Method of producing grain-oriented electrical steel sheet

Abstract

To improve and stabilize magnetic properties, a steel sheet is soaked in a temperature range of 1000° C. or more and 1120° C. or less for 200 sec or less and then soaked in a temperature range of 650° C. or more and 1000° C. or less for 200 sec or less in annealing before final cold rolling, and the amount of Al in precipitates after the annealing before the final cold rolling is limited to 50% or more of the total amount of Al contained in the steel slab.

Claims

1. A method of producing a grain-oriented electrical steel sheet, comprising: heating a steel slab at 1300° C. or less, the steel slab having a chemical composition containing, in mass %, C: 0.002% or more and 0.08% or less, Si: 2.0% or more and 8.0% or less, Mn: 0.02% or more and 1.00% or less, S and/or Se: more than 0.0015% and 0.010% or less in total, N: less than 60 mass ppm, acid-soluble Al: 0.003% or more and less than 100 mass ppm, and a balance being Fe and inevitable impurities; subjecting the steel slab to hot rolling, to obtain a hot rolled steel sheet; optionally subjecting the hot rolled steel sheet to hot band annealing; subjecting the hot rolled steel sheet to cold rolling twice or more with intermediate annealing performed therebetween, to obtain a cold rolled steel sheet; subjecting the cold rolled steel sheet to primary recrystallization annealing; applying an annealing separator to a surface of the cold rolled steel sheet after the primary recrystallization annealing; and then subjecting the cold rolled steel sheet to secondary recrystallization annealing, wherein in the intermediate annealing step immediately before a final cold rolling, the steel sheet is soaked at a first soaking temperature in a range of 1000° C. or more and 1120° C. or less for 10 sec or more and 200 sec or less and then soaked at a second soaking temperature in a range of 650° C. or more and 1000° C. or less for 15 sec or more and 200 sec or less, the second soaking temperature being lower than the first soaking temperature, and an amount of Al in precipitates after the intermediate annealing step immediately before the final cold rolling is limited to 50% or more of a total amount of Al contained in the steel slab.

2. The method of producing a grain-oriented electrical steel sheet according to claim 1, comprising subjecting the cold rolled steel sheet to nitriding treatment.

3. The method of producing a grain-oriented electrical steel sheet according to claim 1, wherein one or more selected from sulfide, sulfate, selenide, and selenate are added to the annealing separator.

4. The method of producing a grain-oriented electrical steel sheet according to claim 1, wherein the chemical composition further contains, in mass %, one or more selected from Sn: 0.001% or more and 0.20% or less, Sb: 0.001% or more and 0.20% or less, Ni: 0.001% or more and 1.50% or less, Cu: 0.001% or more and 1.50% or less, Cr: 0.001% or more and 0.50% or less, P: 0.001% or more and 0.50% or less, Mo: 0.001% or more and 0.50% or less, Ti: 0.001% or more and 0.10% or less, Nb: 0.001% or more and 0.10% or less, V: 0.001% or more and 0.10% or less, B: 0.0002% or more and 0.0025% or less, Bi: 0.001% or more and 0.10% or less, Te: 0.001% or more and 0.10% or less, and Ta: 0.001% or more and 0.10% or less.

5. The method of producing a grain-oriented electrical steel sheet according to claim 4, comprising subjecting the cold rolled steel sheet to nitriding treatment.

6. The method of producing a grain-oriented electrical steel sheet according to claim 4, wherein one or more selected from sulfide, sulfate, selenide, and selenate are added to the annealing separator.

7. A method of producing a grain-oriented electrical steel sheet, comprising: heating a steel slab at 1300° C. or less, the steel slab having a chemical composition containing, in mass %, C: 0.002% or more and 0.08% or less, Si: 2.0% or more and 8.0% or less, Mn: 0.02% or more and 1.00% or less, S and/or Se: more than 0.0015% and 0.010% or less in total, N: less than 60 mass ppm, acid-soluble Al: 0.003% or more and less than 100 mass ppm, and a balance being Fe and inevitable impurities; subjecting the steel slab to hot rolling, to obtain a hot rolled steel sheet; subjecting the hot rolled steel sheet to hot band annealing; subjecting the hot rolled steel sheet to cold rolling once only to obtain a cold rolled steel sheet; subjecting the cold rolled steel sheet to primary recrystallization annealing; applying an annealing separator to a surface of the cold rolled steel sheet after the primary recrystallization annealing; and then subjecting the cold rolled steel sheet to secondary recrystallization annealing, wherein in the hot band annealing step, the hot rolled steel sheet is soaked at a first soaking temperature in a range of 1000° C. or more and 1120° C. or less for 10 sec or more and 200 sec or less and then soaked at a second soaking temperature in a range of 650° C. or more and 1000° C. or less for 15 sec or more and 200 sec or less, the second soaking temperature being lower than the first soaking temperature, and an amount of Al in precipitates after the hot band annealing is limited to 50% or more of a total amount of Al contained in the steel slab.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) In the accompanying drawings:

