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WO2008047999A1 - Agent de separation de recuit pour tole d'acier electrique a grains orientes presentant un film de verre uniforme et d'excellentes proprietes magnetiques, et procede de fabrication associe - Google Patents

Agent de separation de recuit pour tole d'acier electrique a grains orientes presentant un film de verre uniforme et d'excellentes proprietes magnetiques, et procede de fabrication associe Download PDF

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Publication number
WO2008047999A1
WO2008047999A1 PCT/KR2007/003544 KR2007003544W WO2008047999A1 WO 2008047999 A1 WO2008047999 A1 WO 2008047999A1 KR 2007003544 W KR2007003544 W KR 2007003544W WO 2008047999 A1 WO2008047999 A1 WO 2008047999A1
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Prior art keywords
mgo
annealing
annealing separator
steel sheet
melting
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Ceased
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PCT/KR2007/003544
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English (en)
Inventor
Jong-Ho Park
Jong-Soo Woo
Song-Kwon Park
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Posco Holdings Inc
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Posco Co Ltd
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Publication date
Priority claimed from KR1020060101232A external-priority patent/KR100762436B1/ko
Priority claimed from KR1020060101233A external-priority patent/KR100865316B1/ko
Application filed by Posco Co Ltd filed Critical Posco Co Ltd
Priority to CN200780038866XA priority Critical patent/CN101528950B/zh
Publication of WO2008047999A1 publication Critical patent/WO2008047999A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
    • C21D8/1283—Application of a separating or insulating coating

Definitions

  • the present invention relates to an annealing separator for grain-oriented electrical steel sheets having excellent surface properties, and a method of producing grain-oriented electrical steel sheets using the same, and more particularly to an annealing separator for grain-oriented electrical steel sheets having excellent surface properties, which comprises 100 parts by weight of MgO, consisting of 40-95% of active MgO and 5-60% of inactive MgO, and 0.01- 0.5 parts by weight of a low-melting-point compound having a melting point lower than 900 ° C, and to a method for producing grain-oriented steel sheets, which comprises applying said annealing separator in the form of slurry to a steel sheet after stirring the annealing separator in a mixing tank at a revolution speed of 1500-3000 rpm for more than 10 minutes.
  • a material slab containing 2.5-4.0 wt% of Si is hot-rolled, and the hot-rolled sheet is annealed and subjected to one-time cold rolling or to a plurality of cold rolling steps with annealing steps therebetween, so as to attain a final sheet thickness. Then, the cold-rolled sheet is subjected to a decarburization annealing process, in which cold-rolling oils or contaminants are removed by burn-off or cleaning treatment, and P H 2 O /P H2 is controlled in an N 2 +H 2 atmosphere, thus forming an oxide film, based on Fe 2 SiO 4 and SiO 2, which play an important role in decarburization, primary recrystallization and glass film formation.
  • an MgO-based annealing separator is stirred in water to make a slurry, and the slurry is applied on the steel sheet using a roll and then dried. Then, the steel sheet is wound into a coil and subjected to finish annealing. Then, the steel sheet coil is applied with an insulating coating agent in a continuous line and subjected to annealing and heat flattening, thus obtaining a final product.
  • the (110) ⁇ 001> crystal having an ⁇ 001> axis, preferentially develops and grows to erode other crystal grains which inhibit the growth of normal grains by pinning the grain boundary migration of primary recrystallization grains, such as AlN and MnS, so-called inhibitors which are finely dispersed in the steel, during this secondary recrystallization step.
  • primary recrystallization grains such as AlN and MnS
  • the reactivity of the annealing separating agent is very important, because it influences the oxidation or nitrification in coils, which occur during glass film formation in the finish annealing process, and thus it influences not only the formation of the glass film, but also the behavior of inhibitors in secondary recrystallization.
  • the conditions of additives which are added to improve the properties (particularly, reactivity) of the annealing separator, influence the change in the oxide film formed during decarburization annealing, the temperature of initiation of glass film formation, the rate of glass film formation, the uniformity of the glass film, and the degree of oxidation of an atmosphere between the steel sheet surfaces, and, as a result, such factors also influence the stability of inhibitors in steel, thus influencing secondary recrystallization.
  • the activity distribution or particle size distribution of MgO is important in order to smoothly induce a reaction with the decarburized oxide layer.
  • the oxide film formed in the decarburization annealing process influences the change in components or shapes in the finish annealing process, and thus is an important factor that influences the temperature of initiation of glass film formation, the rate of film formation, the film uniformity and the oxidation degree of an atmosphere between steel sheet surfaces. Also, such factors influence the stability of inhibitors in steel, and thus influence secondary recrystallization. Thus, the role thereof in a high-temperature annealing process is very important.
  • the reaction of formation of the glass film refers to a forsterite film, which is formed 5 through a reaction between MgO, which is the main component of the annealing separator, and SiO 2 , which is the main component of the oxide film formed in the decarburization annealing process.
  • MgO which is the main component of the annealing separator
  • SiO 2 which is the main component of the oxide film formed in the decarburization annealing process.
  • the annealing separator is prepared by dispersing MgO in water, if necessary, together with a reaction promoter, to make a slurry, which is then applied on a steel sheet.
  • a reaction promoter As this additive for reaction promotion, oxide, an S compound, a B compound or the like has been used.
  • oxide, an S compound, a B compound or the like has been used.
  • Japanese Patent Publication No. Hei 2650817 suggests the use of MgO having a low degree of hydration.
  • MgO which has a citric acid activity (CAA) of 100-400 seconds at a final reaction rate of 40%, a citric acid activity of0 1000-4000 seconds at a final reaction rate of 80%, a water content of less than 2.5% at slurry adjustment conditions of 20 ° C and 60 minutes, an average particle size of less than 2.5 [M, and a particle size of 5% finer than 325 Mesh.
