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WO2011052858A1 - High-silicon steel sheet production method and high-silicon steel sheet produced using the same - Google Patents

High-silicon steel sheet production method and high-silicon steel sheet produced using the same Download PDF

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Publication number
WO2011052858A1
WO2011052858A1 PCT/KR2010/001828 KR2010001828W WO2011052858A1 WO 2011052858 A1 WO2011052858 A1 WO 2011052858A1 KR 2010001828 W KR2010001828 W KR 2010001828W WO 2011052858 A1 WO2011052858 A1 WO 2011052858A1
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Prior art keywords
steel sheet
silicon steel
silicon
powder
sio
Prior art date
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PCT/KR2010/001828
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French (fr)
Korean (ko)
Inventor
김상범
소준영
변지영
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Korea Electric Power Corp
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Korea Electric Power Corp
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Priority claimed from KR1020090104509A external-priority patent/KR20110047761A/en
Priority claimed from KR1020090130395A external-priority patent/KR101150336B1/en
Priority claimed from KR1020100000806A external-priority patent/KR101190826B1/en
Application filed by Korea Electric Power Corp filed Critical Korea Electric Power Corp
Publication of WO2011052858A1 publication Critical patent/WO2011052858A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/34—Embedding in a powder mixture, i.e. pack cementation
    • C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
    • C23C10/44—Siliconising
    • C23C10/46—Siliconising of ferrous surfaces
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy

Definitions

  • the present invention relates to a method for manufacturing a high silicon steel sheet and a high silicon steel sheet manufactured using the same, and more specifically, to use a metal fluoride powder mixed with a silicon injection source, or to insert a shield between the silicon injection source and the steel sheet And a method for producing a high silicon steel sheet having an economical and good surface state through heat treatment.
  • a silicon steel sheet having a silicon content of less than 3% has been mainly used as an iron core of a transformer or a motor using 60 Hz as a power frequency.
  • silicon content increases, eddy current loss decreases due to increase of electrical resistance, and the maximum permeability has the highest value at 6.5% of silicon content, and noise is minimized because magnetic deformation becomes zero.
  • the reason why the 3% silicon steel sheet has been mainly used for the transformer as described above is that the workability of the silicon steel sheet is significantly worsened at 4% or more of silicon, which makes cold rolling difficult, and therefore, mass production is difficult, thereby increasing manufacturing costs. to be.
  • a method of manufacturing a silicon steel sheet having a silicon content of less than 3% first and then adding silicon therein has been generally used as a method for producing a high silicon steel sheet having a silicon content of 4% or more.
  • the operation of diffusing silicon on the surface of the steel sheet to form a corrosion-resistant coating is referred to as 'siliconizing'.
  • PVD Physical Vapor Deposition
  • CVD Chemical Vapor Deposition
  • SiCl 4 silicon tetrachloride
  • Japan Patent Application Publication No. 1993-049745
  • Fe-Si powder a method using Fe-Si powder, and the like
  • the PVD method has a disadvantage in that a deposition rate is slow by depositing Si on both surfaces of a low silicon steel and diffusion heat treatment, and it is difficult to continuously process a large capacity because it is performed in a vacuum chamber.
  • the CVD method is a method of depositing Si on the surface by using SiCl 4 gas.
  • the acupuncture treatment unit In the continuous process, the acupuncture treatment unit, iron chloride collection stand, and U. It consists of an exhaust gas treatment unit equipped with a reactive silicon chloride recovery tank, a vaporization zone, and a gas heating zone, and because it uses highly reactive silicon tetrachloride, it is necessary to use a reaction chamber for controlling oxygen and water vapor in a gas atmosphere. There was a problem that the manufacturing cost increases due to the complicated process.
  • Fe-Si powder is Fe-Si powder, colloidal silica, aluminum oxide mixture (Korean Patent Publication No. 2004-0046398, 2004-0041773, 2004-41772, 2004-0046401), or Fe-Si powder MgO powder mixture (Korean Patent Publication No. 2004-0041774) is used, which is a solid-solid phase in which the diffusion of Si from the Fe-Si powder to the low silicon steel sheet occurs only when the Fe-Si powder and the solid steel sheet are in contact with each other. Because of the reaction, the reaction time is long and the shape of the surface of the material deteriorates.
  • an object of the present invention is to provide a method for producing a high silicon steel sheet having a good surface state quickly and economically.
  • a mixed powder by mixing the silicon injection source and the metal fluoride powder; Contacting the mixed powder with a low silicon steel sheet having a silicon content of less than 4% by weight; And heat-treating the low silicon steel sheet in contact with the mixed powder in a hydrogen atmosphere.
  • a method for producing a high silicon steel sheet comprising a.
  • the silicon injection source may be SiO 2 powder.
  • the mixed powder may further include a Si powder.
  • the content of Si powder in the mixed powder may be from 0.02% to 2.0% by weight of the mixed powder.
  • the metal fluoride powder may be MgF 2 or AlF 3 powder.
  • the content of the metal fluoride powder in the mixed powder may be 0.05% to 4.0% by weight of the mixed powder.
  • the heat treatment may be performed at 1000 °C to 1200 °C.
  • the heat treatment in the hydrogen atmosphere may be performed in a hydrogen atmosphere having a purity of 99.9% or more.
  • preparing a silicon injection source comprising a.
  • preparing a metal fluoride powder comprising a.
  • the silicon injection source may be a mixed powder in which the metal fluoride powder is mixed with the silicon injection source.
  • the silicon injection source may be one or more selected from the group consisting of SiO 2 , SiC and Si powder.
  • the shield may be a ceramic fabric or ceramic paper.
  • the metal fluoride may be any one selected from the group consisting of MgF 2 , AlF 3 and NaF.
  • the heat treatment in the hydrogen atmosphere may be performed in a hydrogen atmosphere having a purity of 97% or more.
  • the acupuncture composition composed of a mixture of any one of SiO 2 and AlF 3 or MgF 2 powder applied when manufacturing a high silicon steel sheet using a low silicon steel sheet having a silicon content of less than 4% by weight This is provided.
  • the powder mixture may further include Si powder.
  • the content of the AlF 3 or MgF 2 powder may be 0.05% to 4.0% by weight of the mixed powder.
  • the content of the Si powder may be 0.02% to 2.0% by weight of the mixed powder.
  • the silicon dioxide and the metal fluoride powder mixture that is easy to handle is used as a silicon source in manufacturing the high silicon steel sheet, there is an effect that the high silicon steel sheet can be more easily produced with a simpler device.
  • the use of gaseous reactions provides a simple and environmentally friendly method for physically immersing the device and process.
  • the present invention enables the injection of silicon even under a low purity hydrogen atmosphere, thereby providing a more economic process.