(2) FIG. 1 is a graph illustrating a pattern of annealing before final cold rolling;

(3) FIG. 2 is a graph illustrating the relationship between the soaking temperature in the second stage of annealing before final cold rolling and the magnetic flux density (B.sub.8);

(4) FIG. 3 is a graph illustrating the relationship between the soaking temperature in the second stage of annealing before final cold rolling and the proportion of the amount of Al in precipitates to the total amount of Al; and

(5) FIG. 4 is a graph illustrating the relationship between the proportion of the amount of Al in precipitates to the total amount of Al and the magnetic flux density.

DETAILED DESCRIPTION

(6) A method of producing a grain-oriented electrical steel sheet according to one of the disclosed embodiments is described below. The reasons for limiting the chemical composition of steel are described first. In the description, “%” representing the content (amount) of each component element denotes “mass %” unless otherwise noted, and “ppm” denotes “mass ppm” unless otherwise noted.

(7) C: 0.002% or More and 0.08% or Less

(8) C is an element useful in improving primary recrystallized texture. If the C content is more than 0.08%, however, the primary recrystallized texture degrades. The C content is therefore limited to 0.08% or less in the present disclosure. The C content is desirably in a range of 0.002% or more and 0.06% or less, in terms of magnetic properties.

(9) Si: 2.0% or More and 8.0% or Less

(10) Si is an element useful in improving iron loss by increasing electrical resistance. If the Si content is more than 8.0%, however, secondary workability degrades significantly. The Si content is therefore limited to 8.0% or less. The Si content is in a range of 2.0% or more and 8.0% or less, in terms of iron loss.

(11) Mn: 0.02% or More and 1.00% or Less

(12) Mn has an effect of improving hot workability during production. If the Mn content is more than 1.00%, however, the primary recrystallized texture degrades, which leads to degradation in magnetic properties. The Mn content is therefore limited to 1.00% or less. The Mn content is in a range of 0.02% or more and 1.00% or less, in terms of magnetic properties.

(13) N: Less than 60 ppm

(14) Excessive N makes secondary recrystallization difficult. Particularly if the N content is 60 ppm or more, secondary recrystallization is unlikely to occur, and the magnetic properties degrade. The N content is therefore limited to less than 60 ppm.

(15) Acid-Soluble Al (Sol.Al): Less than 100 ppm

(16) Excessive Al also makes secondary recrystallization difficult. Particularly if the sol.Al content is 100 ppm or more, secondary recrystallization is unlikely to occur under the low-temperature slab heating conditions, and the magnetic properties degrade. Al is therefore limited to less than 100 ppm in sol.Al content.

(17) S and/or Se: More than 0.0015% and 0.010% of Less in Total

(18) In the present disclosure, it is most important that the total content of S and/or Se is more than 0.0015% and 0.010% or less. Se and S form precipitates such as an Mn compound or a Cu compound, and also inhibit grain growth as solute Se and solute S, to exhibit a magnetic property stabilizing effect.

(19) If the total content of S and/or Se is 0.0015% or less, the amount of solute S and/or Se is insufficient, causing unstable magnetic properties. If the total content of S and/or Se is more than 0.010%, the dissolution of precipitates in slab heating before hot rolling is insufficient, causing unstable magnetic properties. The total content of S and/or Se is therefore in a range of more than 0.0015% and 0.010% or less.

(20) The basic components according to the present disclosure have been described above. The balance other than the components described above is Fe and inevitable impurities. Additionally, the following elements may be optionally contained as appropriate as components for improving the magnetic properties industrially more stably.

(21) Sn: 0.001% or More and 0.20% or Less

(22) Sn has a function of suppressing the nitriding or oxidation of the steel sheet during secondary recrystallization annealing and promoting the secondary recrystallization of crystal grains having favorable crystal orientation to effectively improve the magnetic properties, in particular iron loss. To achieve this effect, the Sn content is preferably 0.001% or more. If the Sn content is more than 0.20%, cold rolling manufacturability degrades. Accordingly, the Sn content is desirably in a range of 0.001% or more and 0.20% or less.

(23) Sb: 0.001% or More and 0.20% or Less

(24) Sb is a useful element that suppresses the nitriding or oxidation of the steel sheet during secondary recrystallization annealing and promotes the secondary recrystallization of crystal grains having favorable crystal orientation to effectively improve the magnetic properties. To achieve this effect, the Sb content is preferably 0.001% or more. If the Sb content is more than 0.20%, cold rolling manufacturability decreases. Accordingly, the Sb content is desirably in a range of 0.001% or more and 0.20% or less.

