Grain-oriented electrical steel sheet, and method for manufacturing the same

Abstract

An oriented electrical steel sheet and a method of manufacturing the same are provided, and in a method of manufacturing an oriented electrical steel sheet including processes of producing a hot rolled plate by hot rolling a steel slab, performing or omitting hot rolled plate annealing, performing cold rolling, performing decarburization and nitride annealing, and performing final high temperature annealing, the decarburization and nitride annealing process is performed in a dew point range of 35-55 C., and in the final annealing process, a glassless additive including MgO is applied.

Claims

1. An annealing separating agent comprising MgO, an oxychloride material, and a sulfate-based antioxidant, wherein the oxychloride material is included at a ratio of 10-20 wt % to the MgO at 100 weight part, and the sulfate-based antioxidant is included at a ratio of 3.5-7.5 wt % to the MgO at 100 weight part, wherein the oxychloride material is antimony oxychloride (SbOCl).

2. The annealing separating agent of claim 1, wherein the sulfate-based antioxidant is at least one that is selected from an antimony-based (Sb.sub.2(SO.sub.4).sub.3), strontium-based (SrSO.sub.4), or barium-based (BaSO.sub.4) antioxidant.

3. A method of manufacturing an oriented electrical steel sheet, the method comprising: producing a hot rolled steel sheet by hot rolling a steel slab; producing a cold rolled steel sheet by cold rolling the hot rolled steel sheet; performing decarburization annealing and nitride annealing on the cold rolled steel sheet; and applying an annealing separating agent comprising MgO, an oxychloride material, and a sulfate-based antioxidant, and a glassless additive comprising water, and performing final annealing on the electrical steel sheet of which the decarburization annealing and nitride annealing is complete, wherein the oxychloride material is included at a ratio of 10-20 wt % to the MgO at 100 weight part, and the sulfate-based antioxidant is included at a ratio of 3.5-7.5 wt % to the MgO at 100 weight part, wherein the oxychloride material is antimony oxychloride (SbOCl).

4. The method of claim 3, wherein the sulfate-based antioxidant is at least one that is selected from an antimony-based (Sb.sub.2(SO.sub.4).sub.3), strontium-based (SrSO.sub.4), or barium-based (BaSO.sub.4) antioxidant.

5. The method of claim 3, wherein an amount of SiO.sub.2 that is formed at a surface of the electrical steel sheet of which the decarburization annealing and nitride annealing is complete is two times to five times greater than that of Fe.sub.2SiO.sub.4.

6. The method of claim 5, wherein the decarburization and nitride annealing process is performed in a dew point range of 35-55 C.

7. The method of claim 6, wherein an activation level of the MgO is 400-3000 seconds.

8. The method of claim 7, wherein upon the final annealing, a temperature rising speed is 18-75 C./h in a temperature range of 700-950 C., and a temperature rising speed is 10-15 C./h in a temperature range of 950-1200 C.

9. The method of claim 8, wherein in the decarburization and nitride annealing, a temperature is 800-950 C.

10. The method of claim 9, wherein the glassless additive is applied at 5-8 g/m.sup.2.

11. The method of claim 10, wherein the steel slab comprises Sn at 0.03-0.07 wt %, Sb at 0.01-0.05 wt %, and P at 0.01-0.05 wt %, the remaining portion comprises Fe and other inevitably added impurities, and the steel slab satisfies P+0.5Sb at 0.0370-0.0630 wt %.

12. The annealing separating agent of claim 1 excluding chlorides.

13. The annealing separating agent of claim 1 applied to a steel.

Description

MODE FOR INVENTION

(1) These and other objects of the present application and a method of achieving them will become more readily apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples while indicating preferred embodiments of the invention are given by way of illustration only since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

(2) In an exemplary embodiment according to the present invention, as a means for achieving the object, entire control of a process of producing an oriented electrical steel sheet is required. In this case, a use material essentially includes Sn: 0.03-0.07 wt %, Sb: 0.01-0.05 wt %, and P: 0.01-0.05 wt %, and by hot rolling a steel slab essentially including Sn: 0.03-0.07 wt %, Sb: 0.01-0.05 wt %, and P: 0.01-0.05 wt %, a hot rolled plate of a 2.0-2.8 mm thickness is produced, and after annealing and acid pickling of the hot rolled plate, a cold rolled plate having a final thickness of 0.23 mm is produced via cold rolling.

