KR101539751B1 - Oriented electrical steel sheet and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a grain-oriented electrical steel sheet and a method of manufacturing the same, and more particularly, to a grain-oriented electrical steel sheet and a method of manufacturing the same. The grain-oriented electrical steel sheet comprises 2.5 to 4.5 wt.% Si, 0.015 to 0.040 wt.% Of an acid soluble Al, 0.01 to 0.20 wt.% Of Mn, 0.03 to 0.09 wt. 0.001 to 0.006 wt% of S, 0.0010 to 0.006 wt% of S, 0.03 to 0.12 wt% of Cr, 0.03 to 0.07 wt% of Sn, 0.01 to 0.05 wt% of Sb and 0.01 to 0.05 wt% of P, Wherein P and Sb are weight percentages of P + 0.5Sb: 0.0370 to 0.0630%, the balance of Fe and other inevitably added impurities, and Si, C and Cr content satisfy the following formula (1) An electrical steel sheet and a manufacturing method thereof are disclosed.
Si (wt%) x 0.0218? C (wt%) +0.0194? Si (wt%) x 0.0234 + Cr (wt%

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a directional electric steel sheet,

The present invention relates to a directional electric steel sheet and a method of manufacturing the same, and more particularly, to a directional electric steel sheet having improved magnetic properties by controlling Si, C and Cr contents of a directional electric steel sheet containing Sn, Sb and P, ≪ / RTI >

Generally, the grain-oriented electrical steel sheet suppresses the growth of the primary recrystallized grains and selectively grow crystal grains of {110} < 001 > orientation (hereinafter referred to as Goss orientation) in the final annealing process among the grains whose growth is suppressed, And exhibits excellent magnetic properties.

In order to induce secondary recrystallization, fine inhibitors such as MnS and AlN are uniformly dispersed in the steel sheet before the final high-temperature annealing, so that the Goss orientation It is possible to obtain excellent magnetic properties, that is, high magnetic flux density and low iron loss by increasing the degree of integration so that the secondary recrystallization grains have a precise goss orientation by suppressing the growth of primary recrystallized grains having other orientations.

As means for effectively controlling the secondary recrystallization and improving the magnetic properties, it is possible to control the inhibitor excellent in the effect of inhibiting the growth of grains, the proper size and homogeneous size of the nucleation control and primary recrystallization forming the secondary recrystallization in the primary recrystallization Distribution formation is important. Korean Patent Laid-Open Publication No. 2009-0072116 discloses a method for further improving the magnetic properties of the grain-oriented electrical steel sheet, and Sn, Sb and P are added in an appropriate amount range to implement such means.

 As a method for further improving the magnetic property of the grain-oriented electrical steel sheet, there is a method of increasing the silicon content and increasing the resistivity to lower the iron loss. However, since silicon is an element that induces formation of a ferrite phase in the hot rolling and hot-rolled sheet annealing temperature range, the proportion of austenite during the hot rolling and hot-rolled sheet annealing decreases as the silicon content increases. Particularly, the austenite fraction at the temperature at which the hot rolling is actually performed is important. The increase of the silicon content is due to the decrease of the austenite fraction during the hot rolling and the annealing of the hot-rolled sheet, Resulting in a bad influence on the formation of secondary recrystallization. Therefore, there is a need for a countermeasure against the decrease of the austenite fraction with the increase of the Si content.

On the other hand, since carbon is an element that induces formation of austenite phase at a high temperature at which hot rolling is performed, the ferrite-austenite phase transformation is activated during the hot rolling process as the carbon content increases, and the long drawn hot- And ferrite grain growth is suppressed during the hot-rolled sheet annealing process. Also, as the carbon content increases, the cold rolling efficiency can be increased by increasing the structure of the drawn hot rolled steel strip, which is higher in strength than the ferrite structure, and by reducing the initial grain size of the annealed hot rolled steel sheet.

As described above, since Si and C have a contradictory role in the induction of austenite phase transformation in hot rolling and hot-rolled annealing processes, it is important to adjust the phase transformation ratio during hot rolling and annealing of hot- Do.

Particularly, the austenite fraction at the temperature at which the hot rolling is performed affects the increase in the goss fraction of the sub-surface formed by the hot-rolled band formation and the shear deformation among the hot-rolled steel sheet and the hot-rolled sheet annealed structure. That is, it is important to control the silicon and carbon composition within a certain range so as to maintain a proper austenite fraction under the conditions capable of forming the optimal secondary recrystallization in the temperature range in which hot rolling is performed.

In addition, the increase in the C content causes decarburization in the decarburization annealing process, resulting in irregularities in the size of the primary recrystallized grains, and instability in the secondary recrystallization. Therefore, the upper limit of the C content is limited. In the annealing step, SiO ₂ and an Fe ₂ SiO ₄ oxide layer, which are external oxidation layers, are over-formed and densely formed, and the decarburization behavior is delayed.