(25) Ni: 0.001% or More and 1.50% or Less

(26) Ni has a function of improving the magnetic properties by enhancing the uniformity of the hot rolled sheet texture. To achieve this effect, the Ni content is preferably 0.001% or more. If the Ni content is more than 1.50%, secondary recrystallization is difficult, and the magnetic properties decrease. Accordingly, the Ni content is desirably in a range of 0.001% or more and 1.50% or less.

(27) Cu: 0.001% or More and 1.50% or Less

(28) Cu has a function of suppressing the oxidation of the steel sheet during secondary recrystallization annealing and promoting the secondary recrystallization of crystal grains having favorable crystal orientation to effectively improve the magnetic properties. To achieve this effect, the Cu content is preferably 0.001% or more. If the Cu content is more than 1.50%, hot rolling manufacturability decreases. Accordingly, the Cu content is desirably in a range of 0.001% or more and 1.50% or less.

(29) Cr: 0.001% or More and 0.50% or Less

(30) Cr has a function of stabilizing the formation of the forsterite base film. To achieve this effect, the Cr content is preferably 0.001% or more. If the Cr content is more than 0.50%, secondary recrystallization is difficult, and the magnetic properties degrade. Accordingly, the Cr content is desirably in a range of 0.001% or more and 0.50% or less.

(31) P: 0.001% or More and 0.50% or Less

(32) P is a useful element that improves primary recrystallized texture and promotes the secondary recrystallization of crystal grains having favorable crystal orientation to effectively improve the magnetic properties. To achieve this effect, the P content is preferably 0.001% or more. If the P content is more than 0.50%, cold rolling manufacturability decreases. Accordingly, the P content is desirably in a range of 0.001% or more and 0.50% or less.

(33) Mo: 0.001% or More and 0.50% or Less

(34) Mo has a function of suppressing high-temperature oxidation and reducing surface defects called scab. To achieve this effect, the Mo content is preferably 0.001% or more. If the Mo content is more than 0.50%, cold rolling manufacturability decreases. Accordingly, the Mo content is desirably in a range of 0.001% or more and 0.50% or less.

(35) Ti: 0.001% or More and 0.10% or Less

(36) Ti is a useful element that inhibits the growth of primary recrystallized grains and promotes the secondary recrystallization of crystal grains having favorable crystal orientation to improve the magnetic properties. To achieve this effect, the Ti content is desirably 0.001% or more. If the Ti content is more than 0.10%, Ti remains in the steel substrate and causes an increase in iron loss. Accordingly, the Ti content is desirably in a range of 0.001% or more and 0.10% or less.

(37) Nb: 0.001% or More and 0.10% or Less

(38) Nb is a useful element that inhibits the growth of primary recrystallized grains and promotes the secondary recrystallization of crystal grains having favorable crystal orientation to improve the magnetic properties. To achieve this effect, the Nb content is desirably 0.001% or more. If the Nb content is more than 0.10%, Nb remains in the steel substrate and causes an increase in iron loss. Accordingly, the Nb content is desirably in a range of 0.001% or more and 0.10% or less.

(39) V: 0.001% or More and 0.10% or Less

(40) V is a useful element that inhibits the growth of primary recrystallized grains and promotes the secondary recrystallization of crystal grains having favorable crystal orientation to improve the magnetic properties. To achieve this effect, the V content is desirably 0.001% or more. If the V content is more than 0.10%, V remains in the steel substrate and causes an increase in iron loss. Accordingly, the V content is desirably in a range of 0.001% or more and 0.10% or less.

(41) B: 0.0002% or More and 0.0025% or Less

(42) B is a useful element that inhibits the growth of primary recrystallized grains and promotes the secondary recrystallization of crystal grains having favorable crystal orientation to improve the magnetic properties. To achieve this effect, the B content is desirably 0.0002% or more. If the B content is more than 0.0025%, B remains in the steel substrate and causes an increase in iron loss. Accordingly, the B content is desirably in a range of 0.0002% or more and 0.0025% or less.

(43) Bi: 0.001% or More and 0.10% or Less

(44) Bi is a useful element that, by segregating to grain boundaries, inhibits the growth of primary recrystallized grains and promotes the secondary recrystallization of crystal grains having favorable crystal orientation to improve the magnetic properties. To achieve this effect, the Bi content is desirably 0.001% or more. If the Bi content is more than 0.10%, Bi remains in the steel substrate and causes an increase in iron loss. Accordingly, the Bi content is desirably in a range of 0.001% or more and 0.10% or less.

