GRAIN-ORIENTED ELECTRICAL STEEL SHEET AND METHOD OF PRODUCING SAME

Abstract

Disclosed is a grain-oriented electrical steel sheet capable of obtaining excellent magnetic properties stably over the entire coil length. A grain-oriented electrical steel sheet includes: a chemical composition containing, in mass %, C: 0.005% or less, Si: 2.0% to 4.5%, and Mn: 0.01% to 0.5%, and, in mass ppm, N: 20 ppm or less, each of Se, Te, and O: less than 50 ppm, S: less than 30 ppm, and acid-soluble Al: less than 40 ppm, and Ti: less than 30 ppm, of which 5 ppm or more and 25 ppm or less is acid-soluble Ti, with the balance being Fe and inevitable impurities; and precipitates containing Ti and N with a grain size of 200 nm or more at a frequency of 0.05 grains/mm.sup.2 or more.

Claims

1. A grain-oriented electrical steel sheet comprising: a chemical composition containing, in mass %, C: 0.005% or less, Si: 2.0% to 4.5%, and Mn: 0.01% to 0.5%, and, in mass ppm, N: 20 ppm or less, each of Se, Te, and O: less than 50 ppm, S: less than 30 ppm, and acid-soluble Al: less than 40 ppm, and Ti: less than 30 ppm, of which 5 ppm or more and 25 ppm or less is acid-soluble Ti, with the balance being Fe and inevitable impurities; and precipitates containing Ti and N with a grain size of 200 nm or more at a frequency of 0.05 grains/mm.sup.2 or more.

2. The grain-oriented electrical steel sheet according to claim 1, wherein the chemical composition further contains, in mass %, at least one selected from the group consisting of Ni: 1.50% or less, Sn: 0.50% or less, Sb: 0.50% or less, Cu: 0.50% or less, Mo: 0.50% or less, P: 0.50% or less, Cr: 1.50% or less, B: 0.0050% or less, and Nb: 0.0100% or less.

3. A method of producing the grain-oriented electrical steel sheet as recited in claim 1, the method comprising: casting a steel slab from molten steel, the steel slab having a chemical composition containing, in mass %, C: 0.08% or less, Si: 2.0% to 4.5%, and Mn: 0.01% to 0.5%, and, in mass ppm, Ti: less than 50 ppm, each of Se, Te, and O: less than 50 ppm, S: less than 50 ppm, acid-soluble Al: 20 ppm or more and less than 100 ppm, and N: 80 ppm or less, with the balance being Fe and inevitable impurities; hot rolling the steel slab to obtain a hot-rolled sheet; then annealing and rolling the hot-rolled sheet to obtain a cold-rolled sheet having a final sheet thickness; then subjecting the cold-rolled sheet to primary recrystallization annealing; then subjecting the cold-rolled sheet to secondary recrystallization annealing; and then forming an insulating coating on the cold-rolled sheet, wherein the molten steel contains Ti in an amount of less than 50 ppm, of which 5 ppm or more and 30 ppm or less is acid-soluble Ti.

4. The method of producing the grain-oriented electrical steel sheet according to claim 3, wherein the hot rolling includes an initial rolling reduction after which the steel slab is held at a temperature of 1000° C. or higher for a period of 40 seconds or more, and the molten steel has a chemical composition adjusted such that a Si-containing ferroalloy, an Al-containing ferroalloy, and a Ti-containing ferroalloy are added in order of adding 50% or more of a total amount of the Ti-containing ferroalloy after adding the Si-containing ferroalloy and before adding the Al-containing ferroalloy, to make an amount of Ti in the molten steel at least less than 50 ppm, of which 5 ppm or more and 30 ppm or less is acid-soluble Ti.