In order to overcome this, adding an element for promoting the formation of an oxide layer in an appropriate range in the decarburization annealing process may suppress formation of a dense oxide layer in the surface layer and help formation of a fine oxide layer in the depth direction. This makes it easier to form the primary recrystallization with excellent uniformity.

In order to solve the above-mentioned problems, the present invention controls the C content to an appropriate range as the Si content changes, and as the Si content and the C content increase, the primary recrystallization unevenness phenomenon due to the decarburization delay during the decarburization annealing process The present invention provides a directional electrical steel sheet having a desired size distribution by controlling addition of Cr in a small amount and controlling the contents of Sn, Sb and P to an appropriate range, and a manufacturing method thereof.

In one or more embodiments of the present invention, it is preferred that the amount of Si is from 2.5 to 4.5% by weight, the amount of acid soluble Al is from 0.015 to 0.040% by weight, Mn is from 0.01 to 0.20% by weight, C is from 0.03 to 0.09% 0.001 to 0.006 wt% of S, 0.03 to 0.12 wt% of Cr, 0.03 to 0.07 wt% of Sn, 0.01 to 0.05 wt% of Sb and 0.01 to 0.05 wt% of P, 0.0 &gt; 0% &lt; / RTI &gt; Sb: 0.0370 to 0.0630% by weight, the remainder being Fe and other inevitably added impurities; Reheating the slab in the range of 1050 to 1250 占 폚; Subjecting the reheated slab to hot rolling in the range of 950 to 1050 占 폚 and performing or omitting hot-rolled sheet annealing; Cold-rolling the annealed hot-rolled sheet; Sequentially or simultaneously performing cold-rolled cold-rolled sheet by decarburization annealing and steep annealing; And finally annealing the steel sheet subjected to decarburization annealing and nitriding annealing, wherein the Si, C and Cr contents satisfy the following formula (1).

Si (wt%) x 0.0218? C (wt%) +0.0194? Si (wt%) x 0.0234 + Cr (wt%

And the nitrogen content in the steel sheet after the decarburization annealing and nitriding annealing is 100 to 300 ppm. The size of the primary recrystallized grains after the decarburization annealing and nitriding annealing is 18.0 to 25.0 占 퐉. The decarburization annealing and nitriding annealing step 800 to 900 &lt; 0 &gt; C.

When the decarburization annealing and the nitriding annealing are simultaneously performed, the initial decarburization annealing is performed in the range of 60 to 70 ° C (50% N ₂ + 50% H ₂ ) at 800 to 850 ° C, Simultaneous decarburization annealing and nitriding annealing are performed in the temperature range.

Wherein the final high-temperature annealing step is performed at a temperature in the range of 1020 to 1200 ° C., and the final high-temperature annealing step includes a step of primary cracking, a step of raising temperature, and a step of secondary cracking, The temperature is raised at a rate of 18 to 75 ° C / hr at 700 to 950 ° C, and the temperature is elevated at a rate of 10 to 15 ° C / hr at 950 to 1020 ° C.

In one or more embodiments of the present invention, it is preferable that the content of Si is from 2.5 to 4.5 wt%, the content of acid soluble Al is 0.015 to 0.040 wt%, the content of Mn is 0.01 to 0.20 wt%, the content of C is 0.03 to 0.09 wt% 0.001 to 0.006 wt% of S, 0.03 to 0.12 wt% of Cr, 0.03 to 0.07 wt% of Sn, 0.01 to 0.05 wt% of Sb and 0.01 to 0.05 wt% of P, Sb is a weight percent of P + 0.5Sb: 0.0370 to 0.0630%, the balance of Fe and other inevitably added impurities, Si, C and Cr satisfy the following formula (1) Can be provided.

Si (wt%) x 0.0218? C (wt%) +0.0194? Si (wt%) x 0.0234 + Cr (wt%

According to the embodiment of the present invention, by controlling the content of Si, C and Cr in the low-temperature state, it is possible to prevent the coarsening and miniaturization of the initial grain size of the grain-oriented electrical steel sheet before cold rolling, 001 &gt; orientation can be effectively formed.

In addition, it is possible to produce a grain-oriented electrical steel sheet having a high magnetic flux density and a low iron loss even when the C content is varied over a wide range.

Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described in detail below. However, it is to be understood that the present invention is not limited to the disclosed embodiments, but may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. It is intended that the disclosure of the present invention be limited only by the terms of the appended claims.