(45) Te: 0.001% or More and 0.10% or Less

(46) Te is a useful element that, by segregating to grain boundaries, inhibits the growth of primary recrystallized grains and promotes the secondary recrystallization of crystal grains having favorable crystal orientation to improve the magnetic properties. To achieve this effect, the Te content is desirably 0.001% or more. If the Te content is more than 0.10%, Te remains in the steel substrate and causes an increase in iron loss. Accordingly, the Te content is desirably in a range of 0.001% or more and 0.10% or less.

(47) Ta: 0.001% or More and 0.10% or Less

(48) Ta is a useful element that inhibits the growth of primary recrystallized grains and promotes the secondary recrystallization of crystal grains having favorable crystal orientation to improve the magnetic properties. To achieve this effect, the Ta content is desirably 0.001% or more. If the Ta content is more than 0.10%, Ta remains in the steel substrate and causes an increase in iron loss. Accordingly, the Ta content is desirably in a range of 0.001% or more and 0.10% or less.

(49) The production conditions for a grain-oriented electrical steel sheet according to the present disclosure are described below.

(50) [Heating]

(51) A steel slab adjusted to the above-mentioned chemical composition is heated at 1300° C. or less. Limiting the heating temperature to 1300° C. or less is particularly effective in reducing scale which forms during hot rolling. Moreover, by limiting the heating temperature to 1300° C. or less, crystal texture can be refined and primary recrystallized texture with uniformly-sized grains can be realized.

(52) [Hot Rolling]

(53) After the heating, hot rolling is performed. The hot rolling is desirably performed with a start temperature of 1100° C. or more and a finish temperature of 800° C. or more, in terms of crystal texture refinement. The finish temperature is desirably 1000° C. or less, in terms of uniformizing crystal texture.

(54) [Annealing Before Final Cold Rolling]

(55) Following this, the hot rolled sheet is optionally hot band annealed. In the case of not performing intermediate annealing subsequently, the hot band annealing serves as the annealing before the final cold rolling.

(56) The hot rolled sheet is then cold rolled once, or twice or more with intermediate annealing performed therebetween, to obtain a cold rolled sheet. In the case of not performing hot band annealing, intermediate annealing is definitely performed. This intermediate annealing serves as the annealing before the final cold rolling.

(57) For high development of Goss texture in the product sheet, the annealing before the final cold rolling is performed in a two-stage heat pattern made up of soaking treatment in a first stage in a temperature range of 1000° C. or more and 1120° C. or less and soaking treatment in a second stage in a temperature range of 650° C. or more and 1000° C. or less, which is lower than that in the first stage. The temperature in the soaking treatment in each of the first stage and the second stage need not be constant, as long as the temperature stays in the corresponding temperature range for a predetermined time.

(58) If the soaking temperature in the first stage is less than 1000° C., recrystallization is insufficient, and the magnetic properties degrade. If the soaking temperature in the first stage is more than 1120° C., the grain size before cold rolling coarsens excessively, and the magnetic properties degrade. Accordingly, the soaking temperature in the first stage is 1000° C. or more and 1120° C. or less. If the soaking time is more than 200 sec, the coarsening of sulfides progresses, and the inhibiting capability decreases, as a result of which the magnetic properties degrade. Accordingly, the soaking time in the first stage is 200 sec or less.

(59) If the soaking temperature in the second stage is less than 650° C., the amount of precipitated Al after the annealing before the final cold rolling decreases, and the grain boundary segregation amount of solute S and/or Se decreases, as a result of which the magnetic properties decrease. If the soaking temperature in the second stage is more than 1000° C., the amount of precipitated Al after the annealing decreases, and secondary recrystallization is unstable, as a result of which the magnetic properties decrease. Accordingly, the soaking temperature in the second stage is 650° C. or more and 1000° C. or less. If soaking time in the second stage is more than 200 sec, the grain boundary precipitation of carbides progresses, and solute C decreases, as a result of which the magnetic properties decrease. Accordingly, the soaking time in the second stage is 200 sec or less.

(60) In the cold rolling, it is effective to perform the rolling with the rolling temperature increased to 100° C. or more and 250° C. or less, or perform aging treatment once or more in a range of 100° C. or more and 250° C. or less during the cold rolling, in terms of developing Goss texture.

(61) [Primary Recrystallization Annealing]

(62) The obtained cold rolled sheet is subjected to primary recrystallization annealing. An objective of the primary recrystallization annealing is to cause the primary recrystallization of the cold rolled sheet having rolled microstructure to adjust it to an optimal primary recrystallized grain size for secondary recrystallization. For this objective, the annealing temperature in the primary recrystallization annealing is desirably about 800° C. or more and less than about 950° C. The annealing atmosphere may be a wet hydrogen nitrogen atmosphere or a wet hydrogen argon atmosphere so that the primary recrystallization annealing also serves as decarburization annealing.