  • CAA citric acid activity
  • Japanese Patent Publication No. Sho 58-006783 discloses a method of using an annealing separator, which is based on MgO and contains S or an S compound and a Sr compound
  • Japanese Patent Publication No. Sho 57-032716 discloses a method of using an annealing separator, which is based on MgO and contains an Sr compound and/or a Ti compound.
  • the additives suggested in such methods are SrSO 4 , Sr(OH) 2 1 SH 2 O and the like, and such Sr compounds are effective in thickening the forsterite film, but have problems in that a carburization phenomenon caused by the generation of decomposed gas occurs in the final annealing process, thus deteriorating the magnetic properties of the sheet.
  • Hei 2895645 discloses a method for producing grain-oriented electrical steel sheets, which comprises adding one or more selected from among SrZrO 3 and
  • SrSnO 3 in an amount of 0.1-10 wt% (as Sr).
  • the invention disclosed in this publication aims to improve the shortcomings of the above-described Sr compound addition technology and discloses that the film and magnetic properties of the grain-oriented electrical steel sheet were further improved by maximizing the forsterite suspension using an annealing separator containing an Sr-containing compound.
  • it is a technology which is still unsatisfactory, because a sufficient effect of improving reactivity is not obtained.
  • an annealing separator is obtained by controlling the activity or impurity of MgO, and dispersing the MgO, together with a reaction promoter, if necessary, in pure water in a mixing tank using a stirring device equipped with a propeller rotor, thus preparing a slurry, which is then applied on steel sheets.
  • This MgO is fine particulate MgO, which is obtained by rehydrating Mg(OH) 2 , obtained from brine water or sea water, and calcining the rehydrated Mg(OH) 2 in a box-type batch kiln or a continuous rotary kiln.
  • oxide, an S compound, a B compound or the like has generally been used as a reaction promoter for the formation of a forsterite film.
  • Japanese Patent Publication No. Hei 2650817 suggests the use of MgO having a low degree of hydration.
  • MgO which has a citric acid activity (CAA) of 100-400 seconds at a final reaction rate of 40%, a citric acid activity of 1000-4000 seconds at a final reaction rate of 80%, a hydrated water content of less than 2.5% after stirring at 20 °C for 60 minutes, an average particle size of less than 2.5 ⁇ m, and a particle size of 5% finer than 325 Mesh.
  • CAA citric acid activity
  • the publication indicates that the occurrence of additional oxidation can be inhibited through the use of lower-activity MgO, and thus a uniform film is formed even on a unidirectional silicon steel sheet containing Al-Sb.
  • the effect of making the film uniform is acknowledged, but the description of a decrease in reactivity is insufficient, and the description of film thickness and adhesion is also insufficient.
  • a technology for controlling the particle size distribution of annealing separators is disclosed in Japanese Patent Publication No. Hei 6-116736.
  • This publication discloses that, in a method of forming a forsterite film on unidirectional electrical steel sheets, when (85 + 15 loga)[%] ⁇ X[%]>(55 + 35 loga)[%] ("a" represents particle diameter, and "X%” represents integration amount, and (X[%] ⁇ 100)) is satisfied at an annealing separator particle size of more than 0.5 ⁇ m, and when a temperature elevation rate in the range of 900- 1200 ° C in the finish annealing process is in the range of 2-30 ° C/hr, a stable and good forsterite film is obtained.
  • Japanese Patent Laid-Open Publication No. Sho 52-31296 discloses the application of an annealing separator, which has a particle size distribution of 40-70% at less than 3 ⁇ m and 10-25% at more than 10 ⁇ m and a bulk specific gravity of 0.18-0.30 g/cm 3 .
  • Japanese Patent Laid- Open Publication No. Sho 58-193373 discloses a method for producing grain- oriented electrical steel sheets having excellent magnetic properties, in which an annealing separator, which has a particle size of 0.08-0.18 ⁇ m, as measured by powder X-ray diffraction, is used.
  • Japanese Patent Publication No. Sho 60-14103 discloses a method of producing unidirectional electrical steel sheets, having an insulating film and showing excellent magnetic properties, using an annealing separator containing an Mo compound in an amount of 0.1-10 wt% (as Mo).
  • Japanese Patent Publication No. Hei 2895645 discloses a method for producing grain-oriented electrical steel sheets, which comprises adding one or more selected from among SrZrO 3 and SrSnO 3 in an amount of 0.1-10 wt% (as Sr).
  • the invention disclosed in this publication aims to improve the shortcomings of the above-described Sr compound addition technology, and discloses that the film and magnetic properties of the grain-oriented electrical steel sheet can be further improved by maximizing the suspension of forsterite using an annealing separator containing an Sr-containing compound.
  • the present invention has been made in order to solve the above- described problems occurring in the prior art, and it is an object of the present invention to provide an annealing separator for grain-oriented electrical steel sheets, which achieves a remarkable effect of improving the formation of a glass film, inhibits additional oxidation or additional nitrification during a finish annealing process so as to form a uniform and excellent glass film over the entire surface of a coil, and has excellent magnetic properties.
  • Another object of the present invention is to provide an annealing separator for grain-oriented electrical steel sheets having excellent surface properties, and a method for producing grain-oriented electrical steel sheets using the same, in which low-hydrated MgO, obtained by suitably mixing active MgO with inactive MgO, is used, the mixing conditions of an annealing separator slurry are controlled, an additive having a melting point lower than 900 ° C is used to improve the reactivity of MgO, a remarkable effect of improving the formation of a glass film is obtained even upon the application of low-hydrated MgO, so as to inhibit additional oxidation or additional nitrification during a finish annealing process, thus providing very good film properties and magnetic properties, and the physical property values of coarse MgO particles in low-hydrated MgO, obtained by suitably mixing active MgO with inactive MgO, are adjusted to be within a suitable range, thus solving appearance problems occurring in the coil annealing process.