In an embodiment of the present invention, the grain-oriented electrical steel sheet according to the present invention comprises 3.0 to 5.0 wt% of Si, 0.015 to 0.040 wt% of an acid soluble Al, 0.01 to 0.20 wt% of Mn, 0.001 to 0.006 wt% of S, 0.0010 to 0.006 wt% of S, 0.03 to 0.12 wt% of Cr, 0.03 to 0.07 wt% of Sn, 0.01 to 0.05 wt% of Sb, 0.01 to 0.05 wt% of P, 0.05% by weight, P and Sb in weight percent, P + 0.5Sb: 0.0370-0.0630%, and the remainder Fe and other inevitably added impurities, is heated by slab low temperature heating , Decarburization annealing and nitriding annealing are performed by SRDGN (Simultaneous Recrystallization, Decarburization, Grain Growth and Nitriding) method.

The slab low-temperature heating system refers to a technique of making the necessary inhibitor nitriding at the final thickness of the steel sheet, not depending only on the inhibitor formed in the low-grade steel, thereby supplementing the restraining force required for the secondary recrystallization. The SRDGN method means a method in which nitriding, recrystallization, decarburization, and grain growth are simultaneously performed in the nitriding process in the primary recrystallization annealing process after the low-temperature heating of the slab.

According to the embodiment of the present invention, the slab is reheated at a temperature of 1050 to 1250 ° C, subjected to hot rolling, hot rolled sheet annealing is performed or omitted, cold rolling is performed, and annealing is performed simultaneously with decarburization and dipping, And secondary recrystallization annealing is performed on the directional electric steel sheet. At this time, decarburization annealing and nitriding annealing are simultaneously performed in a temperature range of 800 to 900 ° C.

In the embodiment according to the present invention, the content of Si, C and Cr is adjusted so that the austenite phase fraction in the equilibrium state can be maintained at a level of 10 to 20% at 950 to 1050 ° C, ).

Si (wt%) x 0.0218? C (wt%) +0.0194? Si (wt%) x 0.0234 + Cr (wt%

Hereinafter, the reasons for limiting the numerical values of the components of the grain-oriented electrical steel sheet slab used in the examples according to the present invention will be described.

Hereinafter, unless otherwise stated, the unit is% by weight.

Si: 3.0 to 5.0%

Si plays a role of lowering the core loss, that is, the iron loss, by increasing the resistivity of the oriented electrical steel sheet material. When the Si content is less than 3.0%, the resistivity is decreased and the iron loss is deteriorated. When the Si content is over 5.0%, the brittleness of steel is increased and the toughness is decreased, so that the occurrence rate of plate fracture during rolling process is increased, A load is applied to the rolling operation, the temperature falls below the plate temperature required for pass aging during cold rolling, and the formation of secondary recrystallization becomes unstable. In addition, during the decarburization annealing, the SiO ₂ and Fe ₂ SiO ₄ oxide layers, which are the outer oxide layers, are excessively and densely formed to retard the decarburization behavior, and the primary recrystallization texture structure becomes dull and the primary recrystallization grain becomes uneven, The formation becomes unstable. Therefore, Si in the embodiment according to the present invention is limited to 3.0 to 5.0%.

C: 0.03 to 0.09 wt%

C is an element which induces the formation of austenite phase. As the carbon content increases, ferrite-austenite phase transformation is activated during the hot rolling process, and the elongated hot rolled steel strip structure formed during the hot rolling process is increased, The ferrite grain growth is suppressed. In addition, as the carbon content increases, the texture of the hot rolled steel strip, which is higher in strength than that of the ferrite steel, and the grain size of the hot rolled annealed steel, do. This is because the effect of pass aging during cold rolling is increased by the residual carbon present in the steel sheet after annealing the hot rolled steel sheet, thereby increasing the goss fraction in the primary recrystallized grains. Therefore, the larger the C content, the longer the decarburization annealing time in decarburizing annealing, and the deterioration in productivity. If the decarburization at the initial stage of heating is insufficient, the primary recrystallization grain becomes uneven and makes the secondary recrystallization unstable. In addition, since magnetic properties may be deviated due to the magnetic aging phenomenon, the C content in the examples according to the present invention is limited to 0.03 to 0.09%.

In addition, since Si and C play a contradictory role in the induction of austenite phase transformation in hot rolling and hot-rolled sheet annealing, they can be added at appropriate ratios to adjust the phase transformation ratio during hot rolling and hot-rolled sheet annealing. As the Si content increases, the austenite fraction decreases at a hot rolling temperature of 950 ° C to 1050 ° C. For example, when the Si content is 3.2%, the phase fraction of austenite in the equilibrium state at 950 ° C. to 1050 ° C. is 10 to 20%, and when the Si content is increased to 3.4%, the phase fraction is 8 to 16 %. The actual phase fraction can be higher because the phase transformation is more active in the deformed state. As the Si content increases, it is important to maintain the phase fraction of the lowering austenite at the previous upward level (10-20% in equilibrium). That is, it is important to regulate the composition of Si, C and Cr within a certain range so as to have a proper austenite fraction under the conditions capable of forming the optimal secondary recrystallization.