(63) In the primary recrystallization annealing, the average heating rate in a temperature range of 500° C. or more and 700° C. or less is preferably 50° C./s or more. Since this temperature range is the temperature range corresponding to the recovery of the texture after the cold rolling, by rapidly heating the cold rolled sheet at the above-mentioned average heating rate to suppress the recovery phenomenon and cause recrystallization, the amount of Goss-oriented crystal grains is enhanced and the crystal grain size after secondary recrystallization is reduced, with it being possible to improve the iron loss property.

(64) [Nitriding Treatment]

(65) During the primary recrystallization annealing, or before applying an annealing separator after the annealing, nitriding treatment may be further performed. The nitriding treatment can stabilize secondary recrystallization.

(66) The method of nitriding treatment is not limited. For example, gas nitriding may be performed using NH.sub.3 atmosphere or gas in coil form, or transported strips may be gas-nitrided continuously. Salt bath nitriding with higher nitriding ability than gas nitriding may also be used. As the salt bath in the case of using salt bath nitriding, a salt bath mainly composed of cyanate is suitable. The nitriding temperature and the nitriding time are preferably 500° C. or more and 1000° C. or less and about 20 sec to 600 sec in the case of gas nitriding, and 300° C. or more and 600° C. or less and about 20 sec to 600 sec in the case of salt bath nitriding.

(67) [Application of Annealing Separator]

(68) An annealing separator is applied to the surface of the steel sheet after the primary recrystallization annealing and before the secondary recrystallization annealing.

(69) In the case where one or more selected from sulfide, sulfate, selenide, and selenite are added to the annealing separator, decomposition occurs at about 700° C. and the grain growth inhibiting capability is enhanced, with it being possible to improve the magnetic properties. While this effect is achieved even with a comparatively small amount, the effect is low if the additive amount is less than 1 part by mass relative to 100 parts by mass of MgO. If the additive amount is more than 30 parts by mass, oxidizability is excessively high, and the forsterite film is excessively thick, so that the bending peeling property of the formed forsterite film decreases. Accordingly, one or more selected from sulfide, sulfate, selenide, and selenite added to the annealing separator is preferably 1 part by mass or more and 30 parts by mass or less relative to 100 parts by mass of MgO.

(70) [Secondary Recrystallization Annealing]

(71) After this, secondary recrystallization annealing also serving as purification annealing is performed.

(72) By setting the purification temperature in the secondary recrystallization annealing to more than 1180° C. and using a H.sub.2 gas atmosphere as the gas atmosphere in the purification where, for example, H.sub.2 is 10 vol % or more, components such as C, N, Al, S, and Se that are detrimental to the magnetic properties even in extremely small amounts can be purified thoroughly. The purification time is not limited, but is typically about 2 hr to 20 hr.

(73) [Insulation Coating]

(74) After the secondary recrystallization annealing, an insulating coating may be further applied to the surface of the steel sheet and baked, to form an insulation coating. The type of the insulating coating is not limited, and may be any conventionally well-known insulating coating. For example, a method of applying an application liquid containing phosphate-chromate-colloidal silica to the steel sheet and baking it at about 800° C. is preferable.

(75) [Flattening Annealing]

(76) After this, flattening annealing may be performed to arrange the shape of the steel sheet. This flattening annealing may also serve as the insulating coating baking treatment. The annealing temperature in the flattening annealing is preferably 800° C. to 900° C. The annealing time in the flattening annealing is preferably 10 sec or more and 120 sec or less.

(77) The other production conditions may comply with typical grain-oriented electrical steel sheet production methods.

EXAMPLES

Example 1

(78) Each steel slab having a composition containing C: 0.03%, Si: 3.4%, Mn: 0.10%, Cu: 0.06%, Sb: 0.06%, P: 0.06%, Mo: 0.06%, sol.Al: 60 ppm, N: 45 ppm, S: 50 ppm, Se: 1 ppm, and the balance being Fe and inevitable impurities was heated to 1250° C., and then hot rolled to obtain a hot rolled sheet with a sheet thickness of 2.4 mm. After this, the hot rolled sheet was subjected to hot band annealing under the conditions listed in Table 1. After the hot band annealing, the amount of Al in precipitates was measured.