(3) In a process of performing a decarburization and nitriding treatment after cold rolling, by controlling the temperature, atmosphere, and dew point of a furnace, an amount of an oxidation layer that is generated at a material surface is adjusted so that SiO.sub.2 becomes 2-5 times the Fe.sub.2SiO.sub.4. In this case, the dew point is adjusted to 35-55 C.

(4) By mixing an annealing separating agent that is formed with MgO: 100-200 g, an oxychloride material: 10-20 g of an inorganic compound form having an insoluble property in an aqueous solution, and a sulfate-based antioxidant: 1-5 g with water: 800-1500 g in a material that is produced with the above method, by producing the mixture in a slurry, by drying, applying, and winding the slurry at 300-700 C., by maintaining a temperature rising rate of 15 C./h or more at a segment of 700-1200 C. in a 10% nitrogen-containing hydrogen atmosphere, by performing final high temperature annealing that soaks for 20 hours or more at a temperature of 120010 C., and by finally applying an insulating coating agent, an oriented electrical steel sheet is produced.

(5) In an exemplary embodiment according to the present invention, an activation level of activated MgO that is used in the annealing separating agent is limited to 400-3000 seconds, and an oxychloride material of an inorganic compound form that is insoluble in an aqueous solution may be applied to an antimony-based or bismuth-based material.

(6) Further, in an exemplary embodiment according to the present invention, as a sulfate-based material that is used as an anti-oxidizing agent, at least one of an antimony-based, strontium-based, and barium-based material may be used.

(7) In an exemplary embodiment according to the present invention, when producing an oriented electrical steel sheet not having a base coating, a base coating free type of oriented electrical steel sheet in which a surface has very good roughness and gloss and in which iron loss is thus remarkably enhanced can be produced, compared with when producing a conventional glassless oriented electrical steel sheet, through a complex process not having economic efficiency such as acid pickling or chemical polishing or a process of evaporating at a surface after enabling an FeCl.sub.2 film to form, as the chloride reacts with a material surface while high temperature annealing by adding a chloride to an annealing separating agent.

(8) Hereinafter, a reason for limiting a component of an oriented electrical steel sheet according to an exemplary embodiment of the present invention will be described. This is because it is very appropriate in producing a base coating free type of electrical steel sheet that is suggested in an exemplary embodiment according to the present invention. Each element metallurgically contributes to improve magnetism of an oriented electrical steel sheet by the following operation.

(9) In an exemplary embodiment according to the present invention, unless particularly described, a component content is measured in weight percent.

(10) Sn: 0.03-0.07 wt %

(11) When adding Sn, in order to reduce a size of a secondary grain, by increasing the number of secondary nuclei of a {110}<001> orientation, iron loss can be improved. Further, Sn performs an important function in suppressing grain growth through segregation in a grain boundary, and prevents AlN particles from coarsening and compensates weakening of an effect of suppressing grain growth by increasing a Si content. Therefore, even with a relatively high Si content, successful forming of the {110}<001> secondary recrystallization texture can be resultantly guaranteed. That is, a Si content can be increased and a final thickness can be reduced without weakening completeness of a {110}<001> secondary recrystallization structure. As described above, it is preferable that such a content of Sn is 0.03-0.07 wt % within a range in which a content of other components is appropriately adjusted. That is, as described above, when a content range of Sn is adjusted to 0.03-0.07 wt %, a discontinuous and remarkable iron loss reduction effect that could not be conventionally predicted may be determined, and thus a Sn content in an exemplary embodiment according to the present invention is limited to the range.

(12) Further, when a Sn content excessively exists, there may be a problem that brittleness increases, and thus when adjusting Sn to the above-described range, it is effective in improving brittleness.

(13) Sb: 0.01-0.05 wt %

(14) Sb performs operation of suppressing excessive growth of a primary re-grain by segregating at a grain boundary. By removing non-uniformity of a primary recrystallized grain size according to a thickness direction of a sheet and simultaneously stably forming secondary recrystallization by suppressing grain growth at a primary recrystallization step by adding Sb, an oriented electrical steel sheet having excellent magnetism may be formed. Particularly, such an effect of Sb can be largely improved to a level that could not be predicted in a conventional document when containing Sb at 0.01-0.05 wt %.