It is necessary to raise the Si content and the C content to an appropriate range as described above. The increase in the C content is due to the slow decarburization in the decarburization annealing process, resulting in irregularities in the size of the primary recrystallized grains and unstable secondary recrystallization. Therefore, the upper limit of the C content is limited and the Si content is also increased in the decarburization annealing process SiO2 and an Fe2SiO4 oxide layer, which are external oxidation layers, are over-formed and densely formed, and the decarburization behavior is delayed.

To solve this problem, Cr is added in the practice of the present invention.

Cr: 0.03% to 0.12%

Cr is a raw material for promoting the formation of oxide layer in the decarburization annealing process, suppressing the formation of dense oxide layer in the surface layer and helping to form a fine oxide layer in the depth direction. It is possible to further facilitate formation of the primary recrystallization with excellent uniformity by adding Cr in an appropriate range. In the embodiment of the present invention, by adding 0.03% to 0.12% of Cr, the decarburization due to the increase of the Si content and the C content is retarded to overcome the phenomenon that the primary recrystallized grains are uneven, thereby forming the primary recrystallized grains having excellent uniformity , And has an effect of increasing the magnetism.

When the Cr content is added in the above range, the inner oxide layer is formed deeper and the decarburization rate is increased. Therefore, the upper limit of the C content can be increased according to the Si content with the upper limit due to the decarburization delay problem. It is possible to overcome the difficulty in controlling the size and uniformity of the primary recrystallized grains due to the formation of a dense and thin oxide layer due to the addition. If the Cr content is less than 0.03%, the effect is insignificant. If the Cr content exceeds 0.12%, the effect of addition is not large and the cost increases due to the addition of the expensive alloy. Therefore, The content is limited to 0.03% ~ 0.12%.

In order to achieve the above-mentioned effects, in the embodiment according to the present invention, the C content range according to the Si content and the Cr content is Si (wt%) x 0.0218? C (wt%) +0.0194? Si (wt%) x 0.0234 + Cr (wt%) x 0.1.

When the Si (%) x 0.0218> C (%) + 0.0194 is exceeded, the austenite fraction formed in the pre-annealing step of the hot-rolled steel sheet becomes extremely low, The unevenness after cold rolling becomes so great that the formation of grains having a goss orientation in the sub-surface portion of the hot rolling and hot-rolled sheet annealing is not performed well, and the degree of integration of the final secondary recrystallization is prevented.

On the other hand, when the upper limit of the range is exceeded, that is, when C (%) + 0.0194> Si (%) x 0.0234 + Cr (wt%) x 0.1, the microstructure after the hot rolling and hot- The secondary recrystallization is incompletely formed or the decarburization during the primary recrystallization and grain growth is not sufficiently performed due to the inability to survive the Goss orientation of the surface layer portion of the goss after the cold rolling so that the inner crystal grains are unevenly distributed and the secondary recrystallization is unstable I make it. Particularly in the case of simultaneous decarburization processes, this is more so since decarburization is very important in the early stages of heating.

Al: 0.015 to 0.040%

Al bonds with N and precipitates into AlN. However, N and AlN type nitride are formed as fine precipitates (Al, Si, Mn) in the annealing for simultaneous decarburization and sedimentation, so that they act to inhibit strong grain growth. At this time, more than a certain amount of solid solution Al is necessary. If the content of Al is 0.015% or less, the number and the volume fraction of the precipitates to be formed are low, so that the effect of inhibiting the growth of grain growth is insufficient. When the content of Al exceeds 0.040%, the precipitates grow coarser, . Therefore, the acid soluble Al in the embodiment according to the present invention is limited to 0.015 to 0.040%.

N: 0.0010 to 0.006%

N is an element that reacts with Al or the like to refine the crystal grains. When these elements are appropriately distributed, as described above, it is possible to appropriately fine-structure the structure after cold rolling to ensure proper primary recrystallization grain size. However, if the content is excessive, the primary recrystallization grain becomes excessively fine, As a result, due to the fine crystal grains, the driving force causing crystal grain growth during the secondary recrystallization becomes large, so that it can grow to the crystal grains of an undesirable orientation. If N is contained in excess of 0.010%, the secondary recrystallization starting temperature rises and magnetic properties deteriorate. Therefore, N is set to 0.010% or less. In the case of performing the treatment for increasing the nitrogen amount between the cold rolling and the secondary recrystallization annealing, it is sufficient that the N content of the slab is 0.006% or less, so that the content of N in the embodiment of the present invention is 0.0010 to 0.006% It limits.