(79) TABLE-US-00001 TABLE 1 Magnetic First stage Second stage Al flux Iron Soaking Soaking precipitation density loss temperature Time temperature Time ratio B.sub.8 W.sub.17/50 No. (° C.) (s) (° C.) (s) (%) (T) (W/kg) Remarks 1 1100 30 900 60 100 1.940 0.79 Example 2 1100 30 700 120 100 1.943 0.78 Example 3 1100 10 800 120 100 1.938 0.80 Example 4 1075 60 800 30 90 1.933 0.82 Example 5 1075 60 800 120 100 1.949 0.77 Example 6 1075 60 800 15 60 1.929 0.83 Example 7 1025 60 800 120 100 1.930 0.84 Example 8 1100 30 None — 10 1.831 1.03 Comparative Example 9 900 30 800 60 80 1.885 1.00 Comparative Example 10 1150 30 800 60 80 1.842 1.02 Comparative Example 11 1100 300 900 60 100 1.901 0.93 Comparative Example 12 1075 30 1025 60 20 1.844 1.03 Comparative Example 13 1075 30 550 60 30 1.858 1.01 Comparative Example 14 1075 60 800 500 100 1.900 0.91 Comparative Example

(80) Subsequently, the steel sheet was cold rolled at 200° C., to obtain a cold rolled sheet with a sheet thickness of 0.23 mm. The cold rolled sheet was then subjected to primary recrystallization annealing also serving as decarburization at 850° C. for 120 sec in an atmosphere of H.sub.2: 55%, N.sub.2: 45%, and dew point: 55° C., with the heating rate from 500° C. to 700° C. being 150° C./s.

(81) After the primary recrystallization annealing, an annealing separator having MgO as a main ingredient was applied to the primary recrystallized sheet by 12.5 g/m.sup.2 per both sides, and dried. Following this, the primary recrystallized sheet was subjected to secondary recrystallization annealing under the conditions of heating to 800° C. at a heating rate of 15° C./h, heating from 800° C. to 850° C. at a heating rate of 2.0° C./h, then retaining at 850° C. for 50 hr, then heating to 1160° C. at 5.0° C./h, and soaking for 5 hr. As the atmosphere gas, N.sub.2 gas was used up to 850° C., and H.sub.2 gas was used at 850° C. or more.

(82) A treatment solution containing phosphate-chromate-colloidal silica at a mass ratio of 3:1:3 was applied to the surface of the secondary recrystallization annealed sheet obtained under the above-mentioned conditions, to perform flattening annealing. The magnetic flux density after the flattening annealing was measured.

(83) As is clear from Table 1, by setting the total content of S and/or Se in the steel slab to more than 0.0015% and 0.010% or less and performing annealing before final cold rolling in a predetermined heat pattern, the amount of precipitated Al can be increased and the grain boundary segregation of solute S and/or Se can be facilitated to achieve favorable magnetic properties.

Example 2

(84) Each steel slab having a composition containing the components listed in Table 2 and the balance being Fe and inevitable impurities was heated to 1250° C., and then hot rolled to obtain a hot rolled sheet with a sheet thickness of 2.6 mm. After this, the hot rolled sheet was subjected to hot band annealing in a two-stage heat pattern. Soaking in the first stage was performed at 1075° C. for 30 s, and soaking in the second stage was performed at 850° C. for 60 s.

(85) After the hot band annealing, the amount of Al in precipitates was measured.

(86) TABLE-US-00002 TABLE 2 Magnetic Al flux Iron precipitation density loss C Si Mn N sol. Al S Se ratio B.sub.8 W.sub.17/50 No. (%) (%) (%) (%) (%) (%) (%) (%) (T) (W/kg) Remarks 1 0.03 3.3 0.12 0.004 0.005 0.0075 0.0001 100 1.940 0.88 Example 2 0.04 3.2 0.09 0.005 0.004 0.0093 0.0001 100 1.943 0.87 Example 3 0.02 3.2 0.08 0.003 0.003 0.0005 0.0050 100 1.948 0.84 Example 4 0.04 3.5 0.04 0.005 0.007 0.0005 0.0080 100 1.949 0.83 Example 5 0.03 3.4 0.14 0.004 0.006 0.0030 0.0030 100 1.945 0.84 Example 6 0.03 3.3 0.10 0.003 0.008 0.0070 0.0030 100 1.950 0.82 Example 7 0.02 3.4 0.12 0.003 0.004 0.0020 0.0001 100 1.933 0.90 Example 8 0.04 3.2 0.07 0.004 0.006 0.0010 0.0001 100 1.878 1.00 Comparative Example 9 0.03 3.3 0.10 0.004 0.006 0.0170 0.0001 100 1.853 1.05 Comparative Example 10 0.03 3.3 0.10 0.004 0.006 0.0005 0.0180 100 1.843 1.07 Comparative Example

(87) Subsequently, the steel sheet was cold rolled at 180° C., to obtain a cold rolled sheet with a sheet thickness of 0.27 mm. The cold rolled sheet was then subjected to primary recrystallization annealing also serving as decarburization at 840° C. for 150 sec in an atmosphere of H.sub.2: 55%, N.sub.2: 45%, and dew point: 58° C., with the heating rate from 500° C. to 700° C. being 100° C./s.