  • a ceramic fabric or ceramic paper as a shield between the silicon injection source and the steel sheet, it is possible to provide a method for manufacturing a high silicon steel sheet which can maintain a good surface roughness of the steel sheet after immersion.
  • 1 is a view showing a precipitation method using a SiO 2 -metal fluoride mixture.
  • FIG. 2 is a view showing a method of immersing by placing a low silicon steel sheet in and inside the SiO 2 -metal fluoride mixture, respectively.
  • FIG. 5 is a graph showing the result of increasing the silicon content as compared with the case where NaF powder was disposed after the deposition of NaF powder as a metal fluoride in the vicinity of the specimen.
  • silicon injection source 2 low silicon steel plate
  • SiO 2 -AlF 3 mixed powder 22 alumina crucible
  • the metal fluoride powder is MgF 2 Or AlF 3 Powder is preferred.
  • the silicon dioxide (SiO 2 ) Is a silicon oxide, silicon tetrachloride (SiCl) that easily reacts with moisture and oxygen in the air. 4 It is used as a silicon source instead of).
  • the added magnesium fluoride (MgF 2 ) reacts with silicon dioxide in a hydrogen atmosphere to contain silicon tetra-fluoride (SiF 4 ), silicon tri-fluoride (SiF 3 ), containing silicon and fluorine elements, Form various chemical species such as silicon di-fluoride (SiF 2 ), silicon fluoride (SiF), and silicon hydrides (SiHF 3 , SiH 2 F 2 , SiH 3 F, SiH 4 ) . These various species migrate to the low silicon steel surface through pores present in the silicon dioxide powder and magnesium fluoride powder mixture, and silicon is deposited on the surface by decomposition reaction or reduction by hydrogen. Silicon reduced at high temperature is diffused into the low silicon steel to produce high silicon steel.
  • the low silicon steel When the powder mixture is placed in a container such as alumina, the low silicon steel is brought into contact with the inside of the mixed powder, and elevated to a high temperature in a hydrogen atmosphere.
  • SiF 4 , SiF 3 , SiF 2 , SiF, Various species such as SiHF 3 , SiH 2 F 2 , SiH 3 F, and SiH 4 are formed, which migrate to the surface of the low silicon steel through the pores present in the mixed powder, and are used for decomposition reaction or reduction by hydrogen at the surface. Silicon will be deposited by.
  • the heat treatment is preferably performed at 1000 °C to 1200 °C.
  • the reaction temperature should be 1000 ° C or higher because the deposition rate decreases exponentially if the precipitation temperature is too low, and it is difficult to control the temperature industrially if it exceeds 1200 ° C.
  • the content of the metal fluoride powder in the mixed powder is preferably 0.05% to 4.0% by weight of the mixed powder. If the addition amount of the metal fluoride is less than 0.05% by weight, the sintering speed is too slow. If the magnesium fluoride content is increased, the sintering speed is increased, but the amount becomes constant when the amount exceeds 4% by weight.
  • the step of heat treatment in the hydrogen atmosphere is preferably carried out in a hydrogen atmosphere having a purity of 99.9% or more.
  • a hydrogen atmosphere having a purity of 99.9% or more.
  • expensive hydrogen having a high purity of 99.9999% or more should be used.
  • SiO 2 the possibility of moving to the right side in Equation (1) below will be examined in terms of thermodynamics.
  • Si can be formed by hydrogen reduction of SiO 2 when P H 2 O / P H 2 is 10 ⁇ 5 , that is, when the purity of hydrogen gas is about 5N, or more than 1612 K. have. If the value of P H2O / P H2 is 10 -6 , 1397K or more; if the value of P H2O / P H2 is 10 -7 , 1233K or more; if the value of P H2O / P H2 is 10 -8, It is possible to produce and the resulting Si is diffused into the low silicon steel sheet at that temperature.
  • Equation (1) Since the generated Si reacts with Fe or diffuses into the Fe matrix, the activity of Si is lowered rather than 1 in a pure state as shown in Equation (1). Assuming that Si generated by hydrogen reduction goes through an intermediate process of reacting with Fe to form FeSi, the free energy of formation of FeSi is expressed as -85,754 + 9.75 T (Joule). In view of this, equation (5) is expressed by equation (6).
  • the deposition of Si becomes possible at 1320K or more. This means that the operating temperature can be reduced by about 290 ° C or more than when pure Si is produced. If the value of P H2O / P H2 is 10 -6 or more, 1137K (approximately 260 ° C temperature drop), and if the value of P H2O / P H2 is 10 -7 , the temperature can be maintained at 1000K or more, it is possible to generate Si element. Si diffuses into the low silicon steel sheet at that temperature.
  • metal fluoride MgF 2
  • Gas species are formed, and they move to the surface of the low silicon steel sheet through the pores present in the powder mixture, and silicon is deposited on the surface by decomposition reaction or reduction by hydrogen (Yun Jin-kuk, Ji-young Byun, Jae-soo Kim, Choi Sul-sul, “ Thermodynamics and Kinetic Studies on Pack Siliconizing of Mo ”, Journal of the Korean Metal Society, vol.36, No.1 (1998) pp. 59-69).
  • the deposited silicon penetrates into the inside of the steel sheet by the diffusion reaction in the heat treatment process for a longer time to produce a high silicon steel sheet.
  • This method provides the great advantage of producing a better surface steel sheet through the movement of gas species including Si while using solid powders that are easy to handle.
  • Equation (7) considers that the solid phase-solid phase reaction between SiO 2 and AlF 3 takes place, but the vapor pressure of AlF 3 is high at that temperature, and it can be seen that the solid phase SiO 2 and AlF 3 in the gas phase participate in the reaction. Solid-solid reactions are slow because the reaction occurs only at the point of contact between the two materials. Based on this, equation (7) can be expressed by equation (8).
  • the Gibbs free energy change at standard conditions at 1400K is calculated as +77,263 Joules (I. Barin, Thermochemical Data of Pure Substances Part I and Part II, VCH, Germany, 1989).