Mn: 0.01 to 0.20%

Mn has the same effect of increasing the specific resistance as Si and reducing the iron loss. It reacts with the nitrogen introduced by the nitriding treatment together with Si to form precipitates of N (Al, Si, Mn), whereby the growth of the primary recrystallized grains And it is an important element for causing secondary recrystallization. In order to exhibit such an effect, 0.01 wt% or more is required. However, when 0.20% or more is added, a large amount of (Fe, Mn) and Mn oxide are formed on the surface of the steel sheet in addition to Fe ₂ SiO ₄ , which hinders formation of a base coat formed during high- temperature annealing, The size of the primary recrystallized grains becomes uneven due to the unevenness of the phase transformation between the ferrite and the austenite, and as a result, the secondary recrystallization becomes unstable. Therefore, Mn in the examples according to the present invention is limited to 0.01 to 0.20%.

S: 0.0010 to 0.006%

S is preferably an element which has a high solid solution temperature during hot rolling and is not contained in the segregated element as much as possible, but it is a kind of an impurity which is inevitably contained in steelmaking. Also, since S forms MnS and affects the primary recrystallized grain size, the content of S in the examples according to the present invention is limited to 0.0010 to 0.006%.

P: 0.01 to 0.05%

P can segregate in grain boundaries and can play an auxiliary role of suppressing grain growth and has an effect of improving primary recrystallization texture. The effect is exhibited when the addition amount is 0.01% or more. When the addition amount exceeds 0.05%, the brittleness is strong and the cold rolling becomes difficult. Therefore, the content of P in the examples according to the present invention is 0.01 to 0.05%.

Sb: 0.01 to 0.05%

Sb is a grain boundary segregation element and has an effect of suppressing grain growth growth and also has an effect of improving core loss. However, since Sb has a low melting point, diffusion behavior toward the surface during the primary recrystallization annealing is generated to suppress the formation of the surface oxide layer. Therefore, the excessive addition of Sb causes the surface oxidation layer formed during the primary recrystallization annealing, And the crystal grain growth inhibiting ability is excessively increased to grow to other texture tissues which are not correlated with the Goss texture, thereby deteriorating the secondary recrystallization texture and damaging the magnetic properties. If Sb is added in an amount of 0.01 wt% or more, the effect of suppressing grain growth is exhibited. If the amount of Sb is more than 0.05 wt%, the effect of suppressing crystal grain growth is excessively high and stable secondary recrystallized microstructure can not be obtained. Base coating can not be obtained. Therefore, in the examples according to the present invention, Sb is limited to the range of 0.01 to 0.05 wt%.

Sn: 0.03 to 0.07 wt%

Sn has an effect of suppressing crystal grain growth as a grain boundary segregation element like Sb and has an effect of improving iron loss. However, since Sn has a low melting point, diffusion behavior toward the surface occurs during the primary recrystallization annealing to suppress the formation of the surface oxide layer. Therefore, the excessive addition of Sn causes the surface oxide layer formed during the primary recrystallization annealing And the crystal grain growth inhibiting ability is excessively increased to grow to other aggregate tissues which are not correlated with the Goss aggregate structure, thereby destroying the secondary recrystallized aggregate structure, thereby hindering the magnetic properties. When Sn is added in an amount of 0.03% by weight or more, the effect of inhibiting grain growth is exhibited. When the amount of Sn is more than 0.07% by weight, the effect of suppressing grain growth is excessively excessive, so that a stable secondary recrystallized microstructure can not be obtained. A stable base coating can not be obtained. Therefore, in the embodiment of the present invention, Sn is limited to 0.03 to 0.07% by weight.

Hereinafter, a method for producing a grain-oriented electrical steel sheet having excellent magnetic properties using the grain steel slab having the above composition will be described in more detail.

In the practice of the present invention, when reheating the slab before hot rolling, N and S which are dissolved are incompletely dissolved in a predetermined temperature range. If N and S are completely dissolved, the nitride after annealing of the hot- Since a large amount of sulphide is formed in a large amount, it is impossible to carry out a subsequent cold rolling step, which is a subsequent step, and an additional process is required. Therefore, a manufacturing cost may increase and a primary recrystallized grain size may become extremely small Secondary recrystallization may not be able to occur.

The directional electric steel plate slab having the above composition is reheated before the hot rolling, and the slab is preferably heated at a temperature of 1,280 ° C or lower, more preferably 1,250 ° C or lower, to partially refine the precipitate. If the heating temperature of the slab is increased, the manufacturing cost of the steel sheet is increased, and the melting of the surface of the slab can repair the heating furnace and shorten the life of the heating furnace. In addition, it is possible to prevent the columnar structure of the slabs from being grown to a great extent, thereby preventing cracks from being generated in the width direction of the plate in the subsequent hot rolling process, thereby improving the slurry rate. If the slab heating temperature is less than 1050 ° C, hot rolling is difficult, so the slab heating temperature in the embodiment of the present invention is limited to 1050 to 1250 ° C.