5. A method of producing the grain-oriented electrical steel sheet as recited in claim 2, the method comprising: casting a steel slab from molten steel, the steel slab having a chemical composition containing, in mass %, C: 0.08% or less, Si: 2.0% to 4.5%, and Mn: 0.01% to 0.5%, and, in mass ppm, Ti: less than 50 ppm, each of Se, Te, and O: less than 50 ppm, S: less than 50 ppm, acid-soluble Al: 20 ppm or more and less than 100 ppm, and N: 80 ppm or less, and further contains, in mass %, at least one selected from the group consisting of Ni: 0.005% to 1.50%, Sn: 0.01% to 0.50%, Sb: 0.005% to 0.50%, Cu: 0.01% to 0.50%, Mo: 0.01% to 0.50%, P: 0.0050% to 0.50%, Cr: 0.01% to 1.50%, B: 0.0001% to 0.0050%, and Nb: 0.0005% to 0.0100%, with the balance being Fe and inevitable impurities; hot rolling the steel slab to obtain a hot-rolled sheet; then annealing and rolling the hot-rolled sheet to obtain a cold-rolled sheet having a final sheet thickness; then subjecting the cold-rolled sheet to primary recrystallization annealing; then subjecting the cold-rolled sheet to secondary recrystallization annealing; and then forming an insulating coating on the cold-rolled sheet, wherein the molten steel contains Ti in an amount of less than 50 ppm, of which 5 ppm or more and 30 ppm or less is acid-soluble Ti.

6. A hot-rolled steel sheet for use in production of a grain-oriented electrical steel sheet, the hot-rolled steel sheet comprising Ti in an amount of less than 50 ppm, of which 5 ppm or more and 30 ppm or less is acid-soluble Ti.

7. The hot-rolled steel sheet for use in production of a grain-oriented electrical steel sheet according to claim 6, further comprising precipitates containing Ti and N with a grain size of 200 nm or more at a frequency of 0.05 grains/mm.sup.2 or more.

8. The method of producing the grain-oriented electrical steel sheet according to claim 5, wherein the hot rolling includes an initial rolling reduction after which the steel slab is held at a temperature of 1000° C. or higher for a period of 40 seconds or more, and the molten steel has a chemical composition adjusted such that a Si-containing ferroalloy, an Al-containing ferroalloy, and a Ti-containing ferroalloy are added in order of adding 50% or more of a total amount of the Ti-containing ferroalloy after adding the Si-containing ferroalloy and before adding the Al-containing ferroalloy, to make an amount of Ti in the molten steel at least less than 50 ppm, of which 5 ppm or more and 30 ppm or less is acid-soluble Ti.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0033] In the accompanying drawings:

[0034] FIG. 1A illustrates SEM images and EDX analysis results of precipitates on a surface of a steel sheet; and

[0035] FIG. 1B illustrates SEM images and EDX analysis results of precipitates on a surface of another steel sheet.

DETAILED DESCRIPTION

[0036] The present disclosure will now be described in detail based on its production method.

[0037] First, the reason for limiting the chemical composition of a steel slab, which is the starting material when producing a grain-oriented electrical steel sheet, is described. In the following, the indications of “%” and “ppm” for components shall mean mass % and mass ppm unless otherwise specified.

[0038] C: 0.08% or Less

[0039] C suppresses crystal grain coarsening during hot rolling and improves the pre-cold-rolled microstructure. In cold rolling, C improves the texture after primary recrystallization by interaction with dislocations. However, if it remains in a steel sheet as a finished product, it causes magnetic aging and magnetic deterioration. If it is contained in the slab in an amount of more than 0.08%, the load becomes high during the decarburization process and cannot be reduced sufficiently. Therefore, the C content is limited to 0.08% or less. To obtain the above-mentioned microstructure improving effect, the lower limit of the C content is desirably 0.01%.

[0040] Si: 2.0% to 4.5%

[0041] Si is a useful element that improves iron loss by increasing electrical resistance. If the Si content is less than 2.0%, sufficient iron loss reduction effect cannot be obtained, and if the Si content is more than 4.5%, cold rolling becomes extremely difficult. Therefore, the Si content is limited to the range of 2.0% to 4.5%. The Si content is preferably 2.0% or more. It is preferably 4.0% or less.