  • the conditions under which the reaction proceeds to the right are calculated on the assumption that the vapor pressure of AlF 3 is 91 mbar at 1400 K and 1.5 mol of SiF 4 and 1 mol of H 2 O are produced when 1 mol of hydrogen is consumed. It can be seen that it is necessary to have more than%.
  • metal fluoride AlF 3 may reduce the purity of hydrogen to about 97%. It can be seen that the addition of metal fluoride is very effective industrially.
  • the mixed powder may further include a Si powder, the content of the Si powder may be from 0.02% to 2.0% by weight of the mixed powder. That is, a SiO 2 -Si-metal fluoride powder mixture using oxides SiO 2 and Si at the same time as a Si source can be used.
  • the pure Si has an activity of 1, which is greater than that of Si in SiO 2 This is because the partial pressures of the various species contained are higher when using SiO 2 -Si-MgF 2 powder mixtures than when only SiO 2 is used. This increases the supply of Si-containing gas species to the low silicon steel sheet surface, resulting in an increase in the deposition rate.
  • the SiO 2 -Si-metal fluoride mixed powder according to the present invention is made by mixing SiO 2 powder, Si powder, and metal fluoride powder. Next, the mixed powder is placed in a container such as alumina and low silicon steel is brought into contact with the inside of the mixed powder. When it is raised to a high temperature under a hydrogen atmosphere, various chemical species such as SiF 4 , SiF 3 , SiF 2 , SiF, SiHF 3 , SiH 2 F 2 , SiH 3 F, and SiH 4 , which contain Si and fluorine, are described as described above. It is formed, which moves through the pores present in the mixed powder to the surface of the low silicon steel, and silicon is deposited on the surface by decomposition reaction or reduction by hydrogen.
  • the content of Si in the SiO 2 -Si-MgF 2 mixture which is a siliceous composition according to the present invention, is preferably 0.02% by weight to 2.0% by weight.
  • Si is added in excess of 2.0% by weight, there is a problem that the surface of the silicon steel sheet produced by the direct contact between the Si powder and the low silicon steel sheet in the mixed powder has a problem, and when it is less than 0.02% by weight, there is no effect of increasing the deposition rate. Because.
  • Method for producing a high silicon steel sheet is to prepare a low silicon steel sheet having at least one silicon injection source selected from the group consisting of SiO 2 , SiC and Si in the form of powder, and silicon content less than 4% step; Inserting a shield between the silicon injection source and a low silicon steel sheet to form a laminated structure; And heat treating the laminated structure in a hydrogen atmosphere.
  • the present invention has devised a method of isolating each other by inserting a medium having a low reactivity with the steel sheet between the steel sheet and the powder mixture to solve the problems of the prior art. Such media are referred to herein as shields.
  • ceramics have a weak reactivity with iron, so they were used as shields.
  • Ceramics or ceramic papers are made of oxides in the form of fibers or whiskers, or woven into paper or paper. They have a space through which gas can pass and have a weak reactivity with steel sheets. Therefore, such a ceramic fabric or ceramic paper serves as a smooth passage in the immersion method using a gas phase movement including Si, and at the same time, isolates the silicon injection source and the steel sheet to maintain a good steel sheet state. Do it.
  • the medium serving as a shield can be used as long as the medium is not ceramic cloth or paper, but has a space through which gas can pass, and is weak in reactivity with a steel sheet or a silicon injection source.
  • Another aspect of the present invention is a method of heat-treating the silicon injection source 1 with the shield (3) between the low silicon steel sheet (2) as shown in FIG. .
  • a method of placing a shield and a silicon injection source on one low silicon steel sheet and on both sides or a cross section may be used to infiltrate a continuous process in the form of a single plate or a long coil.
  • the shield is a ceramic fabric or ceramic paper containing SiO 2
  • the metal fluoride in powder form may be applied in the form of spray or slurry to the ceramic fabric or ceramic paper.
  • the silicon injection source is unnecessary.
  • the silicon itself serves as a source of silicon, it is possible to settle without a separate powder source of silicon. In this case, however, it is desirable to manufacture the metal fluoride together in an industrially fast and economical manner.
  • the metal fluoride when the metal fluoride is in the form of powder, it is preferable to spray the shield in an appropriate amount or to apply it in the form of a slurry, and the metal fluoride is preferably any one selected from the group consisting of MgF 2 , AlF 3 and NaF.
  • the heat treatment of the laminated structure in a hydrogen atmosphere may be performed in a hydrogen atmosphere having a purity of 97% or more.
  • the pure SiO 2 and SiO 2 and AlF 3 1.0 wt% (SiO 2 -AlF 3 powder mixture total weight) to a mixture SiO 2 -AlF 3 powder mixture of two kinds of silicon steel sheet by using a silicon source was produced.
  • the mixed powder 11 was immersed in a 30 ml volume alumina crucible 12, and the silicon mixture having a size of 1 cm x 1 cm x 0.15 mm in silicon was 3% by weight.
  • the steel plate 13 was put in. Thereafter, the silicon steel sheet 13 was placed in an Inconel tube and heated in the same state as shown in FIG. 1.
  • Two silicon steel sheets having a silicon content of 3% by weight were changed as shown in FIG. 2 to prepare silicon steel sheets in the same manner as in Example 1.