  • the present invention provides an annealing separator for grain-oriented electrical steel sheets having a uniform film and excellent magnetic properties, which comprises 100 parts by weight of MgO, and 0.01-0.5 parts by weight of a low-melting-point compound having a melting point lower than 900 "C.
  • the annealing separator further comprises, as an additive for controlling the atmosphere between steel sheet surfaces, 0.5-10 parts by weight, based on 100 parts by weight of MgO, of one or two selected from Ti, V, Nb, Cr and Mn oxides, which have a particle diameter of less than 0.5 ⁇ m.
  • the low-melting-point compound contains a compound having a melting point lower than 750 ° C , in an amount of 30% based on the total weight of the low-melting-point compound.
  • the low-melting-point compound is one or more selected from the group consisting of antimony compounds, amide compounds, chlorides, chloroxides, chlorates, chromates, oxides, bromides, hydroxides, hydrides, carbonates, nitrates, tellurates, vanadates, fluorides, borates, phosphates, sulfides, sulfates, iodides, and hydroiodides.
  • the low-melting-point compound comprises one or more elements selected from the group consisting of H, Li, Na, K, Cu, Rb, Ag, Cs, Ba, Be, Mg, Ca, Zn, Sr, Cd, Ba, B, Al, Ga, Y, In, Tl, Ti, Ge, Sn, P, V, Nb, Sb, Ta, Bi, S, Cr, Mo, Te, W, Mn, Fe, Co, and Ni.
  • said MgO has a 40% CAA value of 50-120 seconds, and a hydrated water content of 1.0-2.5%.
  • a silicon steel slab containing, in addition to 2.5-4.0% Si, one or more inhibitors selected from MnS, AlN, Al, Cu, Sn, Sb and Mo depending on the intended use of the desired steel material, is hot-rolled according to a known method.
  • the hot-rolled steel sheet is subjected to one-time cold rolling or to a plurality of cold rolling steps with annealing steps therebetween, thus achieving a final sheet thickness.
  • the cold-rolled steel sheet is subjected to decarburization annealing in a continuous line to form a SiO2-based oxide film on the surface of the steel sheet.
  • the inventive annealing separator is prepared by adding, to MgO, one or more low-melting-point additives, having a melting point lower than 900 ° C , in an amount of 0.01-0.5 parts by weight based on 100 parts by weight of MgO, and optionally adding 0.5-10 parts by weight of one or more oxides selected from among Ti, B and Nb.
  • the annealing separator is sufficiently stirred in water to make a slurry, and the slurry is applied on the steel sheet and dried at a temperature of about 200-300 °C . Then, the dried steel sheet is wound into a coil.
  • the steel sheet coil is subjected to glass film formation, annealing and secondary recrystallization in a batch-type or continuous furnace at a temperature of about 1170-1220 0 C for 15-20 hours while the temperature elevation rate and the amount of nitrogen, as an atmospheric gas, are adjusted.
  • the coil thus treated is washed with water to remove excess annealing separator, and is washed with acid. Then, it is coated with an insulating coating agent, and subjected to heat flattening at a temperature of about 850 °C for the annealing of the insulating coating film, shape correction and stress-removing annealing, thus producing a final product.
  • the glass film and magnetic properties are determined through such a series of processes, and the formation conditions of the oxide film formation conditions in the decarburization annealing process and the conditions of the annealing separator are very important.
  • the annealing separator influences not only the formation time, formation rate, formation amount and uniformity of the glass film, but also additional oxidation or nitrification, which influences the formation of the film during temperature elevation in the finish annealing process.
  • it influences the decomposition rates of important inhibitors, AlN and MnS, or other components in steel sheets, and thus also influences the magnetic properties of the steel products.
  • the annealing separator is obtained by adding, to 100 parts by weight of MgO, 0.01-0.5 parts by weight of one or more selected from the group consisting of antimony compounds, amide compounds, chlorides, chloroxides, chlorates, chromates, oxides, bromides, hydroxides, hydrides, carbonates, nitrates, tellurates, vanadates, fluorides, borates, phosphates, sulfides, sulfates, iodides, and hydroiodides, which have a melting point lower than 900 0 C .
  • the low- melting-point additive contains an additive having a melting point lower than 750 ° C, in an amount of more than 30%, additional oxidation or nitrification does not substantially occur, and thus a uniform glass film is formed over the entire length and width of the coil, and the stabilization of magnetic properties is achieved.
  • Additional oxidation or nitrification of the coil during finish annealing readily occurs in a portion showing a rapid increase in temperature during the process of annealing the coil, that is, the edge of the coil or the outer winding portion of the coil.
  • the use of a given amount of the low-melting-point reaction promoter, as disclosed in the present invention, can provide the following two effects. First, before the initiation of an oxidation or nitrification reaction during coil temperature elevation, the low-melting-point compound forms a glassy, compact and molten layer on the oxide film of the steel sheet, thus inhibiting a reaction with the oxide film.
  • a low- melting-point additive which contained additives having a melting point lower than 750 ° C, in an amount of more than 30%, was highly advantageous for the stability of a glass film formation reaction, because a glassy layer protecting the oxide film starting from low temperatures was formed, and the reaction of MgO with the decarburized oxide layer progressed in a more reliable and stable manner. Also, it was found that this addition of the low-melting-point compound was more advantageous for increasing the uniformity of the glass film, because, when sulfides, sulfates, chlorides, hydroiodides, bromides, phosphates or hydroxides were added alone, the adverse effects of the elements of the compounds could be inhibited.
  • the amount of addition of the additive is below 0.01 part by weight based on 100 parts by weight of MgO, the effect of promoting the formation of the low-melting-point glassy layer or the formation of the glass film will not be sufficiently obtained.