After the directional electric steel slab is reheated, hot rolling is performed. A hot rolled sheet having a thickness of 2.0 to 3.5 mm is prepared by hot rolling. After the hot rolled sheet is manufactured, the hot rolled sheet is annealed if necessary and then cold rolled. In the case of annealing the hot-rolled steel sheet, the steel sheet can be annealed by heating at a temperature of 1,000 to 1,250 ° C, followed by cracking at a temperature of 850 to 1,000 ° C, followed by cooling. The hot-rolled sheet annealing is performed according to need, and this can be omitted. At this time, the average size of the precipitates after hot rolling or after hot-rolled sheet annealing is 300 to 3000 Å.

The cold rolling may be performed through one time of cold rolling, and the final thickness is made to be 0.15 to 0.35 mm through rolling. The cold-rolled sheet is subjected to decarburization, recrystallization of the deformed structure, and nitriding treatment using ammonia gas.

In the embodiment according to the present invention, decarburization annealing and nitriding annealing may be performed sequentially or simultaneously, but in order to perform nitriding treatment, it is necessary to provide a special annealing furnace at the rear end of the decarburization annealing furnace, It is preferable to perform decarburization annealing and nitriding annealing at the same time.

Simultaneous decarburization steep annealing is performed simultaneously with decarburization and soaking, and secondary recrystallization annealing is performed. The simultaneous decarburization annealing is performed in a temperature range of 800 to 900 ° C.

The simultaneous decarburization annealing step is performed in the initial decarburization annealing step performed at a dew point of 60 to 70 ° C (50% N ₂ + 50% H ₂ ) in a temperature range of 800 to 850 ° C and in the simultaneous decarburization annealing step performed in a temperature range of 850 to 900 ° C And performing annealing by nitriding.

In the initial decarburization annealing step, it is important to induce grain growth by the complete removal of the surface portion of the microparticulate area and to partially remove the inner microparticulate region, thereby reducing the amount of residual carbon in the steel sheet to be supplied to the simultaneous decarburization annealing to less than 100 ppm.

Decarburization is mainly caused by the reaction that the carbon inside is diffused into the surface layer and the carbon is released into the CO gas through oxygen and the reaction below.

C + H ₂ O -> CO (gas) + H ₂

The carbon in the steel sheet is present in the tissue at a rate of about 10%, mostly in pearlite or bainite (locally depending on the cooling pattern) phase transformed from the austenite produced in the hot rolling operation, and finely fractured It exists locally in pearlite form and exists in the form of strip along the rolling direction. These are decomposed in the decarburization annealing process and the carbon coming out from the ferrite particles and the grain boundaries through the grain boundaries must reach the surface layer. At low temperatures, the diffusion rate of carbon is low and the carbon solubility of ferrite is low.

In addition, oxygen must penetrate into the surface layer of the steel sheet to penetrate the carbon to meet the reaction. When the temperature is less than 700 ° C, the amount of oxygen entering the steel tube is small. To 700 ~ 850 ℃ started getting to oxygen permeation in the thickness direction at intervals in earnest, wherein oxygen are made to meet with the carbon in the decarburization reaction earnest entering, at the same time, SiO ₂ inside the Si and to meet the thickness direction in the surface layer the steel sheet of the inner An oxide layer is formed. Experiments have confirmed that decarburization occurs more frequently in steel sheets with deep internal oxide layers.

Therefore, in order to achieve good decarburization, the plate temperature must be raised to 800 ° C or more for penetration of the surface of the inner carbon and penetration of oxygen in the thickness direction, and at the same time, an oxidizing atmosphere must be formed to penetrate oxygen in the thickness direction. It should be noted that the austenite phase transformation occurs locally when the temperature is too high in the state where the decarburization is not completed. This phenomenon occurs mainly at the center where decarburization is most delayed, which interferes with crystal grain growth and forms a local microstructure, which causes severe irregularity of the texture. Therefore, the initial decarburization reaction in the practice of the present invention is preferably carried out at 850 ° C or lower.

In addition, proper decontamination of oxygen is very important for decarburization. The amount of oxygen to be supplied must take into account the oxidizing atmosphere (dew point, hydrogen atmosphere), the shape of the oxide layer in the surface layer, and the plate temperature. When it is judged only by the oxidizing ability, it is better to increase the oxidizing ability because the oxygen partial pressure becomes higher as the oxidizing ability is higher. However, when the oxidizing ability is excessively high, oxides such as SiO ₂ , ferric oxide (Fe ₂ SiO ₄ , fayalite) are densely formed in the surface layer, and when dense oxides are formed, they act as obstacles preventing penetration of oxygen into the depth direction And consequently interferes with the internal penetration of oxygen.

The low-temperature Si reacts with moisture present in the annealing atmosphere gas to form an oxide layer, and this tendency becomes greater as the Si content increases. Therefore, there is a proper oxidizing ability for decarburization and, in the present invention in the practice in the component system of Example several experiments dew point 60 ~ 70 ℃ in the temperature range of 800 ~ 850 ℃ (50% N 2 + 50% H 2) atmosphere under The best decarburization occurred.