(88) After the primary recrystallization annealing, an annealing separator having MgO as a main ingredient was applied to the primary recrystallized sheet by 12.5 g/m.sup.2 per both sides, and dried. Following this, the primary recrystallized sheet was subjected to secondary recrystallization annealing under the conditions of heating to 800° C. at a heating rate of 5° C./h, heating from 800° C. to 840° C. at a heating rate of 2.0° C./h, then retaining at 840° C. for 50 hr, then heating to 1160° C. at 5.0° C./h, and soaking for 5 hr. As the atmosphere gas, N.sub.2 gas was used up to 840° C., and H.sub.2 gas was used at 840° C. or more.

(89) A treatment solution containing phosphate-chromate-colloidal silica at a mass ratio of 3:1:3 was applied to the surface of the secondary recrystallization annealed sheet obtained under the above-mentioned conditions, to perform flattening annealing. The results of measuring the magnetic flux density (B.sub.8) and the iron loss (W.sub.17/50) after the flattening annealing are listed in Table 2.

(90) As is clear from Table 2, by setting the total content of S and/or Se in the steel slab to more than 0.0015% and 0.010% or less and performing annealing before final cold rolling in a predetermined heat pattern, the amount of precipitated Al can be increased and the grain boundary segregation of solute S and/or Se can be facilitated to achieve favorable magnetic properties.

Example 3

(91) Each steel slab having a composition containing the components listed in Table 3 and the balance being Fe and inevitable impurities was heated to 1260° C., and then hot rolled to obtain a hot rolled sheet with a sheet thickness of 2.8 mm. After this, the hot rolled sheet was subjected to hot band annealing at 1025° C. for 30 sec. The hot rolled sheet was then cold rolled at 120° C., to obtain a cold rolled sheet of 1.8 mm. Subsequently, intermediate annealing was performed in a two-stage heat pattern. Soaking in the first stage was performed at 1050° C. for 30 s, and soaking in the second stage was performed at 800° C. for 90 s. After the intermediate annealing, the amount of Al in precipitates was measured.

(92) TABLE-US-00003 TABLE 3 Magnetic Al flux Iron precipitation density loss C Si Mn N sol. Al S Se Others ratio B.sub.8 W.sub.17/50 No. (%) (%) (%) (%) (%) (%) (%) (%) (%) (T) (W/kg) Remarks 1 0.03 3.3 0.10 0.004 0.006 0.008 0.0001 — — 100 1.925 0.80 Example 2 0.03 3.3 0.10 0.004 0.006 0.001 0.0070 Sn 0.08 100 1.932 0.75 Example 3 0.01 3.3 0.09 0.001 0.003 0.005 0.0001 Sb 0.06 100 1.935 0.76 Example 4 0.03 3.2 0.12 0.003 0.004 0.007 0.0010 Ni 0.45 100 1.938 0.77 Example 5 0.03 3.3 0.08 0.005 0.007 0.005 0.0020 Cu 0.10 100 1.934 0.77 Example 6 0.05 3.5 0.15 0.005 0.009 0.008 0.0001 Cr 0.10 100 1.932 0.76 Example 7 0.03 3.3 0.10 0.004 0.004 0.004 0.0010 P 0.08 100 1.936 0.77 Example 8 0.02 3.2 0.07 0.003 0.005 0.003 0.0001 Mo 0.10 100 1.938 0.76 Example 9 0.03 3.5 0.15 0.002 0.009 0.008 0.0001 Ti 0.01 80 1.935 0.78 Example 10 0.04 3.4 0.14 0.004 0.004 0.005 0.0020 Nb 0.005 90 1.940 0.75 Example 11 0.03 3.3 0.13 0.003 0.003 0.008 0.0001 V 0.04 90 1.933 0.77 Example 12 0.02 3.2 0.10 0.005 0.006 0.006 0.0020 B 0.001 90 1.935 0.78 Example 13 0.03 3.3 0.10 0.004 0.007 0.002 0.0020 Bi 0.01 100 1.941 0.77 Example 14 0.03 3.3 0.08 0.004 0.007 0.008 0.0001 Te 0.01 100 1.938 0.78 Example 15 0.03 3.3 0.08 0.004 0.007 0.004 0.0001 Ta 0.02 100 1.939 0.76 Example

(93) Subsequently, the steel sheet was cold rolled at 180° C., to obtain a cold rolled sheet with a sheet thickness of 0.20 mm. The cold rolled sheet was then subjected to primary recrystallization annealing also serving as decarburization at 840° C. for 100 sec in an atmosphere of H.sub.2: 55%, N.sub.2: 45%, and dew point: 53° C., with the heating rate from 500° C. to 700° C. being 50° C./s.