  • One of the 1 cm x 1 cm x 0.15 mm silicon steel sheets (23a) was placed on the surface of the mixed powder 21 in which SiO 2 and 1.0% by weight of AlF 3 (based on the total weight of the SiO 2 -AlF 3 mixed powder) were mixed. More specifically, 1.0 wt% of the mixed powder of SiO 2 and AlF 3 was covered with pure SiO 2 powder so that the AlF 3 and the silicon steel sheet could not be directly contacted, and then the 3 wt% silicon steel sheet was placed on the SiO 2 powder. .
  • the other one of the silicon steel sheets 23b was placed inside the SiO 2 -AlF 3 mixed powder 21 as in Example 1, and then subjected to a precipitation treatment for 8 hours at 1100 ° C. using 99.9% hydrogen.
  • SiO 2 -AlF 3 increased weight is 2.05% of the silicon steel sheet in a mixed powder surface, the weight of the silicon steel sheet in the SiO 2 -AlF 3 powder mixture inside was able to observe that the increase of 2.09%.
  • the results of the electron probe microanalysis (EPMA) analysis showed that the former silicon concentration was 5.10 wt% and the latter silicon concentration was 5.12 wt%.
  • the weight of the silicon steel sheet increased 0.98% when the immersion temperature was set to 1000 ° C, and the weight of the silicon steel sheet increased by 3.65% when the temperature was set to 1200 ° C.
  • the silicon content was found to be 4.03% by weight and 6.55% by weight, respectively, as a result of analysis by the electron probe microanalyzer (EPMA).
  • the concentration of AlF 3 in the SiO 2 -AlF 3 mixture was changed to 0.05%, 0.25%, 0.50%, 1.00%, 2.00%, 3.00%, 4.00% by weight with 99.9% purity hydrogen. It was settled for 8 hours at 1100 ° C.
  • the concentration of AlF 3 is 0.05 wt%, 0.25 wt%, 0.50 wt%, 1.00 wt%, 2.00 wt%, 3.00 wt%, 4.00 wt%
  • the weight of the silicon steel sheet is 0.80%, 1.31%, 1.52%, 2.09%, 2.54%, 3.45%, 3.40% increased
  • the results of the analysis by the electron probe microanalyzer (EPMA) showed that the silicon content was 3.87%, 4.42%, 4.58%, 5.12% by weight. , 5.65% by weight, 6.48% by weight, it could be confirmed that the 6.46% by weight.
  • SiO 2 silicon dioxide
  • MgF 2 magnesium fluoride
  • the powder mixture is immersed in an alumina crucible having a volume of about 30 ml, and 3% silicon steel sheet having a size of 1 cm ⁇ 1 cm ⁇ 0.15 mm is placed in the powder. In that state, it is placed in an inconel tube and heated to 1100 ° C. The atmosphere used hydrogen of 99.9% purity. After maintaining at 1100 ° C. for 6 hours, the furnace was cooled and the weight of the specimen was measured.
  • Example 5 and the experimental method is the same, but 3% silicon steel sheet of 11 cm ⁇ 1 cm ⁇ 0.15 mm size was used.
  • the content of MgF 2 in the mixed powder was increased to 2% by mass percentage, and 99.9% pure hydrogen was used to immerse at 1100 ° C.
  • the weight change of the silicon steel sheets in the powder was 0.8%, 1.6%, 1.9%, 2.8%, 3.2%, respectively, when the immersion time was changed to 1 hour, 4 hours, 6 hours, 14 hours, 20 hours.
  • Each EPMA silicon analysis was 3.9%, 4.6%, 5.0%, 5.9% and 6.4%.
  • the amount of precipitation increases in proportion to the square root of the reaction time. This suggests that the gas phase diffusion in which Si-containing gas species move to the surface of the silicon steel sheet through the pores of the mixed powder is a reaction rate.
  • SiO 2 + Si + MgF 2 mixed powder acts as a silicon source.
  • SiO 2 + 0.13 wt% Si + 2.0 wt% MgF 2 mixed powder was used as the siliceous composition.
  • the mixed powder 11 is immersed in an alumina crucible 12 having a volume of about 30 ml, and a 3% silicon steel sheet 13 having a size of 1 cm ⁇ 1 cm ⁇ 0.25 mm is placed in the powder. Placed in the Inconel tube in the same state as above, heated to 1100 ° C., using 99.9% purity hydrogen. After maintaining for 6 hours at 1100 °C, the weight change of the specimen was measured by blast furnace and the weight increase of 2.8% was observed.
  • the EPMA (Electron Probe Micro Analyzer) analysis showed that silicon steel sheet containing 5.9% of silicon was obtained.
  • Example 7 and the experimental method were the same, but a 3% silicon steel sheet having a size of 11 cm ⁇ 1 cm ⁇ 0.25 mm was used.
  • the content of MgF 2 in the mixed powder was fixed at 2% by mass percentage and subjected to time immersion at 1100 ° C. using 99.9% purity hydrogen.
  • the silicon content in the siliceous composition was changed to 0%, 0.05%, 0.25%, 0.52%, and 1.0%.
  • the weight change of silicon steel sheet was 1.2%, 1.7%, 3.8%, 6.5%, and 10.7%, respectively
  • the analysis of EPMA silicon was 4.2%, 4.8%, 6.7%, 9.2%, and 12.8%, respectively.
  • Example 8 The experiment was carried out in the same manner as in Example 8, the content of MgF 2 in the mixed powder was 2% by weight, the content of Si was 0.52% by weight. 99.5% pure hydrogen was used to immerse at 1100 ° C. At this time, the weight change of the silicon steel sheet in the powder was 3.1%, 3.8%, and 4.2%, respectively.
  • the EPMA silicon analysis values were 6.0% and 6.7, respectively. %, 7.2%.
  • the surface roughness of the steel sheet with a silicon content of 6.2% manufactured by using a ceramic fabric containing silica (SiO 2 ) as a shield increased three times compared to a 3% state, thereby obtaining a relatively good surface state. Even in SiO 2 + AlF 3 system, when the ceramic fabric containing silica (SiO 2 ) is used to immerse up to 6% of silicon, the surface roughness increases about 4 times compared to that of 3% of silicon. And it was found.
  • a ceramic fabric i.e., a silica fabric, comprising silica (SiO 2 ) having a width of 12 cm, a length of 14 cm, and a thickness of 0.8 mm, on both sides of a 3% silicon steel specimen of 0.15 mm thickness, 12 cm length, and 10 cm width. Buil safetech) was wrapped and heat-treated at 1200 °C for hours under hydrogen atmosphere to confirm the silicon content by the furnace cooling. As a result, as shown in FIG.
  • FIG. 5 shows that after the NaF powder is placed as a metal fluoride in the vicinity of the specimen, the silicon content is increased as compared with the case without NaF. As shown in FIG. 5, it was confirmed that the silicon content was relatively increased as compared with the case without the metal fluoride.