  • it exceeds 0.5 parts by weight the effect of the low-melting-point additive will excessively occur depending on the conditions of MgO or the finish annealing atmosphere, leading to local melt defects, such as pinholes.
  • the element of the low-melting-point additive is one or more selected from the group consisting of H, Li, Na, K, Cu, Rb, Ag, Cs, Ba, Mg, Ca, Zn, Sr, Cd, Ba, B, Al, Ga, Y, In, Tl, Ti, Ge, Sn, P, B, Nb, Sb, Ta, Bi, S, Cr, Mo, Te, W, Mn, Fe, Co, and Ni. If a compound containing such elements is used, an excellent glass film and improved magnetic properties can be realized.
  • a forsterite film by finish annealing it is very important to reduce the melting points of MgO and a steel sheet SiO 2 layer.
  • the atmosphere is extremely dry, sufficient reactivity is not obtained, in some cases, over the entire length and width of a coil only by the effect of the low-melt-point compound.
  • one or more selected from Ti, V, Nb, Cr and Mn oxides are added. More specifically, one or more selected from among TiO 2 , Ti 2 O 3 , TiO, VO 2 , V 2 O 5 , V 2 O 3 , VO, Nb 2 O 5 , Nb 2 O 3 , NbO, CrO 3 , Cr 2 O 3 , MnO 2 , Mn 2 O 3 and MnO are used.
  • the temperature elevation process in finish annealing is based on a hydrogen gas-containing atmosphere, and when oxygen is slowly decomposed from this oxide to suitably partially wet an atmosphere between steel sheet surfaces, the fayalite layer of the decarburized oxide layer can be stably maintained until the formation of forsterite is initiated. Also, it is thought that this oxide, together with the low-melting-point compound, causes the effect of promoting the glass film formation. In fact, it was observed by X-ray analysis that this oxide was present as a spinel phase in the glass film.
  • this oxide has a particle diameter of more than 0.5 ⁇ m, color variation will occur in the film, and pinhole-like defects will also occur.
  • the amount of the oxide that is added is determined depending on the components, thickness, and finish annealing conditions of the applied steel sheet. When the amount of addition of the oxide is below 0.5 parts by weight, the effect of partially wetting the atmosphere or promoting the reaction will not be insufficient. On the other hand, if it exceeds 10 parts by weight, the atmosphere between steel sheet surfaces can be excessively oxidative. Depending on the annealing conditions, the color variation of the steel sheet occurs, leading to deterioration in the quality of the glass film. Also, the inactivation of inhibitors is accelerated, thus deteriorating the magnetic properties.
  • MgO as the main component of the annealing separator, MgO, showing a 40% CAA value of 50-120 seconds and having a hydrated water content of 1.0-2.5%, is used in combination with the low-melting- point additive.
  • CAA is widely used as an index for evaluating the reactivity of MgO.
  • the activity of MgO is excessively high and has a high content of hydrated water, making it difficult to stably control the hydrated water content. As a result, the content of water in a coil is increased, and thus color variation in the coil is likely to occur.
  • the use of MgO having a very low degree of hydration is not suitable for the technology of using the effect of the low-melting-point additive. Meanwhile, if the 40% CAA value exceeds 120 seconds, the MgO activity will be greatly reduced, leading to a decrease in the hydration thereof, making it impossible to suitably partially wet the atmosphere between the steel sheet surfaces, and the reactivity of MgO itself will be extremely reduced, thus causing a problem in the film thickness of the coil inner winding portion.
  • the hydrated water content varies depending on stirring conditions, including the solution temperature, stirring time and stirring speed in the slurry adjustment step, and on drying conditions.
  • the hydrated water content is less than 1.0%, the oxide film on the steel sheet will be difficult to maintain stable until the time point of formation of forsterite, because the extremely low content of hydrated water makes it difficult to partially wet an atmosphere between the steel sheet surfaces, as described above. For this reason, the formation of a stable glass film is not achieved, even when the low-melting-point additive of the present invention is used.
  • the hydrated water content exceeds 2.5%, the atmosphere will be excessively wetted, and thus variation caused by the difference in atmosphere between the steel sheet surfaces will occur.
  • a high-magnetic-flux-density, grain-oriented electrical steel sheet material comprising, in wt %, 0.0078% of C, 3.18% of Si, 0.068% of Mn, 0.024% of S, 0.028% of Al, 0.0080% of N, and a balance of Fe and other unavoidable impurities, was subjected to hot rolling, annealing and cold rolling to a final thickness of 0.30 mm. Then, the cold-rolled sheet was subjected to decarburization annealing at 850 ° C for 150 seconds in an atmosphere of N 2 50% + H 2 50% (63 ° C DP) in a continuous annealing line.
  • the content of oxygen in the steel sheet was 750 ppm.
  • a slurry comprising a base composition, obtained by adding 5 parts by weight of TiO 2 to 100 parts by weight of MgO, having a 40% CAA value of 65 seconds, and low-boiling-point additives shown in Table 1 below, was applied at a ratio of 6.5 g (as dried weight) /m ! of the sheet surface and dried.
  • the resulting steel sheet was wound into a coil.
  • the coil was subjected to finish annealing at 1200 ° C for 20 hours. Then, the coil was applied with an insulating coating solution, containing aluminum phosphate and colloidal silica as main components, in a continuous line, and then was subjected to annealing at 850 ° C .
  • Example 2 A high-magnetic-flux-density, grain-oriented electrical steel sheet material, comprising, in wt %, 0.0060% of C, 3.20% of Si, 0.070% of Mn, 0.029% of Al, and a balance of Fe and other unavoidable impurities, was subjected to hot rolling, annealing and cold rolling to a final thickness of 0.23 mm. Then, the cold-rolled sheet was subjected to decarburization annealing at 850 ° C for 130 seconds in an atmosphere of N 2 50% + H 2 50% (DP 62 ° C) in a continuous annealing line.