(94) After the primary recrystallization annealing, an annealing separator obtained by adding MgSO.sub.4 to MgO at a weight ratio of 10% was applied to the primary recrystallized sheet by 12.5 g/m.sup.2 per both sides, and dried. Following this, the primary recrystallized sheet was subjected to secondary recrystallization annealing under the conditions of heating to 800° C. at a heating rate of 5° C./h, heating from 800° C. to 880° C. at a heating rate of 2.0° C./h, then retaining at 880° C. for 50 hr, then heating to 1160° C. at 5.0° C./h, and soaking for 5 hr. As the atmosphere gas, N.sub.2 gas was used up to 840° C., and H.sub.2 gas was used at 840° C. or more.

(95) A treatment solution containing phosphate-chromate-colloidal silica at a mass ratio of 3:1:3 was applied to the surface of the secondary recrystallization annealed sheet obtained under the above-mentioned conditions, to perform flattening annealing. The results of measuring the magnetic flux density (B.sub.8) and the iron loss (W.sub.17/50) after the flattening annealing are listed in Table 3.

(96) As is clear from Table 3, by setting the total content of S and/or Se in the steel slab to more than 0.0015% and 0.010% or less and performing annealing before final cold rolling in a predetermined heat pattern, the amount of precipitated Al can be increased and the grain boundary segregation of solute S and/or Se can be facilitated to achieve favorable magnetic properties.

Example 4

(97) Each steel slab having a composition containing C: 0.02%, Si: 3.1%, Mn: 0.10%, Cu: 0.06%, Sb: 0.06%, P: 0.06%, Mo: 0.06%, Cr: 0.06%, sol.Al: 50 ppm, N: 45 ppm, S: 70 ppm, Se: 10 ppm, and the balance being Fe and inevitable impurities was heated to 1240° C., and then hot rolled to obtain a hot rolled sheet with a sheet thickness of 2.4 mm. After this, the hot rolled sheet was subjected to hot band annealing. The hot band annealing was performed in a two-stage heat pattern. Soaking in the first stage was performed at 1100° C. for 20 s, and soaking in the second stage was performed at 800° C. for 60 s. After the hot band annealing, the amount of Al in precipitates was measured.

(98) Subsequently, the steel sheet was cold rolled at 180° C., to obtain a cold rolled sheet with a sheet thickness of 0.22 mm. The cold rolled sheet was then subjected to primary recrystallization annealing also serving as decarburization at 840° C. for 150 sec in an atmosphere of H.sub.2: 55%, N.sub.2: 45%, and dew point: 55° C., with the heating rate from 500° C. to 700° C. being 100° C./s. Following this, nitriding treatment was performed under the conditions listed in Table 4.

(99) TABLE-US-00004 TABLE 4 Amount Magnetic of N Additive Al flux Iron after in precipitation density loss Nitriding Temperature Time treatment MgO ratio B.sub.8 W.sub.17/50 method (° C.) (s) (ppm) (%) (%) (T) (W/kg) Remarks 1 None — — — None 100 1.940 0.79 Example 2 NH.sub.3 gas 750 60 280 None 100 1.950 0.77 Example 3 Salt bath 550 140 350 None 100 1.954 0.76 Example 4 None — — — MgSO.sub.4 5% 100 1.948 0.76 Example 5 None — — — MgS 5% 100 1.950 0.75 Example 6 None — — — MgSe 2% 100 1.945 0.77 Example 7 NH.sub.3 gas 750 30 230 MgSO.sub.4 5% 100 1.954 0.74 Example

(100) After the primary recrystallization annealing, an annealing separator obtained by adding the agent listed in Table 4 to MgO as a main ingredient was applied to the primary recrystallized sheet by 12.5 g/m.sup.2 per both sides, and dried. Following this, the primary recrystallized sheet was subjected to secondary recrystallization annealing under the conditions of heating to 800° C. at a heating rate of 5° C./h, heating from 800° C. to 880° C. at a heating rate of 2.0° C./h, then retaining at 880° C. for 50 hr, then heating to 1160° C. at 5.0° C./h, and soaking for 5 hr. As the atmosphere gas, N.sub.2 gas was used up to 880° C., and H.sub.2 gas was used at 880° C. or more.

(101) As is clear from Table 4, the magnetic properties can be improved more stably by, in addition to setting the total content of S and/or Se in the steel slab to more than 0.0015% and 0.010% or less and performing annealing before final cold rolling in a predetermined heat pattern, performing nitriding treatment and/or adding one or more selected from sulfide, sulfate, selenide, and selenite to the annealing separator applied to the steel sheet before secondary recrystallization annealing.