[0042] Mn: 0.01% to 0.5%

[0043] Mn is a useful element to improve hot workability. However, when the Mn content exceeds 0.5%, the primary recrystallized texture deteriorates and it becomes difficult to obtain secondary recrystallized grains that are highly accorded with the Goss orientation. To improve the hot workability, it is necessary to contain Mn in an amount of 0.01% or more. The Mn content is preferably 0.03% or more. It is preferably 0.15% or less.

[0044] Each of Se, Te, and O: Less Than 50 ppm

[0045] When Se and Te are present in excess, selenides and tellurides are formed and secondary recrystallization becomes difficult. The reason for this is that the precipitates coarsened by slab heating make the primary recrystallized texture non-uniform. Therefore, the content of Se and Te should be suppressed to less than 50 ppm each to prevent them from acting as inhibitors. The content of Se and Te is preferably 30 ppm or less each. In addition, O forms oxides, which remain as inclusions in the final product and degrade the magnetic properties. Therefore, the O content needs to be kept below 50 ppm. The content of these elements may be 0%.

[0046] Acid-Soluble Al: 20 ppm or More and Less Than 100 ppm, S: Less Than 50 ppm, N: 80 ppm or Less

[0047] When an inhibitor-less method is applied, these precipitate-forming elements are not necessarily contained if only secondary recrystallization is considered. However, when contained in a proper amount, Al can form a dense Al.sub.2O.sub.3 film on the surface during secondary recrystallization annealing and reduce the effects of nitriding, for example, from the annealing atmosphere. Therefore, the Al content is 20 ppm or more and less than 100 ppm.

[0048] If S and N are each contained in an amount of 50 ppm or more and more than 80 ppm, respectively, as in the case of Se and Te, the precipitates formed during slab heating become coarse and deteriorate the primary recrystallized texture. Therefore, the upper limit is limited to the values mentioned above.

[0049] The lower limit of the amount of S and N added is preferably 0%. However, these elements are difficult to remove completely, and actually reducing S to less than 10 ppm and N to less than 20 ppm significantly increases the production cost. The inhibitor-less method is intended to produce high-quality grain-oriented electrical steel sheets at low cost, and the above values are specified as the lower limit from the viewpoint of reducing the burden during production.

[0050] The present disclosure can stabilize the magnetic properties of steel sheet coils by fixing the sulfides and nitrides formed by such S and N with an appropriate amount of Ti to achieve pseudo high purity.

[0051] Next, regarding Ti, in the molten steel to be subjected to continuous casting, the amount of Ti should be less than 50 ppm, of which 5 ppm or more and 30 ppm or less should be acid-soluble Ti.

[0052] The Ti in the steel forms grains such as TiO.sub.2 and TiN. If the inclusions and precipitates formed in this way are present in excess, they lead to deterioration of magnetic properties, especially hysteresis loss. Therefore, the Ti content should be controlled to less than 50 ppm. Then, the acid-soluble Ti, which leads to TiN precipitation in the subsequent process, is controlled within the range of 5 ppm to 30 ppm. If high-purity ferroalloys that do not contain Ti as an impurity are to be used as the raw material, it is necessary to add alloying elements that serve as Ti sources separately. Therefore, in order to reduce the production cost, the present disclosure can take measures to increase the amount of Ti by actively using ferroalloys with low purity.

[0053] In the present disclosure, it is preferable that the molten steel has a chemical composition adjusted such that a Ti-containing ferroalloy, a Si-containing ferroalloy, and an Al-containing ferroalloy are added in order of adding 50% or more of a total amount of the Ti-containing ferroalloy after adding the Si-containing ferroalloy and before adding the Al-containing ferroalloy. Since Ti is a strong deoxidation element, when it is added at a stage where the oxygen content in the molten steel is high, it combines with the oxygen to form TiO.sub.2, which makes it difficult to form acid-soluble Ti. Therefore, it is preferable to adopt the procedure of adding Si before the addition of Ti source.

