of 70 ℃/s, and then curling at 550 ℃ to obtain a hot rolled plate with the thickness of 1 mm;
(3) Normalizing the hot-rolled plate at 1100 ℃ for 150 seconds, normalizing the hot-rolled plate at 900 ℃ for 50 seconds, pickling the hot-rolled plate in HCl with the volume concentration of 5% at 70 ℃ for 50 seconds, and then cold-rolling the hot-rolled plate and controlling the total deformation to be 85%, thereby obtaining a cold-rolled plate with the thickness of 0.15 mm;
(4) Alkali washing and drying the cold-rolled sheet in sodium hydroxide solution, and then raising the temperature to 850 ℃ at a heating rate of 35 ℃/s for decarburization annealing for 4min, wherein the decarburization annealing atmosphere comprises 70% of H by volume 2 And a volume fraction of N of 30% 2 Composition, dew point temperature 50 ℃;
(5) Coating MgO release agent on the decarburized and annealed cold-rolled sheet, and then carrying out high-temperature annealing in a hood-type annealing furnace, wherein the atmosphere of the hood-type annealing furnace is H with the volume fraction of 75 percent 2 And 25% by volume of N 2 The hood-type annealing furnace is firstly heated to 600 ℃ for 2 hours, then heated to 960 ℃ at the heating rate of 20 ℃/H, then heated to 1100 ℃ at the heating rate of 10 ℃/H, and then the atmosphere is converted into pure H 2 And heating to 1200 ℃ at 10 ℃ per hour, preserving heat for 25 hours, and then converting the atmosphere into H with the volume fraction of 75 percent 2 And 25% by volume of N 2 And cooled to 600 c at 55 c/h, after which the atmosphere was switched to pure nitrogen and taken out with furnace cooling to 190 c.
Example 3
A high magnetic induction oriented silicon steel and a preparation method thereof specifically comprise the following steps:
(1) The molten steel with qualified component smelting (the molten steel components are shown in table 1) is sedated for 25min, molten steel is poured into a tundish from a ladle through a long nozzle, molten steel in the tundish is poured between two rollers of a double-roller thin-strip continuous casting machine through a submerged nozzle, a thin strip billet with the thickness of 2mm is produced by the double-roller thin-strip continuous casting machine, the pulling speed is 100m/min, and the export temperature of the thin strip billet is 1400 ℃;
(2) Hot rolling the thin strip at 1150 ℃, wherein the total rolling reduction is 50%, the final rolling temperature is 950 ℃, then cooling with mist water with the cooling speed of 70 ℃/s, and then curling at 580 ℃ to obtain a hot rolled plate with the thickness of 1 mm;
(3) Normalizing the hot-rolled plate at 1100 ℃ for 180 seconds, normalizing at 900 ℃ for 40 seconds, pickling in HCl with the volume concentration of 5% at 90 ℃ for 50 seconds, and then cold-rolling and controlling the total deformation to be 90%, so as to obtain a cold-rolled plate with the thickness of 0.1 mm;
(4) Alkali washing and drying the cold-rolled sheet in sodium hydroxide solution, and then raising the temperature to 850 ℃ at a heating rate of 35 ℃/s for decarburization annealing for 4min, wherein the decarburization annealing atmosphere comprises 70% of H by volume 2 And a volume fraction of N of 30% 2 Composition, dew point temperature 50 ℃;
(5) Coating MgO release agent on the decarburized and annealed cold-rolled sheet, and then carrying out high-temperature annealing in a hood-type annealing furnace, wherein the atmosphere of the hood-type annealing furnace is H with the volume fraction of 75 percent 2 And 25% by volume of N 2 The hood-type annealing furnace is firstly heated to 600 ℃ for 2 hours, then heated to 960 ℃ at the heating rate of 20 ℃/H, then heated to 1100 ℃ at the heating rate of 10 ℃/H, and then the atmosphere is converted into pure H 2 And heating to 1200 ℃ at 10 ℃ per hour, preserving heat for 25 hours, and then converting the atmosphere into H with the volume fraction of 75 percent 2 And 25% by volume of N 2 And cooled to 600 c at 55 c/h, after which the atmosphere was switched to pure nitrogen and taken out with furnace cooling to 195 c.
Comparative example 1
The molten steel composition in example 1 was adjusted to the molten steel composition of comparative example 1 in table 1, and the rest was the same as in example 1.