(15) Sb suppresses excessive growth of a primary recrystallized grain by segregating at a grain boundary, but when Sb at 0.01 wt % or less is contained, it is difficult to appropriately exhibit suppression thereof, and when Sb at 0.05 wt % or more is contained, a primary recrystallized grain size excessively decreases and thus a secondary recrystallization start temperature is lowered, whereby a magnetic characteristic is deteriorated or a suppressing force of grain growth excessively increases and thus secondary recrystallization may not occur Therefore, in an exemplary embodiment according to the present invention, a content of Sb is limited to the range.

(16) P: 0.01-0.05 wt %

(17) P promotes growth of a primary recrystallized grain in an oriented electrical steel sheet of a low temperature heating method and thus enhances integration of {110}<001> orientation in a final product by raising a secondary recrystallization temperature. When a primary recrystallized grain is excessively large, secondary recrystallization becomes unstable, but as long as secondary recrystallization occurs, it is advantageous in magnetism that a primary recrystallized grain is large to raise the secondary recrystallization temperature. P lowers iron loss of a final product by increasing the number of grains having the {110}<001> orientation in a primarily recrystallized steel sheet and improves {110}<001> integration of a final product by strongly developing a {111}<112> texture in a primary recrystallization plate and thus a magnetic flux density increases. Further, P reinforces a suppressing force by delaying decomposition of deposition by segregating at a grain boundary to a high temperature of about 1000 C. upon secondary recrystallization annealing. When such a content of P is limited to 0.01-0.05 wt %, a remarkable effect that could not be predicted in a conventional art can be obtained. In order to appropriately exhibit an effect of P, it is necessary to limit a content of P to 0.01 wt % or more, and when a content of P is 0.05 wt % or more, a size of a primary recrystallized grain is reduced and thus secondary recrystallization becomes unstable and brittleness is increased and thus cold rolling is impeded. Therefore, in an exemplary embodiment according to the present invention, a content of P is limited to the range.

(18) P+0.5Sb: 0.0370-0.0630%

(19) Further, in an exemplary embodiment according to the present invention, in addition to a case of adding the several elements, by adjusting a content of the P+0.5Sb to the above-described range, iron loss was further improved. This is because, by adding the elements together, a synergistic effect can be obtained, and when a synergistic effect satisfies the equation range, the synergistic effect is discontinuously maximized, compared with other numeral ranges. Therefore, in an exemplary embodiment according to the present invention, in addition to each component content, the P+0.5Sb is limited to the range.

(20) In addition to the above metallurgical merit, Sn and Sb that are used as major elements are added to steel, and in an FeSi alloy like an oriented electrical steel sheet, high temperature oxidation resistance is improved.

(21) This is a very important precondition for producing a base coating free product that is suggested in an exemplary embodiment according to the present invention, and for base coating free production, only an appropriate amount of a base coating layer should be generated through a selective reaction between a SiO.sub.2 oxidation layer inevitably occurring during a decarburization annealing process and a MgO slurry that is used as an annealing separating agent, and it is very important to suppress an Fe-based oxidation layer that may produce other by-products.

(22) Therefore, in an exemplary embodiment according to the present invention, in order to control quality of an oxidation layer that performs a most important function in a base coating free process as well as a meaning as a metallurgical element for improving magnetism of an oriented electrical steel sheet, a slab including Sn and Sb in steel is used as a start material.

(23) Hereinafter, a method of producing an oriented electrical steel sheet according to an exemplary embodiment of the present invention will be described.

(24) A hot rolled plate of 2.0-2.8 mm is produced by hot rolling the above-described steel slab, and after annealing and acid pickling of the hot rolled plate, cold rolling of the hot rolled plate is performed to a thickness of 0.23 mm, which is a final thickness. Thereafter, the cold rolled steel sheet undergoes decarburization annealing and recrystallization annealing, and this will be described in detail.

(25) In order to generate an inhibitor that appropriately controls secondary recrystallization growth upon high temperature annealing while removing carbon that is included in steel, the cold rolled steel sheet undergoes decarburization and nitride annealing in a mixed gas atmosphere of ammonia+hydrogen+nitrogen. By setting a temperature within a furnace to about 800-950 C. under a humid atmosphere and at a temperature lower than 800 C., a sufficient decarburization annealing effect does not occur. As grains are maintained in a micro-state, upon secondary recrystallization, crystals of an undesirable orientation may grow, and when a temperature within a furnace is higher than 950 C., primary recrystallized grains may excessively grow. Upon decarburization and nitride annealing in an exemplary embodiment according to the present invention, a temperature within a furnace is limited to 800-950 C.