[0054] Through this procedure, the oxygen in the molten steel rises to some extent in the slag in the form of SiO.sub.2 and is removed from the steel. This will increase the Ti yield and increase the amount of acid-soluble Ti in a moderate range.

[0055] On the other hand, Al is known to be a stronger deoxidation element than Ti. Therefore, the oxygen in the molten steel after the addition of Al is removed by Al in the form of Al.sub.2O.sub.3, and most of the added Ti is expected to be all in the form of acid-soluble Ti, which may cause the acid-soluble Ti in the molten steel to exceed 30 ppm.

[0056] Therefore, in the case of performing component adjustment using an inexpensive ferroalloy having relatively low purity and containing Ti as an impurity, after adding a Si-containing ferroalloy, a Ti-containing ferroalloy is added at 50% or more of the total amount to the moderately-dissolved oxygen, and after analyzing the acid-soluble Ti after the addition, the Al-containing ferroalloy is added. Then, the rest of the Ti-containing ferroalloy can be added at a higher Ti yield, and the Ti content can be controlled to an appropriate range. Such a method makes it possible to control the Ti content within an appropriate range without using a particularly pure ferroalloy. Of course, such a method is not always necessary if the chemical composition is adjusted by high purity ferroalloys.

[0057] Although the essential elements and inhibiting elements have been described above, in the present disclosure, one or more of the other elements described below may be selected and contained as appropriate.

[0058] Ni: 0.005% to 1.50%

[0059] Ni serves to increase the uniformity of the microstructure of a hot rolled sheet, and thus improve the magnetic properties. However, if the Ni content is less than 0.005%, the effect of the addition is poor, while if the content exceeds 1.50%, secondary recrystallization becomes unstable and magnetic properties deteriorate. Therefore, it is desirable to contain Ni in the range of 0.005% to 1.50%.

[0060] Sn: 0.01% to 0.50%, Sb: 0.005% to 0.50%, Cu: 0.01% to 0.50%

[0061] These elements are sometimes regarded as auxiliary inhibitors through grain boundary segregation, but they may be useful in inhibitor-less methods that do not actively utilize inhibitors by precipitation. If the value of each element is less than the lower limit, the addition effect is poor, while if the value exceeds the upper limit, the possibility of secondary recrystallization failure increases.

[0062] P: 0.0050% to 0.50%, Cr: 0.01% to 1.50%

[0063] These elements have the effect of making the reaction good during forsterite film formation. If the content of each element is less than the lower limit, the addition effect is poor, while if the content of each element is greater than the upper limit, the formation of forsterite film will be accelerated too much, causing problems such as peeling of the film.

[0064] Mo: 0.01% to 0.50%, B: 0.0001% to 0.0050%, Nb: 0.0005% to 0.0100%

[0065] All of these elements contribute to the suppression of grain growth and have the effect of improving the texture and stabilizing secondary recrystallization. In order to obtain such effects efficiently, it is preferable to contain each of them in the above range. When added in excess, each added element precipitates in the steel and acts as a strong inhibitor. Therefore, it is not desirable to contain any of these elements more than the upper limit in the inhibitor-less method.

[0066] The balance consists of iron and impurities other than those mentioned above, especially inevitable impurities.

[0067] A steel slab adjusted to the aforementioned suitable chemical composition range is, after or without being reheated, hot rolled. In the case of reheating the slab, the reheating temperature is desirably about 1000° C. or higher. It is desirably about 1300° C. or lower. In particular, slab heating above 1300° C. is unnecessary because it is meaningless for the present disclosure, which contains almost no inhibitor in the steel at the slab stage, and ends up increasing the cost.