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Abstract

The present invention relates to a method for producing high-silicon steel sheet and to high-silicon steel sheet produced using the same, and more specifically relates to a method for producing high-silicon steel sheet which is economic and at the same time has a good surface condition by using a metal fluoride powder in a mixture with a silicon injection source, or inserting a shield between a silicon injection source and steel plate and carrying out a heat treatment. The present invention has the advantageous effect that high-silicon steel sheets can be made relatively easily by means of a relatively uncomplicated device by using an easy-to-handle silicon dioxide and metal fluoride powder mixture as a silicon source in the production of high-silicon steel sheets. Also, a physical siliconising method is provided which is environmentally friendly and which involves an uncomplicated device and process since a reaction in the gas-phase rotation is employed. Also provided is a process which is relatively economic as it allows silicon to be injected even in a low-purity hydrogen atmosphere. In particular, a production method for a high-silicon steel sheet can be provided which allows good steel sheet surface roughness to be maintained after siliconising, by inserting a ceramic textile or ceramic fibre as a shield between a silicon-injection source and a steel plate when producing high-silicon steel sheets.

Description

고규소강판 제조방법 및 이를 이용하여 제조된 고규소강판 Manufacturing method of high silicon steel sheet and high silicon steel sheet manufactured using the same

본 발명은 고규소강판을 제조하는 방법 및 이를 이용하여 제조된 고규소강판 에 관한 것으로, 보다 구체적으로는 금속불화물 분말을 규소주입원에 혼합하여 사용하거나, 규소주입원과 강판 사이에 실드를 삽입하고 열처리를 거쳐 경제적이면서 양호한 표면상태를 가지는 고규소강판을 제조하는 방법에 관한 것이다.The present invention relates to a method for manufacturing a high silicon steel sheet and a high silicon steel sheet manufactured using the same, and more specifically, to use a metal fluoride powder mixed with a silicon injection source, or to insert a shield between the silicon injection source and the steel sheet And a method for producing a high silicon steel sheet having an economical and good surface state through heat treatment.

종래에는 전력주파수로 60Hz를 사용하는 변압기나 전동기의 철심 소재로 규소함량이 3% 이내인 규소강판이 주로 사용되어 왔다. 한편, 규소함량이 증가하면 전기저항이 증가하여 와류손(eddy current loss)이 감소하고, 규소함량 6.5%에서는 최대투자율 (maximum permeability)이 최고값을 가지며, 자기 변형이 0이 되기 때문에 소음을 최소화할 수 있는 장점이 있다. 그럼에도 불구하고 상기와 같이 변압기용으로 3% 규소강판이 주로 사용되어 온 이유는 규소함량 4% 이상에서는 규소강판의 가공성이 현저하게 나빠져 냉간 압연이 어려워지고 이에 따라 대량 생산이 힘들어 제조 원가가 높아지기 때문이다. 이러한 이유 때문에, 규소함량이 3% 이내인 규소강판을 먼저 제조한 후 거기에 규소를 더 첨가하는 방법이 규소함량이 4% 이상인 고규소강판의 제조방법으로써 일반적으로 쓰이고 있는 실정이었다. 한편, 상기와 같이 고규소강판을 제조하기 위해 규소를 강판 표면에 확산시켜 내식성 피막을 만드는 조작을 '침규(浸硅, siliconizing)'라 한다.Conventionally, a silicon steel sheet having a silicon content of less than 3% has been mainly used as an iron core of a transformer or a motor using 60 Hz as a power frequency. On the other hand, as silicon content increases, eddy current loss decreases due to increase of electrical resistance, and the maximum permeability has the highest value at 6.5% of silicon content, and noise is minimized because magnetic deformation becomes zero. There is an advantage to this. Nevertheless, the reason why the 3% silicon steel sheet has been mainly used for the transformer as described above is that the workability of the silicon steel sheet is significantly worsened at 4% or more of silicon, which makes cold rolling difficult, and therefore, mass production is difficult, thereby increasing manufacturing costs. to be. For this reason, a method of manufacturing a silicon steel sheet having a silicon content of less than 3% first and then adding silicon therein has been generally used as a method for producing a high silicon steel sheet having a silicon content of 4% or more. On the other hand, in order to produce a high silicon steel sheet as described above, the operation of diffusing silicon on the surface of the steel sheet to form a corrosion-resistant coating is referred to as 'siliconizing'.

이러한 침규법과 관련하여 지금까지 PVD(물리적 증기증착법, Physical Vapor Deposition)법(한국 특허공개번호 2002-0050012), 사염화규소(SiCl4) 가스를 이용한 CVD(화학적 증기증착법, Chemical Vapor Deposition)법(일본 공개특허공보 1993-049745), Fe-Si 분말을 이용하는 방법 등이 제안되어왔다. 그러나, PVD법은 Si을 저규소강 표면 양면에 증착하고 확산 열처리하는 것으로 증착속도가 느리며, 진공 챔버 내에서 수행되기 때문에 대용량을 연속적으로 처리하기가 곤란한 단점이 있었다. 한편, CVD법은 SiCl4 가스를 이용하여 표면에 Si을 증착시키는 방법으로써 연속 공정에서는 입구 측으로부터 저규소강판 가열대, 침규대, 확산대, 냉각대가 순서대로 배치된 침규처리부와 염화철회수대, 미반응 염화규소회수대, 기화대, 가스가열대로 구비된 배기가스처리부로 구성되고, 반응성이 강한 사염화규소를 사용하기 때문에 가스분위기 내 산소와 수증기의 제어를 위해 반응 챔버 등을 이용해야 하는 등 장치와 공정이 복잡하여 제조 원가가 상승하는 문제점이 있었다. In connection with this deposition method, PVD (Physical Vapor Deposition) method (Korean Patent Publication No. 2002-0050012), CVD (Chemical Vapor Deposition) method using silicon tetrachloride (SiCl 4 ) gas (Japan) Patent Application Publication No. 1993-049745), a method using Fe-Si powder, and the like have been proposed. However, the PVD method has a disadvantage in that a deposition rate is slow by depositing Si on both surfaces of a low silicon steel and diffusion heat treatment, and it is difficult to continuously process a large capacity because it is performed in a vacuum chamber. On the other hand, the CVD method is a method of depositing Si on the surface by using SiCl 4 gas. In the continuous process, the acupuncture treatment unit, iron chloride collection stand, and U. It consists of an exhaust gas treatment unit equipped with a reactive silicon chloride recovery tank, a vaporization zone, and a gas heating zone, and because it uses highly reactive silicon tetrachloride, it is necessary to use a reaction chamber for controlling oxygen and water vapor in a gas atmosphere. There was a problem that the manufacturing cost increases due to the complicated process.