(26) Further, it is advantageous for management of an oxidation layer to set about 50-70 C. to have a lower temperature by about 2-4 C. than that of a component system that does not contain Sn, Sb, and P, and it is more advantageous for grain orientation control or iron loss improvement of a final product.

(27) As described above, from a metallurgical viewpoint, in a decarburization and nitride annealing process, an oxidation layer may be inevitably generated at a surface in a conventional oriented electrical steel sheet production process, and by applying a generated oxidation layer and a MgO slurry (aqueous solution in which MgO is dispersed in water), in a high temperature annealing process, a base coating (Mg.sub.2SiO.sub.4) layer is formed. A forsterite layer, i.e., a base coating that is generated in this way, generally prevents fusion-bonding between a plates of an oriented electrical steel sheet coil and gives tension to the plate, and thus it is known that iron loss is reduced and an insulating property is imparted to a material.

(28) However, currently, while demand for a low iron loss and high magnetic flux density material increases, a thin thickness trend of a product is accelerated and thus a magnetic property that is damaged at the material surface side gradually becomes an important factor. From this viewpoint, a base coating that is generated through a reaction with an oxidation layer that is generated in a decarburization and nitride process and a MgO slurry that is used as an annealing separating agent operate to generate a pinning point that disturbs flow of magnetic domains moving through a material surface, and research for removing this has been performed.

(29) When a cold rolled plate passes through a heating furnace that is controlled in a humid atmosphere for decarburization nitriding, Si having highest oxygen affinity in steel reacts with oxygen that is supplied from a water vapor within the furnace and thus SiO.sub.2 is first formed at a surface, and as oxygen penetrates to the steel, an Fe-based oxide is generated. SiO.sub.2 that is generated in this way forms the base coating through the following chemical reaction equation.
2Mg(OH).sub.2+SiO.sub.2.fwdarw.Mg.sub.2SiO.sub.4+2H.sub.2O(1)

(30) As in the reaction equation 1, when SiO.sub.2 reacts with the MgO slurry in a solid state, in order to perform a complete chemical reaction, a material with a catalyst function of connecting between two solids is required, and fayalite (Fe.sub.2SiO.sub.4) performs the catalyst function. Therefore, conventionally, appropriate fayalite forming as well as a SiO.sub.2 forming amount was important.

(31) However, in an exemplary embodiment according to the present invention, after minimally forming a base coating layer that disturbs magnetic domain movement of a material in a front end portion of a high temperature annealing process, the base coating layer is removed in a rear end portion, and thus it is unnecessary to form a large amount of SiO.sub.2 and fayalite on a material surface to enable the SiO.sub.2 and fayalite to react with MgO like a conventional production method. In such a case, in a decarburization and nitriding annealing process, it is advantageous to form a thin SiO.sub.2 layer at a material surface through the control of a dew point, a soaking temperature, and an atmosphere gas, and to generate a very small amount of fayalite. This is because, in a conventional case, in order to perfectly induce a reaction between SiO.sub.2 and MgO, fayalite, which is a relatively large amount of a catalyst material, is required, and in order to generate fayalite, Fe-based oxides such as FeO and Fe.sub.2SiO.sub.3 are essentially generated together. The generated FeO and Fe.sub.2SiO.sub.3 do not basically react with a glassless-based addition material and are attached to a material surface to form an FeO system of an oxide mound (hereinafter, Fe mound), and in such a case, a product having an enhanced surface in which base coating is excluded and excellent gloss cannot be obtained.

(32) Therefore, in an exemplary embodiment according to the present invention, upon decarburization and nitride annealing, by imparting a change to a dew point temperature within a furnace, a change of an oxidation layer composition was induced, and an amount of fayalite and SiO.sub.2 that is induced in this way was quantified through FT-IR.

(33) As a result, in an amount of an oxidation layer that is formed at a surface, when SiO.sub.2 is adjusted to two times to five times that of fayalite, roughness and glossiness of a surface were excellent, and when SiO.sub.2 is adjusted to two times or less that of fayalite, an Fe mound defect occurs and thus surface roughness is deteriorated, while when SiO.sub.2 is adjusted to five times or more that of fayalite, forsterite forming is very weak and thus fostelite forming is very poor, whereby at a material surface, much residual material exists.

(34) Therefore, in an exemplary embodiment according to the present invention, SiO.sub.2 is formed at two times to five times that of fayalite.