[0068] After this, hot rolling is carried out. it is desirable that after the first rolling (initial rolling reduction) is performed, the material is held at a temperature of 1000° C. or higher for a period of 40 seconds or more. This is because it is an even more effective process to make the acid-soluble Ti into TiN, the precipitates of which have a grain size of 200 nm or more. In other words, the above holding after the initial pass may introduce dislocations around TiN, which is already in the precipitation state, and increase the diffusion rate of N or the like around TiN, thereby making it easier to control the grain size of precipitates containing Ti and N in an appropriate range. Although no upper limit is placed on the holding time, from a manufacturing standpoint, the upper limit is desirably 600 seconds or less. From the viewpoint of ensuring 1000° C. after the initial pass of hot rolling, the lower limit of the slab heating temperature is desirably 1100° C. or higher.

[0069] The grains containing both Ti and N with an appropriate grain size thus formed are hardly changed in the subsequent process, and exhibit the effect of achieving pseudo high purity by providing precipitation sites of sulfides and nitrides in the subsequent process. The present inventors believe that this effect is similar to the effect used in the technology of trapping C in steel by adding Ti, for example, to make IF steel.

[0070] Then, the hot-rolled sheet is subjected to hot-rolled sheet annealing as necessary, and then subjected to cold rolling once, or twice or more with intermediate annealing performed therebetween to obtain a final cold-rolled sheet. The cold rolling may be performed at room temperature. Alternatively, warm rolling where rolling is performed with the steel sheet temperature raised to a temperature higher than room temperature, e.g., around 250° C., is also applicable.

[0071] The final cold-rolled sheet is subjected to primary recrystallization annealing. The aim 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. The annealing atmosphere is wet hydrogen nitrogen or wet hydrogen argon, which decarburizes the carbon contained in the steel and at the same time forms an oxide film on the surface in the annealing atmosphere. For this purpose, it is desirable that the annealing temperature (holding temperature) of primary recrystallization annealing is approximately from 800° C. or higher to lower than 950° C. In addition, it is effective to increase the heating rate in the heating process of primary recrystallization annealing in order to make the texture even better. Specifically, an improvement can be expected by increasing the heating rate between 500° C. and 700° C. to 80° C./s or higher.

[0072] After the primary recrystallization annealing described above, an annealing separator is applied to the steel sheet surface. Magnesia (MgO) is used as the main annealing separator to form a forsterite film on the surface of the steel sheet after the subsequent secondary recrystallization annealing. The formation of a forsterite film can be further favored by adding an appropriate amount of Ti oxides, Sr compounds, or the like to the separator. In particular, the addition of auxiliaries that promote uniform forsterite film formation is also advantageous for improving peeling properties. This is followed by final annealing for secondary recrystallization and forsterite film formation. The annealing atmosphere for such final annealing can be N.sub.2, Ar, H.sub.2, or mixed gas of any of these. Since precipitation of trace components in the final product will lead to degradation of magnetic properties, the maximum annealing temperature is preferably 1100° C. or higher for component purification.

[0073] Since the steel sheet of the present disclosure has little variation in magnetic properties in a coil, it is desirable to perform final annealing in a coil with a mass of 5 tons or more, more preferably 10 tons or more, for economic reasons.

[0074] After the above-mentioned final annealing, an insulating coating can be further applied to the steel sheet surface and baked. Such an insulation coating is not limited to a particular type, and any conventionally known insulation coating is applicable. For example, preferred methods are described in JPS50-79442A and JPS48-39338A where a coating liquid containing phosphate-chromate-colloidal silica is applied on a steel sheet and then baked at a temperature of around 800° C.