  • the content of oxygen in the steel sheet was 730 ppm.
  • a slurry comprising a base composition obtained by adding 5 parts by weight of TiO 2 to 100 parts by weight of MgO, having different 40% CAA value, and low-boiling-point additives shown in Table 2 below, was applied on the steel sheet at a ratio of 6.0 g (as dried weight)/ m ! of the sheet surface and dried.
  • the resulting steel sheet was wound into a coil.
  • the coil was subjected to finish annealing at 1200 ° C for 20 hours. Then, the coil was applied with an insulating coating solution, containing aluminum phosphate and colloidal silica as main components, in a continuous line, and was then subjected to annealing at 850 ° C .
  • the inventions 11-20 employed the annealing separator, in which an additive having a melting point lower than 750 ° C accounted for more than 30% of the weight of the low-melting- point additive, and the 40% CAA value of MgO was controlled to 50-105 seconds.
  • the glass films were uniform and had good tension and adhesion. Also, the glass films had very good magnetic properties.
  • Example 2 The same starting material as used in Example 2 was rolled to a final thickness of 0.23 mm and subjected to decarburization annealing under the same conditions. Then, the sheet coil was applied with an annealing separator, which had the composition shown in Table 4 below and contained TiO 2 , V 2 O 5 , Nb 2 O 4 and/or MnO 2 as additives for adjusting the atmosphere between the steel sheet surfaces. Then, the sheet coil was subjected to finish annealing and insulation coating under the same conditions as in Examples 1 and 2, and was evaluated for glass film properties and magnetic properties. The results obtained in this Example are shown in Table 4 below. [Table 4]
  • the present invention provides an annealing separator for grain-oriented electrical steel sheets having excellent surface properties and a method of producing grain-oriented electrical steel sheets using the same, wherein the annealing separator comprises: 100 parts by weight of MgO, consisting of 40- 95% of active MgO and 5-60% of inactive MgO; and 0.01-0.5 parts by weight of a low-melting-point compound, having a melting point lower than 900 "C and serving as a reaction promoter.
  • the active MgO has an average particle diameter of less than 5 ⁇ m and a 40% CAA value of 35-80 seconds, and the inactive MgO has an average particle diameter of more than 10 ⁇ m and a 40% CAA value of 250-1500 seconds.
  • the active MgO comprises coarse MgO particles having a BET value of less than 5 and a particle diameter of more than 30 ⁇ m, in an amount of more than 25 wt% based on the total weight of coarse MgO particles, and the inactive MgO is round and granular in shape and has a BET value of less than 10, a bulk specific gravity of more than 0.35 and a particle diameter of 10-100 ⁇ m.
  • the total amount of SO 3 and Cl is less than 1 wt%, and the hydrated water content of MgO is less than 2.5%.
  • 900 ° C is one or more selected from the group consisting of antimony compounds, amide compounds, chlorides, chloroxides, chlorates, chromates, oxides, bromides, hydroxides, hydrides, carbonates, nitrates, tellurates, vanadates, fluorides, borates, phosphates, sulfides, sulfates, iodides, and hydroiodides.
  • the low-melting-point compound having a melting point lower than 900 ° C comprises one or more elements selected from the group consisting of H, Li, Na, K, Cu, Rb, Ag, Cs, Ba, Be, Mg, Ca, Zn, Sr, Cd, Ba, B, Al,
  • the present invention provides a method for producing a grain-oriented electrical steel sheet, comprising heating a steel slab containing 0.030-0.1 wt% of C and 2.5-4.0 wt% of Si, hot-rolling the heated sheet, subjecting the hot-rolled sheet to one-time cold rolling or to a plurality of cold rolling steps with annealing steps therebetween so as to attain a final sheet thickness, subjecting the cold-rolled sheet to decarburization annealing, coating the sheet with an MgO-based annealing separator, subjecting the coated sheet to finish annealing, and then subjecting the finish-annealed sheet to insulation coating and heat flattening, wherein the annealing separator is in the form of a slurry comprising 100 parts by weight of MgO, consisting of 40-95% of active MgO and
  • inactive MgO 5-60% of inactive MgO, and 0.01-0.5 parts by weight of a low-melting-point compound, having a melting point lower than 900 ° C and serving as an additive for reaction promotion, and is applied on the steel sheet after it is stirred in a mixing tank at a revolution speed of 1500-3000 rpm for more than 10 minutes.
  • a silicon steel slab containing 2.5-4.0 wt% Si and one or more inhibitors selected from MnS, AlN, Al, Cu, Sn, Sb and Mo, depending on the intended use of the desired steel material, is hot-rolled according to a known method.
  • the hot-rolled sheet is subjected to one-time cold rolling or to a plurality of cold rolling steps with annealing steps therebetween, so as to attain a final sheet thickness.
  • the cold-rolled steel sheet is subjected to decarburization annealing in a continuous line so as to form a SiO 2 -based oxide film on the surface of the steel sheet.
  • the annealing agent which is in the form of a slurry comprising 100 parts by weight of MgO and 0.01-0.5 parts by weight of one or more low- melting-point compounds, having a melting point lower than 900 °C and serving as an additive for promoting the reaction, is applied on the steel sheet in a continuous line.
  • the slurry is preferably stirred at a high revolution speed of 1500-3000 rpm.
  • the steel sheet is dried at a temperature of about 200-300 ° C and wound into a coil. Then, in a finish annealing process, the steel sheet coil is maintained in a batch-type or continuous furnace at a temperature of about 1170-1220 ° C for 15-20 hours, while the temperature elevation rate or the amount of nitrogen as atmospheric gas are adjusted. In this case, glass film formation, annealing and secondary recrystallization occur at the same time.