(35) As described above, on a specimen in which an oxidation layer of a material is adjusted, a conventional glassless additive like BiCl.sub.3 was mixed with MgO and water, applied, and finally annealed in a coil shape. Upon final annealing, a primary soaking temperature was 700 C., a secondary soaking temperature was 1200 C., and a temperature rising condition of a temperature rising segment was 18-75 C./h at a temperature segment of 700-950 C. and was 10-15 C./h at a temperature segment of 950-1200 C. A soaking time at 1200 C. was processed as 15 hours. An atmosphere upon final annealing was a mixed atmosphere of 25% nitrogen+75% hydrogen up to 1200 C., and after arriving at 1200 C., a 100% hydrogen atmosphere was maintained and the furnace was cooled.

(36) In a specimen that is processed in this way, roughness and glossiness enhancement was excellent compared to that of a conventional glassless process, but an enhanced surface property of an acid pickling and chemical polishing level may not be obtained and a limitation exists in magnetism enhancement.

(37) Therefore, in an exemplary embodiment according to the present invention, when components that are used for an annealing separating agent are applied and dried at a surface of a material, a material remaining at a surface after high temperature annealing and reaction mechanism on each component basis was researched.

(38) First, after high temperature annealing, when analyzing a residual material of a specimen in which a base coating is not completely removed, the residual material was determined as a spinel-based (MgO.Al.sub.2O.sub.3) compound and an Fe-based oxide. Further, when such a residual material remains, a magnetic characteristic that a low iron loss oriented electrical steel sheet requires may not be satisfied. Therefore, in an exemplary embodiment according to the present invention, in order to ultimately overcome a limitation of a conventional glassless type and to remarkably enhance iron loss of an oriented electrical steel sheet, research has been performed with an emphasis on the above characteristic deterioration material forming mechanism.

(39) When an activation level of MgO which a main component of an annealing coating agent is high, a spinel-based oxide, which is a primary characteristic deterioration cause of characteristic deterioration causes that are suggested in the foregoing description, reacts with SiO.sub.2 existing at a surface like reaction equation 1 to form a base coating layer and reacts with a surface oxidation layer and Al, which is a component among steel existing at a material interface, and thus it is determined that the above spinel-based composite oxide has occurred. In order to prove this, in an exemplary embodiment according to the present invention, by artificially adjusting an activation level of MgO, MgO having various activation levels was produced. An activation level of the MgO is defined as an ability in which MgO powder may cause a chemical reaction with other components, and is measured as a time that is taken for MgO to completely neutralize a predetermined amount of citric acid solution.

(40) In MgO that is generally used as an annealing separating agent for a common oriented electrical steel sheet, high activation is used, with an activation level of about 50-300 seconds, and in an exemplary embodiment according to the present invention, in addition to MgO having a common activation level, by applying an activation level of MgO to adjusted MgO through a high temperature firing process, a spinel-based compound was suppressed from remaining as a residual material.

(41) Particularly, in an exemplary embodiment according to the present invention, an activation level of MgO is limited to 400-3000 seconds, and when an activation level is smaller than 400 seconds, after high temperature annealing, spinel-based oxide remains at a surface like common MgO, while when an activation level is larger than 3000 seconds, an activation level is excessively weak and thus MgO does not react with an oxidation layer existing at a surface and a base coating layer may thus not be formed. Therefore, in an exemplary embodiment according to the present invention, an activation level of MgO is limited to 400-3000 seconds.

(42) A second cause of magnetic characteristic deterioration is Fe-based oxide. As described above, generation of the Fe-based oxide is limited through introduction of Sn and Sb in steel as well as the control of a dew point and an atmosphere within a furnace in a decarburization and nitriding process. However, in spite of such a limitation, a generation cause of the Fe-based oxide is related to a chemical reaction between chloride that is used as a glassless additive and an aqueous solution that is used for distributing an annealing separating agent. When BiCl.sub.3 that is well known as a chloride of a conventional glassless system is generally applied on a specimen as an aqueous solution together with MgO and a high temperature annealing process is performed, the following chemical reaction occurs at a surface.
BiCl.sub.3+H.sub.2O.fwdarw.BiOCl(s)+2HCl(2)

(43) As in the chemical reaction equation 2, 2HCl that is generated on an aqueous solution causes the following chemical reaction together with Fe or FeO existing at a material surface.
(Fe,FeO)+HCl.fwdarw.FeCl.sub.2(s)+H.sub.2O(3)

(44) Therefore, in order to apply an annealing separating agent in which a common glassless additive is introduced and to form the annealing separating agent in a coil shape, when drying the annealing separating agent at 700 C. or less, an Fe-based oxidation layer is already generated, and a material that is generated in this way forms a deep root at a material surface during a high temperature annealing process.