[0075] As a result of purification by final annealing, the final product obtained has a composition such that the steel substrate of the steel sheet after removing the insulating coating and the base film contains C: 0.005% or less, Si: 2.0% to 4.5%, Mn: 0.01% to 0.5%, N: 20 ppm or less, each of Se, Te, and O: less than 50 ppm each, S: less than 30 ppm, acid-soluble Al: less than 40 ppm, Ti: less than 30 ppm, of which 5 ppm or more and 25 ppm or less is acid-soluble Ti, and precipitates containing Ti and N with a grain size of 200 nm or more at a frequency of 0.05 grains/mm.sup.2 or more. Regarding N, S, and Al, 3 ppm or more of N, 5 ppm or more of S, and 5 ppm or more of Al are acceptable from the perspective of production cost. In addition, the grain-oriented electrical steel sheet disclosed herein may further contain, in mass %, at least one selected from the group consisting of Ni: 1.50% or less, Sn: 0.50% or less, Sb: 0.50% or less, Cu: 0.50% or less, Mo: 0.50% or less, P: 0.50% or less, Cr: 1.50% or less, B: 0.0050% or less, and Nb: 0.0100% or less, in order to improve magnetic properties, and the like.

[0076] Among the above-mentioned additive elements, those for which no lower limit is specified are those for which there is no particular lower limit, and are permitted up to below the lower limit of analysis including 0. Other elements may be incorporated into the forsterite film or released into the gas phase, depending on the final annealing conditions, and their content in the steel may decrease, and some of them may be less than the concentration when contained in the slab within the above ranges, respectively.

EXAMPLES

Example 1

[0077] In addition to the main components, C: 0.06%, Si: 3.35%, and Mn: 0.03%, slabs of various compositions containing other components listed in Table 1 were prepared by smelting. The concentrations of Se, Te, and O were all 30 ppm. The concentration of Ti was adjusted using Ti lumps, and the concentrations of other components were adjusted using high-purity ferroalloy or lumpy or granular pure metals that contained almost no impurities such as Ti. Hot rolling was carried out under the condition that after slab heating at 1250° C. and after the initial (first) pass of hot rolling, each slab was held at 1000° C. or higher for 60 seconds to produce a hot-rolled sheet with a thickness of 2.5 mm.

[0078] These hot-rolled sheets were subjected to hot-rolled sheet annealing at 900° C., cold rolled to 1.3 mm, and then subjected to intermediate annealing. In the intermediate annealing, the temperature was gradually changed from the lead end to the tail end of the coil, so that the temperature of the coil lead end was set at 950° C. and the coil tail end at 1050° C. The annealed coils were cold rolled to a final thickness of 0.23 mm, decarburized, and annealed for primary recrystallization. Subsequently, an annealing separator mainly composed of MgO was applied, and final annealing including secondary recrystallization process and purification process was carried out at the maximum temperature of 1150° C. with the soaking time of 10 hours. The resulting coils were coated with an insulation coating consisting of colloidal silica and magnesium phosphate, and baked at 850° C. to make product sheets.

[0079] The iron loss characteristics were evaluated for each product sheet thus obtained. The iron loss (W.sub.17/50) was measured continuously over the entire length of each product sheet coil and the lowest value (minimum), which is the best value, and the highest value (maximum), which is the worst value, were evaluated. For each coil, samples were taken from the center of the longitudinal direction and the center of the widthwise direction and analyzed for Ti concentration. At the same time, a test specimen for L-section observation was taken and observed 90 mm.sup.2 in a continuous field of view, and compositional analysis by EDX was performed for all grains whose diameter was 200 nm or more in the equivalent diameter from the images of grains, and the number of grains containing both Ti and N were counted and divided by the area of the observation field to obtain a grain density in the steel. The results are listed in Table 3. The concentrations of C, Si, and Mn of the product sheets were all C: 0.001%, Si: 3.35%, and Mn: 0.03%. The concentrations of Se, Te, and O were all 30 ppm.

[0080] It can be seen from the table that the variation of magnetic properties is reduced and suitable properties are maintained by following the present disclosure.