  • the coil thus treated is washed with water to remove an excess of the annealing separator, and washed with acid. Then, it is coated with an insulating coating agent, and subjected to heat flattening at a temperature of about 850 °C for the annealing of the insulating coating film, shape correction, and stress-removing annealing, thus producing a final product.
  • the glass film and magnetic properties are determined through such a series of processes, and particularly, the formation conditions of the oxide film in the decarburization annealing process and the conditions in the annealing separator are very important.
  • the annealing separator influences not only the formation time, formation rate, formation amount and uniformity of the glass film, but also additional oxidation or nitrification, which influence the formation of the film during temperature elevation in the finish annealing process.
  • it influences the decomposition rates of important inhibitors, AlN and MnS, or other components in steel sheets, and thus also influences the magnetic properties of the steel products.
  • the particle size or sintering property of an annealing separator influences the movement of a steel sheet during the thermal expansion or thermal shrinkage of the steel sheet coil, and thus also influences the shape of the coil.
  • the annealing separator which comprises the low-melting-point additive
  • the slurry dispersion technology is used in combination with the annealing separator, excellent synergistic effects on the improvement of the glass film and on the coil shape are realized.
  • the annealing separator which is used in the present invention, comprises
  • MgO consisting of a mixture of 40-95 wt% of one or more active MgO particles, having an average particle diameter of less than 5 ⁇ m and a 40% CAA value of 35-80 seconds, with 5-60 wt% of one or more inactive MgO particles, having an average particle diameter of more than 10 ⁇ m and a 40% CAA value of 250-1500 seconds.
  • the MgO for use in the present invention has a total amount of SO 3 and Cl of less than 1 % and a hydrated water content of less than 2.5 wt%. When the hydrated water content is more than 2.5%, the total water content during high- temperature annealing is increased, and thus local water accumulation in the coil occurs, leading to additional oxidation.
  • the active MgO having an average particle diameter of less than 5 ⁇ m and a 40% CAA value of 35-80 seconds, mainly severs as a raw material for forming a forsterite film in a glass film formation process.
  • a trace amount of hydrated water which is produced on the MgO surface in the step of adjusting the slurry of the active MgO, serves to partially wet the atmosphere between the coil sheets in the finish annealing process and to maintain the oxide layer on the steel sheet surface stable until the glass film formation step, thus stabilizing the reaction. If the content of the active MgO is less than 40 wt% based on the total weight of MgO, the activity of the fine particles will be reduced, and thus the formation of the glass film becomes insufficient.
  • the amount of fine MgO particles having a particle diameter of less than 5 ⁇ si is insufficient, the adhesion of the glass film to the steel sheet will be reduced. Thus, the glass film is likely to be thin, or pinhole-like defects are likely to occur.
  • the content of the active MgO exceeds 95 wt%, it will impart an excessively large amount of hydrated water content to the steel sheets, or will reduce the ventilation between the steel sheets, such that peroxide defects are likely to occur on the outer winding portion or edge of the coil. Also, because the content of coarse particles will be excessively reduced, slippage between the steel sheets will be reduced, leading to an increase in the occurrence of distortion defects and embossing defects, which occur due to thermal expansion and thermal shrinkage during finish annealing.
  • the active MgO has a 40% CAA value of less than 35 seconds, it will have excessively strong activity, making it difficult to control hydrated water in the mixing process and making it difficult to reduce impurities. If the 40% CAA value exceeds 80 seconds, the activity of the MgO particles themselves will be reduced, and thus the glass film formation reaction will be unstable.
  • Inactive MgO having a 40% CAA value of 250-1500 seconds mainly contributes to an increase in the ventilation of the atmosphere between steel sheets and to an increase in the slippage between steel sheets. Due to the inactive coarse particles, the hydrated water between steel sheets is smoothly released or the atmosphere between steel sheets becomes uniform, making the glass film uniform. Also, due to the slippage improvement effect of the coarse particles, the movement of the steel sheets during thermal expansion or shrinkage in the finish annealing process is improved, leading to a reduction in shape defects, such as distortion defects or embossing defects. If the content of the inactive MgO is less than 5 wt%, a sufficient effect of improving said ventilation or slippage can be obtained.
  • the content of the inactive MgO exceeds 60 wt%, the amount of the active MgO will be insufficient, making the glass film thin. If the 40% CAA value is less than 250 seconds, it will have an insignificant effect on the improvement of the shape defect problem, and in addition, will influence the total hydration of MgO, and thus have an unfavorable effect on glass film formation. If the 40% CAA value exceeds 1500 seconds, the appearance improvement effect will not be changed, but the inevitable incorporation of very coarse particles will occur, and in addition, the production cost will be increased.
  • the total amount of SO 3 and Cl impurities is maintained at less than 1%.
  • the amount of SO 3 in produced MgO tends to increase.
  • the effects of these impurities were closely examined and, as a result, it was proved that a total amount of SO 3 and Cl of less than 1% was not problematic. If the total amount of SO 3 and Cl exceeds 1%, etching will occur in the high-temperature region of the glass film formation process, thus thinning the glass film or causing surface defects, such as local spots or discoloration.
  • the inactive MgO particles preferably have a granular shape, a BET value of less than 10 and a particle diameter of 10-100 ⁇ m.
  • coarse particles obtained by grinding particles, obtained by calcining clinker or the like at high temperature, are used, the slippage improvement effect will be extremely reduced compared to that of the coarse granular particles used in the present invention, and fine defects will occur on the steel sheet surface along the cracked plane.