또한, Fe-Si 분말에 의한 방법은 Fe-Si 분말과 콜로이달 실리카, 산화알루미늄 혼합체(한국특허공개번호 2004-0046398, 2004-0041773, 2004-41772,2004-0046401), 또는 Fe-Si 분말과 MgO 분말 혼합체(한국특허공개번호 2004-0041774)를 이용하는데, 이 방법은 고체상의 Fe-Si 분말과 고체상의 강판이 접촉해야만 Fe-Si 분말에서 저규소강판으로 Si의 확산이 일어나게 되는 고체상-고체상 반응이므로 반응시간이 길고 소재 표면의 형상이 악화되는 단점이 있었다.In addition, the method by Fe-Si powder is Fe-Si powder, colloidal silica, aluminum oxide mixture (Korean Patent Publication No. 2004-0046398, 2004-0041773, 2004-41772, 2004-0046401), or Fe-Si powder MgO powder mixture (Korean Patent Publication No. 2004-0041774) is used, which is a solid-solid phase in which the diffusion of Si from the Fe-Si powder to the low silicon steel sheet occurs only when the Fe-Si powder and the solid steel sheet are in contact with each other. Because of the reaction, the reaction time is long and the shape of the surface of the material deteriorates.

이와 같은 기술적 배경 하에서, 저규소강판을 침규시켜 고규소강판을 제조시 양호한 표면상태를 가지는 고규소강판을 신속하고 경제적으로 제조하는 방법을 개발하고자 예의 노력한 결과 본 발명을 완성하기에 이르렀다. 결국 본 발명의 목적은 신속하고 경제적으로 양호한 표면상태를 가지는 고규소강판을 제조하는 방법을 제공하는데 있다.Under such technical background, the present invention has been completed as a result of intensive efforts to develop a method of rapidly and economically manufacturing a high silicon steel sheet having a good surface state when the high silicon steel sheet is manufactured by immersing the low silicon steel sheet. After all, an object of the present invention is to provide a method for producing a high silicon steel sheet having a good surface state quickly and economically.

본 발명의 일 측면에 따르면 규소주입원과 금속불화물 분말을 혼합하여 혼합분말을 생성하는 단계; 상기 혼합분말에 규소 함량이 4중량% 미만인 저규소강판을 접촉시키는 단계; 및 상기 혼합분말에 접촉된 상태의 저규소강판을 수소분위기에서 열처리하는 단계; 를 포함하는 고규소강판의 제조방법이 제공된다.According to one aspect of the invention to produce a mixed powder by mixing the silicon injection source and the metal fluoride powder; Contacting the mixed powder with a low silicon steel sheet having a silicon content of less than 4% by weight; And heat-treating the low silicon steel sheet in contact with the mixed powder in a hydrogen atmosphere. Provided is a method for producing a high silicon steel sheet comprising a.

본 발명의 바람직한 실시예에 따르면, 상기 규소주입원은 SiO2 분말일 수 있다.According to a preferred embodiment of the present invention, the silicon injection source may be SiO 2 powder.

본 발명의 바람직한 실시예에 따르면, 상기 혼합분말은 Si 분말을 더 포함할 수 있다.According to a preferred embodiment of the present invention, the mixed powder may further include a Si powder.

본 발명의 바람직한 실시예에 따르면, 상기 혼합분말 중 Si 분말의 함량은 상기 혼합분말 중 0.02 중량% 내지 2.0 중량%일 수 있다.According to a preferred embodiment of the present invention, the content of Si powder in the mixed powder may be from 0.02% to 2.0% by weight of the mixed powder.

본 발명의 바람직한 실시예에 따르면, 상기 금속불화물 분말은 MgF2 또는 AlF3 분말일 수 있다.According to a preferred embodiment of the present invention, the metal fluoride powder may be MgF 2 or AlF 3 powder.

본 발명의 바람직한 실시예에 따르면, 상기 혼합분말 중 금속불화물 분말의 함량은 상기 혼합분말 중 0.05중량% 내지 4.0 중량%일 수 있다.According to a preferred embodiment of the present invention, the content of the metal fluoride powder in the mixed powder may be 0.05% to 4.0% by weight of the mixed powder.

본 발명의 바람직한 실시예에 따르면, 상기 열처리는 1000℃ 내지 1200℃로 행해질 수 있다.According to a preferred embodiment of the present invention, the heat treatment may be performed at 1000 ℃ to 1200 ℃.

본 발명의 바람직한 실시예에 따르면, 상기 수소 분위기에서 열처리하는 단계는 99.9% 이상의 순도를 갖는 수소 분위기에서 행해질 수 있다.According to a preferred embodiment of the present invention, the heat treatment in the hydrogen atmosphere may be performed in a hydrogen atmosphere having a purity of 99.9% or more.

본 발명의 다른 일 측면에 따르면, 규소주입원을 준비하는 단계; 상기 규소주입원에 실드가 적층된 규소 함량이 4중량% 미만인 저규소강판을 접촉시키는 단계; 및 상기 규소주입원에 접촉된 상태의 저규소강판을 수소분위기에서 열처리하는 단계; 를 포함하는 고규소강판의 제조방법이 제공된다.According to another aspect of the invention, preparing a silicon injection source; Contacting the silicon injection source with a low silicon steel sheet having a shielded silicon content of less than 4% by weight; And heat-treating the low silicon steel sheet in contact with the silicon injection source in a hydrogen atmosphere. Provided is a method for producing a high silicon steel sheet comprising a.