(45) In order to suppress such a phenomenon, by using BiCl.sub.3 having strong oxidation or an antimony oxychloride (SbOCl) additive that is not dissociated within an aqueous solution other than chloride of a line similar to BiCl.sub.3 and that originally suppresses Fe-based oxide and antimony sulfate (Sb.sub.2(SO.sub.4)3)) not having a Cl group, an exemplary embodiment according to the present invention is to solve such problem.

(46) That is, in order to produce an oriented electrical steel sheet having excellent gloss, roughness, and iron loss, MgO: 100-200 g in which activation is adjusted by an annealing separating agent, antimony oxychloride (SbOCl): 10-20 g having an insoluble property in an aqueous solution, antimony sulfate (Sb.sub.2(SO.sub.4)3)): 1-5 g, and water 800-1500 g are mixed, are formed in a slurry form, are applied in a thickness of 5-8 g/m2 at a surface of a material in which decarburization and nitriding is terminated, and are dried at 300-700 C. After a specimen that is produced in this way is produced in a coil shape, the specimen undergoes high temperature annealing, and a temperature rising speed of a fast temperature rising speed segment of an initial process of high temperature annealing is determined to be 18-75 C./h, while a slow temperature rising speed is determined to be 10-15 C./h in consideration of secondary recrystallization. In this case, thermal decomposition of a glassless-based additive within an annealing separating agent at a first half of a high temperature annealing process is performed at about 280 C. as follows.
2SbOCl.fwdarw.Sb2(s)+O.sub.2(g)+Cl.sub.2(g)(4)

(47) As in the chemical reaction equation 4, unlike BiCl.sub.3 or SbCl.sub.3 in which a Cl group may be dissociated in an aqueous solution, in a chloride of an oxychloride form, a Cl group is generated only through thermal decomposition, and after antimony oxychloride is produced in a slurry state on an aqueous solution, in an application and drying process, an Fe-based oxide that may ultimately impede roughness, glossiness, and iron loss reduction is not generated.

(48) A Cl gas that is separated in this way forms FeCl.sub.2 at an interface of a material and an oxidation layer while being again diffused toward a material surface rather than being discharged to the outside of a coil by a pressure within a furnace operating in the coil.
Fe(material)+Cl.sub.2.fwdarw.FeCl.sub.2(interface of material and oxidation layer)(5)

(49) Thereafter, at about 900 C., by a MgO and SiO.sub.2 reaction, at an outermost surface of a material, base coating is performed as in Equation 5. Thereafter, at about 1025-1100 C., FeCl.sub.2 that has been formed at an interface of a material and an oxidation layer starts to be decomposed, and while Cl.sub.2 gas that is decomposed in this way is discharged to an outermost surface of the material, the Cl.sub.2 gas separates the base coating that has been formed in an upper portion from the material.

(50) In an exemplary embodiment according to the present invention, after a slurry is produced, when the slurry is dried, an amount of chloride of an oxychloride form that does not impede iron loss reduction and that does not generate the Fe-based oxide is limited and is used at 10-20 g to an injected MgO amount of 100-200 g. When an amount of the chloride is injected to be smaller than 10 g, Cl to form enough FeCl.sub.2 may not be supplied, and thus there is a limitation in improving roughness and glossiness after high temperature annealing, and when an amount of the chloride is injected to be larger than 20 g, an excessively greater amount than that of MgO, which is a major component of an annealing separating agent, disturbs the base coating from being formed and may thus metallurgically have an influence on secondary recrystallization as well as a surface, and thus in an exemplary embodiment according to the present invention, for MgO of 100-200 g, the chloride is limited to 10-20 g.