TABLE 1 molten steel composition (wt%) in examples and comparative examples
| C | Si | Mn | S | Als | N | Cu | Sn | |
| Example 1 | 0.057 | 3.10 | 0.07 | 0.011 | 0.021 | 0.016 | 0.22 | 0.08 |
| Example 2 | 0.062 | 3.07 | 0.05 | 0.013 | 0.023 | 0.017 | 0.43 | 0.15 |
| Example 3 | 0.059 | 3.01 | 0.06 | 0.014 | 0.024 | 0.015 | 0.51 | 0.18 |
| Comparative example 1 | 0.061 | 3.30 | 0.10 | 0.015 | 0.027 | 0.018 | / | / |
The high magnetic induction oriented silicon steel obtained in the examples and the comparative examples was subjected to magnetic property test, and the results are shown in table 2,
table 2 magnetic properties test results of high magnetic induction oriented silicon steel obtained in examples and comparative examples
In summary, the inhibitor inhibition force can be enhanced by improving the Sn content and the Cu content, the stability of the inhibitor in the decarburization and high-temperature annealing process is improved, the characteristic of rapid solidification of the strip casting and rolling process is utilized, the solidification structure of the strip blank is homogenized and fine by virtue of the rapid cooling speed, the inhibitor forming element and the segregation facilitating element are in a solid solution state, the fine dispersion inhibitor is separated out in the subsequent normalizing and annealing stages, and the structure and magnetic performance of the oriented silicon steel finished product are improved. The high magnetic induction oriented silicon steel has the advantages of simple production process, short flow, high efficiency, thin product specification and small loss, can realize continuous production, and can meet the industrial requirements.
Various embodiments of the present application may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be interpreted as a rigid limitation on the scope of the application. It is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In this application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present application, the terms "include", "comprise", "comprising" and the like mean "including but not limited to". Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
The foregoing is merely a specific embodiment of the application to enable one skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The high-magnetic induction oriented silicon steel is characterized by comprising the following molten steel components in percentage by mass: c:0.02% -0.08%; si:3.0 to 3.5 percent; mn:0.02% -0.18%; s: 0.005-0.020%; al:0.020% -0.042%; n:0.015 to 0.040 percent; sn:0.08 to 0.3 percent; cu:0.1 to 0.9 percent.
2. The high magnetic induction oriented silicon steel according to claim 1, wherein the molten steel composition of the oriented silicon steel comprises, in mass fraction: c:0.02% -0.08%; si:3.0 to 3.3 percent; mn:0.04 to 0.90 percent; s:0.01 to 0.015 percent; al:0.020 to 0.030 percent; n:0.015 to 0.025 percent; sn:0.08 to 0.2 percent; cu:0.1 to 0.9 percent.
3. The high magnetic induction oriented silicon steel according to claim 1 or 2, characterized in that the molten steel composition of the oriented silicon steel further comprises at least one of the following: cr:0.01 to 0.2 percent; sb:0.01 to 0.08 percent; mo:0.01 to 0.08 percent; bi:0.01 to 0.08 percent; as:0.01% -0.05%; p:0.05 to 0.3 percent.
4. A method for preparing high magnetic induction oriented silicon steel according to any one of claims 1 to 3, comprising:
pouring molten steel into a tundish after being calmed, and carrying out thin strip continuous casting to obtain a thin strip blank;
carrying out hot rolling, cooling and curling on the Bao Daipi to obtain a hot rolled plate;
carrying out normalizing treatment, acid washing and cold rolling on the hot rolled plate to obtain a cold rolled plate;
and carrying out decarburization annealing, high-temperature annealing and insulating layer coating on the cold-rolled sheet to obtain the high-magnetic induction oriented silicon steel.
5. The method according to claim 4, wherein the reaction parameters of the continuous strip casting include: the pulling speed is 70-100m/min, and the temperature for guiding out the thin strip blank is 1300-1400 ℃; and/or
The thickness of the thin strip blank is 2-3mm.
6. The method according to claim 4, wherein the reaction parameters of the hot rolling include: the hot rolling temperature is 1050-1150 ℃, the rolling reduction is 25-67%, and the final rolling temperature is 900-1000 ℃; and/or
The thickness of the hot rolled plate is 1-1.5mm.
7. The method of claim 4, wherein the normalizing treatment is divided into a first stage normalization and a second stage normalization;
the first-stage normalized reaction parameters include: the temperature is 1050-1150 ℃ and the time is 0.5-5min;
the second-stage normalized reaction parameters include: the temperature is 850-1000 deg.C, and the time is 0-1min.
8. The method according to claim 4, wherein the reaction parameters of the acid washing include: the pickling solution is HCl with the volume concentration of 3-7%, the temperature of the pickling solution is 70-90 ℃, and the pickling time is 0.5-1.5min; and/or
The reaction parameters of the cold rolling include: the total rolling reduction is 80% -95%; and/or
The thickness of the cold-rolled sheet is 0.10-0.20mm.