The formation of a dense oxide layer in the surface layer interferes not only with decarburization but also with formation of a depth direction oxidation layer. When the hydrogen ratio in the furnace atmosphere is high, the hydrogen partial pressure in the surface layer is high and the effect of inhibiting the formation of dense oxide layer is improved. As the hydrogen amount is increased, decarburization is more likely to occur in a dew point atmosphere higher than the same dew point level. For example, the dew point is 62.5 ° C (50% N ₂ + 50% H ₂ ) and the dew point is 70 ° C (50% N ₂ + 50% H ₂ )

In the case of nitriding annealing at the same time as decarburization annealing, it can be carried out in a mixed gas atmosphere of ammonia, hydrogen and nitrogen. According to the method in which the decarburization is first carried out after the temperature elevating process in the first recrystallization annealing and then the nitriding annealing is performed, precipitates such as Si ₃ N ₄ and (Si, Mn) N are generated in the surface layer portion of the steel sheet. (Al, Si, Mn) N, which is thermally stable in the final annealing process, which is a subsequent process, since the annealing temperature is controlled to 700 to 800 ° C. It is possible to perform a role as an inhibitor by re-precipitation.

On the contrary, when the decarburization and the nitriding annealing are performed at the same time, AlN or (Al, Si, Mn) N precipitates are formed at the same time, so that the precipitates can be used as an inhibitor without being transformed during the final annealing. Therefore, It is more preferable to carry out decarburization and nitriding annealing at the same time.

If the residual nitrogen amount is less than 100 ppm, the nitrogen may not form the inhibitor properly, and when the amount of residual nitrogen is more than 300 ppm It may take an excessive amount of time to remove nitrogen in the final annealing process.

In the embodiment of the present invention, the size of the primary recrystallization is controlled to 18.0 to 25.0 탆. If the size of the primary recrystallization is smaller than 18.0 탆, the temperature at which the crystal growth driving force is large and the secondary recrystallization starts The primary recrystallization is suppressed while the selective growth period in which only the secondary recrystallization grows becomes narrower.

In this case, the conditions for the growth of a good secondary recrystallized structure are not well established, so that the degree of secondary recrystallization is poor and the secondary recrystallized grain size becomes large.

On the other hand, if the size of the primary recrystallized grains is larger than 25.0 탆, the crystal growth driving force is low and the temperature at which the secondary recrystallization starts is increased, the inhibitor abruptly loses its strength and the primary recrystallization is suppressed, In the region where the secondary recrystallization does not grow during the secondary recrystallization forming section, the size of the primary recrystallized grains becomes larger and the specimen passes through in the thickness direction. So that a secondary recrystallization fine grain is formed.

The primary recrystallized steel sheet is coated with the annealing separator and then subjected to final annealing for a long period of time at a temperature in the range of 1020 to 1150 DEG C to cause secondary recrystallization so that the {110} face of the steel sheet is parallel to the rolled surface, So that {110} < 001 > The annealing separator may be preferably one produced based on MgO, but is not particularly limited thereto.

The purpose of the final annealing is to form a {110} < 001 > texture by secondary recrystallization, to provide insulating properties by forming a vitreous coating by reaction of the oxide layer and MgO formed during decarburization, and to remove impurities that impair magnetic properties. As the final annealing method, the nitride is inhibited by keeping the mixed gas of nitrogen and hydrogen at the temperature rising period before the secondary recrystallization, and the secondary recrystallization is well developed. After completion of the secondary recrystallization, 100% hydrogen It is kept in the atmosphere for a long time to remove impurities.

The final annealing step in the embodiment according to the present invention comprises a primary cracking step, a heating step and a secondary cracking step, and the step of raising the temperature is performed at a temperature of from 700 to 900 DEG C at a rate of from 18 to 75 DEG C / hr And the temperature is raised at a rate of 10 to 15 ° C / hr at 900 to 1020 ° C. At this time, the final high-temperature annealing for secondary recrystallization is performed in the range of 1020 to 1200 ° C.

Hereinafter, the present invention will be described in more detail with reference to examples.

[Example 1] Examination of change in iron loss for the upper limit of C content due to Cr addition

Si: 3.0 to 4.5%, C: 0.03 to 0.09%, Mn: 0.11%, Sol. The addition amount of Si and C was set to be 0.003 to 0.012 (%) larger than the C content upper limit Si (wt%) 0.0234 to 0.0194 by adding 0.028% of Al, 0.029% of P, 0.0042% of N, 0.0045% of S and 0.0030% %, And the content of Cr was changed as shown in Table 1, and the slabs of the remainder Fe and other inevitably contained directional electric steel sheets were heated at a temperature of 1200 DEG C for 210 minutes and then hot rolled to obtain 2.8 mm thick hot- Plate.