(51) Antimony sulfate (Sb.sub.2(SO.sub.4)3) together with antimony oxychloride (SbOCl) is injected to thinly form a forsterite layer that is generated by a MgO and SiO.sub.2 reaction, and is limited to 1-5 g for 100-200 g of MgO. When antimony sulfate (Sb.sub.2(SO.sub.4)3)) together with antimony oxychloride (SbOCl) of an amount smaller than 1 g is added, an effect as an additional auxiliary agent is slight, and antimony sulfate (Sb.sub.2(SO.sub.4)3)) together with antimony oxychloride (SbOCl) does not contribute to improvement of roughness and gloss, and when with antimony sulfate (Sb.sub.2(SO.sub.4)3)) together with antimony oxychloride (SbOCl) of an amount of more than 5 g is added, base coating forming may be disturbed due to a much greater amount than that of MgO, which is a major component of an annealing separating agent like antimony oxychloride (SbOCl), and thus in an exemplary embodiment according to the present invention, an addition amount of SbOCl and Sb.sub.2 (SO.sub.4)3 is limited to the range.

(52) Hereinafter, an exemplary embodiment according to the present invention will be described in detail.

Exemplary Embodiment 1

(53) In a component system that is suggested in the present invention and a common oriented electrical steel sheet component system, after Si: 3.26%, C: 0.055%, Mn: 0.12%, Sol. Al: 0.026%, N: 0.0042%, and S: 0.0045%, and Sn, Sb, and P contents were applied to a MgO annealing separating agent including common chlorides, roughness and glossiness were measured, and it was determined whether the base coating was formed. Here, the glossiness is Gloss glossiness, and in a reflection angle of 60, an amount of light that is reflected from a surface is measured, where mirror surface glossiness of 1000 is base glossiness.

(54) TABLE-US-00001 TABLE 1 Spec- Sn P Sb imen content content content Glassless Roughness Glossiness number (wt %) (wt %) (wt %) additive (Ra: m) (index) 1 0 0 0 MgCl.sub.2 0.65 54 CaCl.sub.2 0.58 67 2 0 0 0.015 MgCl.sub.2 0.55 72 CaCl.sub.2 0.67 48 3 0 0.02 0 MgCl.sub.2 0.74 66 CaCl.sub.2 0.62 59 4 0 0.035 0.015 MgCl.sub.2 0.59 62 CaCl.sub.2 0.60 57 5 0.01 0.035 0.025 MgCl.sub.2 0.57 82 CaCl.sub.2 0.61 48 6 0.03 0.035 0.025 MgCl.sub.2 0.48 103 CaCl.sub.2 0.45 107 7 0.04 0.035 0.025 MgCl.sub.2 0.49 95 CaCl.sub.2 0.50 89 8 0.05 0.02 0.035 MgCl.sub.2 0.46 106 CaCl.sub.2 0.47 109 9 0.05 0.035 0.045 MgCl.sub.2 0.54 97 CaCl.sub.2 0.51 98 10 0.06 0.35 0.025 MgCl.sub.2 0.43 115 CaCl.sub.2 0.42 121

(55) As shown in Table 1, after mixing a material that is known as a conventional glassless chloride annealing separating agent with MgO in Sn and Sb addition materials that are suggested in the present invention, by applying a slurry thereof, much better glossiness and roughness than a common oriented electrical steel sheet was obtained regardless of a kind of a chloride annealing separating agent. It may be indirectly seen that Sn and Sb in steel are related to improvement of high temperature oxidation resistance, and particularly have an effect that disturbs Fe oxide existing as a residual material from being formed upon performing a removal reaction of a forsterite layer of a chloride, i.e., a base coating in a high temperature annealing process by suppressing external oxidation. In an exemplary embodiment according to the present invention, Sn and Sb addition materials that are advantageous in suppressing external oxidation and removing a base coating were used as a testing material.

(56) In Table 2, after cold rolling is performed to a thickness of 0.23 mm using an Sn and Sb addition steel slab (specimen number 10 component system) that is suggested in Table 1, when performing decarburization and nitride annealing, a change of an oxidation layer composition according to a dew point temperature within a furnace was induced, and base coating removal ability was compared through a difference of roughness and glossiness according to the induced change. In this case, a soaking temperature of a furnace is 875 C., and by simultaneously injecting a mixed atmosphere of hydrogen at 75%, nitrogen at 25%, and dry ammonia gas at 1%, and maintaining the state for 180 seconds, a simultaneous decarburization and nitride processing was performed.