9. The method according to claim 4, wherein the reaction parameters of the decarburization annealing include: the temperature rising rate is 20-50 ℃/s, the decarburization temperature is 780-880 ℃, and the heat preservation time is 1-4min; and/or
The decarburization annealing atmosphere is H with volume fraction of 60-75% 2 And 25-40% by volume of N 2 The dew point temperature of the decarburization annealing atmosphere is 40-60 ℃.
10. The method of manufacturing according to claim 4, wherein the high temperature annealing comprises: coating MgO release agent on the cold-rolled sheet after decarburization annealing, then preserving heat for 1-2 hours at 600-800 ℃, then heating to 960 ℃ at a heating rate of 15-40 ℃/h, then preserving heat for 10-40 hours at 10-20 ℃/h to 1200 ℃, then cooling to 600 ℃ at 50-60 ℃/h, and then cooling to below 200 ℃ along with a furnace; wherein,,
the atmosphere before heating to 1100 ℃ is 25-40% N by volume 2 And 60-75% by volume of H 2 The atmosphere after the temperature is raised to 1100 ℃ and the heat preservation is finished to 1200 ℃ is full H 2 Atmosphere, after the end of the heat preservation at 1200 ℃ until the temperature is cooled to 600 ℃, the atmosphere is H with the volume fraction of 75-85 percent 2 And 15-25% by volume of N 2 The atmosphere after cooling to 600 ℃ to below 200 ℃ was pure nitrogen.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06158169A (en) * | 1992-11-24 | 1994-06-07 | Nippon Steel Corp | High magnetic flux density grain-oriented electrical steel sheet manufacturing method |
| JP2002302742A (en) * | 2001-04-05 | 2002-10-18 | Kawasaki Steel Corp | Hot rolled sheet for grain-oriented electrical steel sheets |
| CN104962815A (en) * | 2015-07-15 | 2015-10-07 | 东北大学 | High magnetic induction oriented silicon steel and manufacturing method thereof |
| CN108546814A (en) * | 2018-04-11 | 2018-09-18 | 北京科技大学 | A method of high magnetic induction grain-oriented silicon steel is produced based on ESP Endless Rolling Technologies |
| CN110055393A (en) * | 2019-04-28 | 2019-07-26 | 首钢智新迁安电磁材料有限公司 | A kind of thin gauge low temperature high magnetic induction grain-oriented silicon steel strip production method |
| WO2021027797A1 (en) * | 2019-08-13 | 2021-02-18 | 宝山钢铁股份有限公司 | High-magnetic-induction oriented silicon steel and manufacturing mathod therefor |
-
2022
- 2022-11-16 CN CN202211436578.2A patent/CN116219272A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06158169A (en) * | 1992-11-24 | 1994-06-07 | Nippon Steel Corp | High magnetic flux density grain-oriented electrical steel sheet manufacturing method |
| JP2002302742A (en) * | 2001-04-05 | 2002-10-18 | Kawasaki Steel Corp | Hot rolled sheet for grain-oriented electrical steel sheets |
| CN104962815A (en) * | 2015-07-15 | 2015-10-07 | 东北大学 | High magnetic induction oriented silicon steel and manufacturing method thereof |
| CN108546814A (en) * | 2018-04-11 | 2018-09-18 | 北京科技大学 | A method of high magnetic induction grain-oriented silicon steel is produced based on ESP Endless Rolling Technologies |
| CN110055393A (en) * | 2019-04-28 | 2019-07-26 | 首钢智新迁安电磁材料有限公司 | A kind of thin gauge low temperature high magnetic induction grain-oriented silicon steel strip production method |
| WO2021027797A1 (en) * | 2019-08-13 | 2021-02-18 | 宝山钢铁股份有限公司 | High-magnetic-induction oriented silicon steel and manufacturing mathod therefor |
Non-Patent Citations (3)
| Title |
|---|
| 刘小飞;黎先浩;赵松山;王爱星;罗海文: "Sn和冷轧板厚度对取向硅钢初次再结晶组织和织构影响", 中国冶金, vol. 31, no. 010, 31 December 2021 (2021-12-31) * |
| 朱诚意;陈先红;李光强;付勇;徐光;: "高品质取向硅钢成分控制的新进展及其对钢磁性能的影响", 材料导报, no. 01, 10 January 2015 (2015-01-10) * |
| 黎先浩;孟小涛;赵鹏飞;贺小国;于海彬;罗海文: "高磁感取向硅钢研发现状与展望", 中国冶金, no. 001, 31 December 2019 (2019-12-31) * |
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