TABLE-US-00001 TABLE 1 Ti concentration of molten steel (ppm) Product sheet evaluation Before Ti concentration Product sheet continuous casting Slab components Steel composition (ppm) Grain properties Total Acid- (ppm) (ppm) Total Acid- density W.sub.17/50 (W/kg) Ti soluble Al S N Others Al S N Others Ti soluble in steel minimum maximum Remarks 25 20 80 25 100 — 34 16 35 — 23 14 0.22 0.852 0.861 Comparative grains/mm.sup.2 example 25 20 80 25 40 — 35 16 12 — 24 13 0.17 0.842 0.848 Example grains/mm.sup.2 25 20 80 25 40 Sb: 300, 35 16 12 Sb: 260, 23 15 0.19 0.835 0.840 Example P: 600 P: 590 grains/mm.sup.2 55 35 80 25 40 Sb: 300, 33 17 16 Sb: 260, 53 31 0.48 0.857 0.866 Comparative P: 600 P: 580 grains/mm.sup.2 example 52 29 80 24 40 Sb: 300, 34 17 15 Sb: 260, 50 25 0.46 0.865 0.864 Comparative P: 600 P: 580 grains/mm.sup.2 example 14 10 50 20 20 Mo: 100, 19 8 9 Mo: 90, 12 8 0.07 0.832 0.836 Example B: 3 B: <1 grains/mm.sup.2 30 20 70 35 30 Cr: 400 30 22 15 Cr: 400 23 13 0.15 0.833 0.838 Example grains/mm.sup.2 30 20 130 40 25 Cr: 400 65 28 11 Cr: 400 22 13 0.12 0.863 0.869 Comparative grains/mm.sup.2 example 20 15 40 30 25 Cu: 200, 14 16 7 Cu: 170, 16 11 0.10 0.833 0.837 Example Nb: 10, Nb: 2, grains/mm.sup.2 P: 50 P: 45 20 15 40 60 25 Cu: 200, 16 36 7 Cu: 180, 13 10 0.12 0.862 0.866 Comparative Nb: 10, Nb: <1, grains/mm.sup.2 example P: 50 P: 40 20 10 60 25 35 Ni: 100 20 11 16 Ni: 100 14 7 0.07 0.831 0.834 Example grains/mm.sup.2 3 <1 60 25 35 Ni: 100 22 13 18 Ni: 100 <1 <1 <0.01 0.831 0.866 Comparative grains/mm.sup.2 example 20 10 65 25 35 Ni: 100, 23 11 16 Ni: 90, 14 8 0.08 0.829 0.832 Example Sn: 500 Sn: 400 grains/mm.sup.2

Example 2

[0081] When preparing a steel by smelting with a target composition of C: 0.05%, Si: 3.2%, Mn: 0.05%, Cr: 0.03%, P: 0.01%, acid-soluble Al: 30 ppm, S: 20 ppm, N: 30 ppm, Se: 50 ppm, Te: 30 ppm, and O: 20 ppm, a slab A was produced by adding ferroalloys such as FeMn, FeCr, and FeP containing Ti as impurities after the addition of FeSi, then, after the analysis of Mn, Cr, P, and Ti, adding lumpy Al, and further adding small amounts of missing components. As a comparison, two slabs B, in which ferroalloys were added before the addition of FeSi and small amounts of missing components were added after the addition of lumpy Al, and two slabs C, in which all the concentrations were adjusted after the addition of lumpy Al, were prepared respectively. In addition, two slabs D to F of the compositions listed in Table 2 were prepared respectively by the production procedure of slab A.

[0082] After that, slab heating was performed to 1200° C., respectively, and hot-rolled sheets with a thickness of 2 mm were prepared under hot rolling condition 1, in which the temperature was held at or above 1000° C. for 60 seconds after the initial pass of hot rolling, and hot rolling condition 2, in which the temperature was lowered to 980° C. within 30 seconds after the initial pass of hot rolling, respectively.