(57) In a decarburization and nitride annealing process, a composition of an oxidation layer and a total oxygen amount that is formed at a material surface is largely affected by a change of a dew point temperature within a furnace. As shown in Table 2, in an amount of an oxidation layer that is formed at a surface, when SiO.sub.2 is adjusted to two times to five times that of Fe.sub.2SiO.sub.4, roughness and glossiness of the surface is excellent, and when SiO.sub.2 is adjusted to two times or less that of Fe.sub.2SiO.sub.4, a Fe mound defect occurs and thus surface roughness is deteriorated, while when SiO.sub.2 is adjusted to five times or more that of Fe.sub.2SiO.sub.4, Fe.sub.2SiO.sub.4 is very weakly formed and thus base coating forming is very poor, whereby at a material surface, much residual material exists. This is because excessively generated FeO and Fe.sub.2SiO.sub.3 do not basically react with a glassless-based additive and are attached to a material surface to form the Fe mound defect. In such a case, it can be seen that a product of an enhanced surface and excellent gloss in which base coating is excluded cannot be obtained.

(58) TABLE-US-00002 TABLE 2 Dew Total Spec- point oxygen imen temper- amount SiO.sub.2/ Glassless Roughness Glossiness number ature (ppm) FeO additive (Ra: m) (index) 1 35 340 7.2 MgCl.sub.2 0.32 114 2 CaCl.sub.2 0.34 120 3 BiCl.sub.3 0.31 126 4 SbCl.sub.3 0.31 132 5 45 480 4.8 MgCl.sub.2 0.32 177 6 CaCl.sub.2 0.34 172 7 BiCl.sub.3 0.31 191 8 SbCl.sub.3 0.31 194 9 55 630 2.3 MgCl.sub.2 0.39 160 10 CaCl.sub.2 0.38 158 11 BiCl.sub.3 0.35 179 12 SbCl.sub.3 0.34 166

(59) Therefore, in order to produce a base coating free type of oriented electrical steel sheet having excellent roughness and glossiness and having very good iron loss due to the excellent roughness and glossiness that is sought in an exemplary embodiment according to the present invention, a condition of an amount and a composition of an oxidation layer and a slab component system was derived from Tables 1 and 2. That is, in a cold rolled plate that is produced with a component system of specimen number 5 of Table 1, a specimen that is produced with an oxidation layer condition (SiO.sub.2/Fe.sub.2SiO.sub.4=4.8) that is derived in Table 2 was used as a testing material, a new annealing separating agent for new base coating free that is suggested in an exemplary embodiment according to the present invention was produced and applied, as in Table 3, and a material characteristic including a magnetic property was compared.

(60) When producing an annealing separating agent, the annealing separating agent was produced based on MgO at 100 g and water at 1000 g. As shown in Table 3, when using MgO having a high activation level and BiCl3 having strong oxidation, and MgO in which an activation level is appropriately adjusted instead of a chloride of a line similar thereto, in a specimen that applies an antimony oxychloride (SbOCl) additive that is not dissociated within an aqueous solution and that thus originally suppresses Fe oxide and antimony sulfate (Sb.sub.2(SO.sub.4)3) not having Cl group, an oriented electrical steel sheet having excellent roughness and gloss and very low iron loss was obtained.

(61) TABLE-US-00003 TABLE 3 MgO Base coating free Magnetic Activity Common annealing flux level glassless separating agent Roughness Glossiness Density Iron loss (S) (BiCl.sub.3) SbOCl Sb.sub.2 (SO.sub.4)3 (Ra: m) (index) B10 (W17/50) Remark 50 1.91 0.87 Common material 5 0.31 191 1.91 0.90 Comparative 10 0.30 200 1.92 0.88 material 5 0.29 215 1.92 0.88 10 0.30 209 1.92 0.89 20 0.28 220 1.92 0.87 5 2.5 0.27 235 1.92 0.86 10 2.5 0.26 280 1.92 0.85 20 2.5 0.28 255 1.92 0.86 500 5 0.26 288 1.92 0.85 Comparative 10 0.25 301 1.92 0.83 material 10 0.5 0.25 299 1.93 0.83 10 3.5 0.24 316 1.93 0.81 Present invention 20 7.5 0.23 330 1.93 0.79 Present invention 20 2.5 0.25 287 1.93 0.82 Comparative material

(62) While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

(63) Therefore, it should be understood that the foregoing exemplary embodiments are not limited but are illustrated. The scope of the present invention is represented by claims to be described later rather than the detailed description, and it should be recognized that the meaning and scope of the claims and an entire change or a changed form that is derived from an equivalent concept thereof are included in the scope of the present invention.

(64) While this invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.