  • the BET value When the BET value is less than 10, an excellent effect of improving the film appearance will be obtained. This is because the BET value is connected with the packing density of the particles, and the hardness of the particles is increased so as to show a stable effect of improving the film appearance. In fact, even when coarse particles, produced by the agglomeration of fine particles, were used, the effect of improving the film appearance was not observed. If the BET value exceeds 10, the effect of improving the film appearance will be extremely reduced, possibly because the hardness of the coarse particles is low. For this reason, the BET value is limited to less than 10.
  • the particle diameter of MgO particles is 10-100 ⁇ m.
  • the MgO particles have a particle diameter of less than 10 ⁇ m, they will not sufficiently exhibit the effect of improving ventilation or film appearance.
  • the coarse particles will cause dent defects on the steel sheet surface.
  • the content of MgO particles having a particle diameter of more than 30 ⁇ m is more than 25 wt% based on the total weight of coarse MgO particles. This is because MgO particles having a particle diameter of about 30-100 ⁇ m are required in a given amount in order to exhibit the above- described spacing effect or slippage improvement effect.
  • the slurry containing MgO is adjusted by stirring it in a mixing tank at a stirring speed of 1500-3000 rpm for at least 10 minutes, and then the stirred slurry is applied on the steel sheet.
  • the stirring mixer is not specifically limited, as long as it is a conventional tank having stirring propellers therein. At a stirring speed of less than 1500 rpm, due to the physical properties of MgO, the uniform dispersion of MgO particles in the slurry and the increase in the adhesion of MgO to the steel sheet, cannot be sufficiently obtained. This can also lead to a decrease in the MgO reactivity for forming the glass film.
  • the stirring speed exceeds 3000 rpm
  • the stirring temperature will be increased due to the friction between MgO particles during the stirring of MgO, making it difficult to control the hydrated water of MgO.
  • the slurry containing the mixture of active MgO and inactive MgO is adjusted by stirring it in a mixing tank at a stirring speed of 1500-3000 rpm, sufficient dispersion of the MgO particles will occur, and thus a grain-oriented electrical steel sheet product having an excellent glass film and coil shape will be obtained.
  • the initiation temperature of glass film formation is generally 900-950 °C .
  • additional oxidation or addition nitrification occurs during glass film formation, depending on steel sheet components or finish annealing conditions, thus causing glass film defects at the outer winding portion or edge of the coil.
  • the additive having a melting point lower than 900 ° C is added to MgO, the initiation temperature of the glass film formation reaction can be significantly reduced to make it possible to suppress the above- described additional oxidation or additional nitrification, and thus a steel sheet product having a more uniform glass film and magnetic properties can be obtained.
  • the additive When the additive is added in an amount of less than 0.01 parts by weight based on 100 parts by weight of MgO, the effect of reducing the initiation temperature of glass film formation will not be sufficient, and thus the effect of improving the glass film will not be obtained.
  • the amount of addition of the additive exceeds 0.5 parts by weight, the effect of the low- melting-point additive will be obtained due to MgO or finish annealing conditions, but pinhole-like or island-like local melt defects will occur due to the excessive action of the additive. In severe cases, color spot defects will occur.
  • This low-melting-point additive comprises one or more elements selected from the group consisting of H, Li, Na, K, Cu, Rb, Ag, Cs, Ba, Be, Mg, Ca, Zn,
  • a high-magnetic-flux-density grain-oriented electrical steel sheet material comprising, in wt%, 0.055% of C, 3.12% of Si, 0.065% of Mn, 0.025% of S, 0.026% of Al, 0.0077% of N, and a balance of Fe and other unavoidable impurities, was subjected to hot rolling, annealing and cold rolling so as to have a final thickness of 0.30 mm. Then, the cold-rolled steel sheet was subjected to decarburization annealing in a continuous line in an atmosphere of 50% N 2 + 50% H 2 (65 0 C DP) at 850 ° C for 150 seconds.
  • the steel sheet contained 765 ppm of oxygen.
  • the steel sheet was subjected to finish annealing at 1200 ° C for 20 hours, and then an insulating coating solution, containing aluminum phosphate and colloidal silica as main components, was applied on the steel sheet in a continuous line. Then, the steel sheet was subjected to annealing decarburization at 850 ° C .
  • a high-magnetic-flux-density grain-oriented electrical steel sheet material comprising, in wt%, 0.067% of C, 3.15% of Si, 0.070% of Mn, 0.025% of Al, and a balance of Fe and other unavoidable impurities, was subjected to hot rolling, annealing and cold rolling so as to have a final thickness of 0.23 mm. Then, the cold-rolled steel sheet was subjected to decarburization annealing in a continuous line in an atmosphere of 50% N 2 + 50% H 2 (65 ° C DP) at 850 ° C for 130 seconds.
  • the steel sheet contained 715 ppm of oxygen.
  • inactive MgO having an average particle diameter of 55 ⁇ m and obtained by grinding MgO clinker, was added. Then, the steel sheet was subjected to finish annealing at 1200 ° C for 20 hours, and then an insulating coating solution, containing aluminum phosphate and colloidal silica as main components, was applied on the steel sheet in a continuous line. Then, the steel sheet was subjected to annealing decarburization at 850 ° C .
  • Example 9 The same starting material as used in Example 4 was rolled to a final thickness of 0.30 mm and subjected to decarburization annealing in the same conditions. Meanwhile, 5 parts by weight of TiO 2 and 0.3 parts by weight of Na 2 B 4 O 7 were added to 100 parts by weight of the same MgO as used in the invention 53 of Example 5, and the mixture was stirred in water at 7 ° C using the addition conditions and mixing conditions of a reaction promoter, as shown in Table 9, thus obtaining slurry. Then, the slurry was applied on the steel sheet at a ratio of 6.5 g/m 2 of the sheet surface, and the steel sheet was wound into a coil. [Table 9]
  • the steel sheet was subjected to finish annealing at 1200 ° C for 20 hours, and then an insulating coating solution, containing aluminum phosphate and colloidal silica as main components, was applied on the steel sheet in a continuous line. Then, the steel sheet was subjected to annealing decarburization at 850 0 C .