[0083] When these hot-rolled sheets were subjected to hot-rolled sheet annealing, the temperature was gradually changed from the lead end to the tail end of each coil, so that the temperature of the coil lead end was set at 1000° C., the center of the coil in the longitudinal direction at 1025° C., and the tail end of the coil at 1050° C. The annealed coils were cold rolled to a final thickness of 0.27 mm, decarburized, and annealed for primary recrystallization. Subsequently, an annealing separator mainly composed of MgO was applied, and final annealing including secondary recrystallization process and purification process was carried out at the maximum temperature of 1200° C. with the soaking time of 10 hours. The resulting coils were coated with an insulation coating consisting of 60% colloidal silica and aluminum phosphate and baked at 800° C.

[0084] For each material, Epstein test pieces were cut from the tip, center, and tail end positions of the coil, and the iron loss (W.sub.17/50) was measured, and the average value was calculated. The average values of the measured results of iron loss are listed in Table 2, corresponding to the temperature at the time of hot-rolled sheet annealing, respectively. The concentrations of C, Si, and Mn in the product sheets were all C: 0.001%, Si: 3.2%, and Mn: 0.05%. The concentrations of Se, Te, and O in the product sheets were all Se: 10 ppm, Te: 5 ppm, and O: 20 ppm.

[0085] The coating and films were removed from the Epstein test pieces on which the iron loss measurement was made, the composition analysis was carried out, and test specimens for L-section observation were taken and observed 90 mm.sup.2 in a continuous field of view. In this observation, compositional analysis by EDX was performed for all grains whose diameter was 200 nm or more in the equivalent diameter from the images of grains, and the number of grains containing both Ti and N was counted and divided by the area of the observation field to obtain a grain density in the steel.

[0086] From Table 2, it can be seen that by following the present disclosure, even if there is a variation in the annealing temperature in the intermediate process, the variation in magnetic properties is reduced and suitable properties are maintained.

TABLE-US-00002 TABLE 2 Ti concentration of molten steel (ppm) Product sheet evaluation Iron loss of product Before Before sheet (W/kg) adding continuous Ti concentration Temperature of hot- Al lump casting Hot Steel composition (ppm) Grain rolled sheet annealing Total Acid- Total Acid- rolling (ppm) Total Acid- density 1000 1025 1050 Slab Ti soluble Ti soluble condition Al S N Others Ti soluble in steel ° C. ° C. ° C. Remarks A 30 15 33 17 1 10 14 9 — 29 15 0.22 0.885 0.882 0.883 Example grains/mm.sup.2 2 9 12 8 — 29 16 0.04 0.892 0.884 0.897 Comparative grains/mm.sup.2 example B 4 3 7 4 1 9 13 7 — 7 3 0.01 0.889 0.882 0.901 Comparative grains/mm.sup.2 example 2 11 14 8 — 6 3 <0.01 0.888 0.881 0.903 Comparative grains/mm.sup.2 example C 2 1 46 37 1 11 14 8 — 43 35 0.47 0.904 0.904 0.906 Comparative grains/mm.sup.2 example 2 12 13 8 — 42 34 0.28 0.901 0.899 0.906 Comparative grains/mm.sup.2 example D 31 20 35 19 1 12 13 8 Mo: 100, 28 15 0.21 0.879 0.880 0.877 Example Sb: 200, grains/mm.sup.2 P: 400 2 11 13 9 Mo: 100, 29 15 0.04 0.888 0.880 0.891 Comparative Sb: 200, grains/mm.sup.2 example P: 400 E 32 18 34 17 1 10 14 7 Cr: 400, 29 13 0.18 0.877 0.875 0.879 Example Cu: 80, grains/mm.sup.2 Nb: 20 2 10 13 8 Cr: 400, 28 14 0.03 0.882 0.888 0.895 Comparative Cu: 80, grains/mm.sup.2 example Nb: 20 F 29 17 32 16 1 11 12 9 Ni: 100, 27 13 0.17 0.878 0.876 0.874 Example Sn: 100, grains/mm.sup.2 B: 10 2 9 14 9 Ni: 100, 27 13 0.03 0.896 0.890 0.884 Comparative Sn: 100, grains/mm.sup.2 example B: 10