The hot-rolled sheet was heated to 1080 占 폚, held at 920 占 폚 for 90 seconds, quenched in water, pickled, and then cold-rolled to a thickness of 0.30 mm. (50% H ₂ + 50% N ₂ ) at a temperature of 800 ° C to 850 ° C during the initial decarburization annealing during the heating, and the ammonia gas was supplied at the same dew point And the mixture was held for 180 seconds to perform simultaneous decarburization and nitriding treatment.

This steel sheet was coated with MgO as an annealing separator and finally annealed in a coiled state. During the final annealing, the primary cracking temperature was 700 ° C and the secondary cracking temperature was 1200 ° C. The temperature rise in the temperature raising range was 45 ° C per hour in the temperature range of 700 ° C to 950 ° C and 15 ° C per hour in the temperature range of 950 ° C to 1200 ° C Respectively. On the other hand, the cracking time at 1200 ° C was treated for 15 hours. The atmosphere at the final annealing was a mixed atmosphere of 25% nitrogen + 75% hydrogen up to 1200 ° C. After reaching 1200 ° C, it was kept in 100% hydrogen atmosphere and then cooled. The magnetic properties measured for each condition are shown in Table 1.

Si (wt%) C (wt%) Cr (wt%) Iron loss (W17 / 50, W / kg) Magnetic flux density (B10, Tesla) division 3.2 0.06 0 1.052 1.855 Comparison 1 3.2 0.059 0.05 0.938 1.930 Inventory 1 3.2 0.063 0.03 1.043 1.872 Comparative material 2 3.2 0.0625 0.1 0.940 1.933 Inventory 2 4.0 0.0750 0 1.109 1.842 Comparative material 3 4.0 0.0775 0.05 0.941 1.928 Inventory 3 4.0 0.082 0.12 0.936 1.923 Invention 4

As can be seen from Table 1, the range of C content according to Si content and Cr content is Si (wt%) x 0.0218? C (wt%) +0.0194? Si (wt%) x 0.0234 + Cr (wt% × 0.1, the inventive materials 1 to 4 controlled in the scope of the present invention were found to be superior to the comparative material in magnetic properties. It can be seen that a grain-oriented electrical steel sheet having excellent magnetic properties can be produced by controlling the content of Si, C and Cr within the range of the above-mentioned relational expression.

While the present invention has been described in connection with certain exemplary embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims.

It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention .

Claims (8)

0.001 to 0.006% by weight of S, 0.0010 to 0.006% by weight of S, 0.0010 to 0.006% by weight of S, 0.03 to 0.09% by weight of C, 0.01 to 0.20% 0.03 to 0.12 wt% of Cr, 0.03 to 0.07 wt% of Sn, 0.01 to 0.05 wt% of Sb and 0.01 to 0.05 wt% of P, wherein P and Sb are P + 0.0630%, and the remainder is composed of Fe and other inevitably added impurities,
Preparing a slab in which the Si, C, and Cr contents satisfy the following formula (1);
Reheating the slab in the range of 1050 to 1250 占 폚;
Subjecting the reheated slab to hot rolling in the range of 950 to 1050 캜 and performing or omitting the hot-rolled sheet annealing;
Cold-rolling the annealed hot-rolled sheet;
Performing decarburization annealing and nitriding annealing of the cold-rolled cold rolled sheet; And
And finally annealing the steel sheet subjected to decarburization annealing and nitriding annealing,
The decarburization annealing and nitriding annealing may be performed at a temperature in the range of 800 to 900 DEG C,
Directional electric furnace where initial decarburization annealing is performed at a dew point of 60 to 70 ° C (50% N ₂ + 50% H ₂ ) at 800 to 850 ° C and simultaneous decarburization annealing and nitriding annealing are performed at a temperature range of 850 to 900 ° C Steel plate manufacturing method.
Si (wt%) x 0.0218? C (wt%) +0.0194? Si (wt%) x 0.0234 + Cr (wt% The method according to claim 1,
Wherein the nitrogen content in the steel sheet after decarburization annealing and nitriding annealing is 100 to 300 ppm. The method according to claim 1,
Wherein the size of the primary recrystallized grains after the decarburization annealing and the nitriding annealing is 18.0 to 25.0 占 퐉. delete delete The method according to claim 1,
In the final high-temperature annealing step,
Is in the range of 1020 to 1200 占 폚. The method according to claim 6,
The final high-temperature annealing may include:
Wherein the step of raising the temperature includes raising the temperature at a rate of 18 to 75 ° C / hr at 700 to 950 ° C, raising the temperature to 10 to 15 ° C at a temperature of 950 to 1020 ° C / hr. &lt; / RTI &gt; delete