  • Comparative Example 62 in which MgO consisting only of active MgO was used, the color tone of the glass film was non-uniform, as in the case of Example 4, and scale defects were generated in a large amount. Also, in Comparative Example 61, in which the additive for reaction promotion was added to the MgO, the glass film was slightly improved, but the film properties and the magnetic properties were all inferior to those of the inventions.
  • the inventive annealing separator for grain-oriented electrical steel sheets having a uniform glass film and excellent magnetic properties, has a low content of hydrated water and contains, as an additive for increasing the reactivity of the MgO, an additive having a melting point lower than 900 ° C, preferably a low-melting-point additive containing an additive having a melting point lower than 750 ° C, in an amount of 30 wt% based on the total amount of the low-melting-point additive.
  • the annealing separator shows a remarkable effect of improving glass film formation, and suppresses the occurrence of additional oxidation or additional nitrification during a finish annealing process, such that a grain-oriented electrical steel sheet having very good film properties and magnetic properties, can be obtained.
  • a grain- oriented electrical steel sheet having a uniform glass film, and excellent magnetic properties and an excellent coil shape, can be obtained.
  • the present invention provides a grain-oriented electrical steel sheet having a uniform glass film formed thereon, excellent magnetic properties, and an excellent coil shape. Thus, the present invention contributes to industrial development.

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Abstract

L'invention concerne un séparateur de recuit pour tôles d'acier électriques à grains orientés présentant d'excellentes propriétés de surface, ainsi qu'un procédé de production de tôles d'acier au moyen dudit séparateur. Le séparateur de recuit selon l'invention contient plus particulièrement : 100 parties en poids de MgO, constituées de 40 à 95% de MgO actif et de 5 à 60% de MgO inactif ; et 0,01 à 5 parties en poids d'un composé à point de fusion bas, inférieur à 900 °C. Le procédé de production de tôles d'acier à grains orientés consiste à appliquer le séparateur de recuit sous forme de bouillie sur une tôle d'acier, après brassage dudit séparateur dans un réservoir de mélange, à une vitesse de rotation comprise entre 1500 et 3000 tours/minute pendant plus de 10 minutes.
PCT/KR2007/003544 2006-10-18 2007-07-23 Agent de separation de recuit pour tole d'acier electrique a grains orientes presentant un film de verre uniforme et d'excellentes proprietes magnetiques, et procede de fabrication associe Ceased WO2008047999A1 (fr)

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CN200780038866XA CN101528950B (zh) 2006-10-18 2007-07-23 具有均匀玻璃覆膜和优良磁性能的晶粒取向电磁钢板用退火隔离剂及制备所述晶粒取向电磁钢板的方法

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KR1020060101232A KR100762436B1 (ko) 2006-10-18 2006-10-18 표면성상이 우수한 방향성 전기강판용 소둔분리제 및 이를이용한 방향성 전기강판의 제조방법
KR10-2006-0101232 2006-10-18
KR1020060101233A KR100865316B1 (ko) 2006-10-18 2006-10-18 균일한 글라스피막과 우수한 자기특성을 갖는 방향성전기강판용 소둔분리제
KR10-2006-0101233 2006-10-18

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US20140251514A1 (en) * 2011-10-20 2014-09-11 Jfe Steel Corporation Grain-oriented electrical steel sheet and method of producing the same (as amended)
EP2765219A4 (fr) * 2011-10-04 2015-07-29 Jfe Steel Corp Agent de séparation de recuit pour une tôle d'acier électromagnétique à grains orientés
JP2016145419A (ja) * 2015-01-30 2016-08-12 Ｊｆｅスチール株式会社 方向性電磁鋼板とその製造方法
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JP2017179461A (ja) * 2016-03-30 2017-10-05 タテホ化学工業株式会社 焼鈍分離剤用酸化マグネシウム及び方向性電磁鋼板
WO2017169853A1 (fr) * 2016-03-30 2017-10-05 タテホ化学工業株式会社 Oxyde de magnésium pour séparateur de recuit, et tôle d'acier électromagnétique à grains orientés
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US9194016B2 (en) 2011-10-04 2015-11-24 Jfe Steel Corporation Annealing separator for grain-oriented electromagnetic steel sheet
US20140251514A1 (en) * 2011-10-20 2014-09-11 Jfe Steel Corporation Grain-oriented electrical steel sheet and method of producing the same (as amended)
US9805851B2 (en) * 2011-10-20 2017-10-31 Jfe Steel Corporation Grain-oriented electrical steel sheet and method of producing the same
JP2014156633A (ja) * 2013-02-15 2014-08-28 Jfe Steel Corp 方向性電磁鋼板の製造方法および方向性電磁鋼板並びに方向性電磁鋼板用表面ガラスコーティング
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JP2019505664A (ja) * 2015-12-18 2019-02-28 ポスコＰｏｓｃｏ 方向性電磁鋼板用焼鈍分離剤、方向性電磁鋼板、および方向性電磁鋼板の製造方法
US11505843B2 (en) 2015-12-18 2022-11-22 Posco Annealing separator for oriented electrical steel sheet, oriented electrical steel sheet, and manufacturing method of oriented electrical steel sheet
US11097955B2 (en) 2016-03-30 2021-08-24 Tateho Chemical Industries Co., Ltd. Magnesium oxide for annealing separator, and grain-oriented electromagnetic steel sheet
WO2017169852A1 (fr) * 2016-03-30 2017-10-05 タテホ化学工業株式会社 Oxyde de magnésium pour séparateurs de recuit, et tôle d'acier magnétique à grains orientés
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