본 발명의 또 다른 일 측면에 따르면, 금속불화물 분말을 준비하는 단계; 상기 금속불화물 분말에 SiO2를 포함한 실드가 적층된 규소 함량이 4중량% 미만인 저규소강판을 접촉시키는 단계; 및 상기 혼합분말에 접촉된 상태의 저규소강판을 수소분위기에서 열처리하는 단계; 를 포함하는 고규소강판의 제조방법이 제공된다.According to another aspect of the invention, preparing a metal fluoride powder; Contacting the metal fluoride powder with a low silicon steel sheet having a silicon content of less than 4% by weight in which a shield including SiO 2 is laminated; And heat-treating the low silicon steel sheet in contact with the mixed powder in a hydrogen atmosphere. Provided is a method for producing a high silicon steel sheet comprising a.

본 발명의 바람직한 실시예에 따르면, 상기 규소주입원은 규소주입원에 금속불화물 분말을 혼합한 혼합분말일 수 있다.According to a preferred embodiment of the present invention, the silicon injection source may be a mixed powder in which the metal fluoride powder is mixed with the silicon injection source.

본 발명의 바람직한 실시예에 따르면, 상기 규소주입원은 SiO2, SiC 및 Si 분말로 이루어지는 군으로부터 선택되는 하나 이상일 수 있다.According to a preferred embodiment of the present invention, the silicon injection source may be one or more selected from the group consisting of SiO 2 , SiC and Si powder.

본 발명의 바람직한 실시예에 따르면, 상기 실드는 세라믹 직물 또는 세라믹 페이퍼일 수 있다.According to a preferred embodiment of the present invention, the shield may be a ceramic fabric or ceramic paper.

본 발명의 바람직한 실시예에 따르면, 상기 금속불화물은 MgF2, AlF3 및 NaF로 이루어지는 군으로부터 선택된 어느 하나일 수 있다.According to a preferred embodiment of the present invention, the metal fluoride may be any one selected from the group consisting of MgF 2 , AlF 3 and NaF.

본 발명의 바람직한 실시예에 따르면, 상기 수소 분위기에서 열처리하는 단계는 97% 이상의 순도를 갖는 수소 분위기에서 행해질 수 있다.According to a preferred embodiment of the present invention, the heat treatment in the hydrogen atmosphere may be performed in a hydrogen atmosphere having a purity of 97% or more.

본 발명의 다른 일 측면에 따르면, 상기 방법 중 어느 하나의 방법으로 제조된 고규소강판이 제공된다.According to another aspect of the invention, there is provided a high silicon steel sheet produced by any one of the above methods.

본 발명의 또 다른 일 측면에 따르면, 규소 함량이 4중량% 미만인 저규소강판을 이용하여 고규소강판을 제조 시 적용하는 SiO2 와, AlF3 또는 MgF2 분말 중 어느 하나의 혼합체로 구성된 침규 조성물이 제공된다.According to another aspect of the present invention, the acupuncture composition composed of a mixture of any one of SiO 2 and AlF 3 or MgF 2 powder applied when manufacturing a high silicon steel sheet using a low silicon steel sheet having a silicon content of less than 4% by weight This is provided.

본 발명의 바람직한 실시예에 따르면, 상기 분말 혼합체는 Si 분말을 더 포함할 수 있다.According to a preferred embodiment of the present invention, the powder mixture may further include Si powder.

본 발명의 바람직한 실시예에 따르면, 상기 AlF3 또는 MgF2 분말의 함량은 상기 혼합분말 중 0.05중량% 내지 4.0 중량%일 수 있다.According to a preferred embodiment of the present invention, the content of the AlF 3 or MgF 2 powder may be 0.05% to 4.0% by weight of the mixed powder.

본 발명의 바람직한 실시예에 따르면, 상기 Si 분말의 함량은 상기 혼합분말 중 0.02중량% 내지 2.0 중량%일 수 있다.According to a preferred embodiment of the present invention, the content of the Si powder may be 0.02% to 2.0% by weight of the mixed powder.

본 발명에 따르면, 고규소강판을 제조함에 있어서, 취급이 용이한 이산화규소와 금속불화물 분말혼합을 규소원으로 사용하므로 보다 간편한 장치로 보다 용이하게 고규소강판을 생산할 수 있는 효과가 있다. 또한, 가스상의 반응을 이용하기 때문에 장치 및 공정이 단순하고 환경 친화적인 물리적 침규방법을 제공한다. 또한, 본 발명은 저순도의 수소 분위기 하에서도 규소의 주입이 가능하므로 보다 경제적인 공정을 제공한다. 특히, 고규소강판을 제조함에 있어서 세라믹 직물 또는 세라믹 페이퍼를 실드로서 규소주입원과 강판 사이에 삽입함으로써 침규 후 강판의 표면 조도를 양호하게 유지할 수 있는 고규소강판의 제조방법을 제공할 수 있다.According to the present invention, since the silicon dioxide and the metal fluoride powder mixture that is easy to handle is used as a silicon source in manufacturing the high silicon steel sheet, there is an effect that the high silicon steel sheet can be more easily produced with a simpler device. In addition, the use of gaseous reactions provides a simple and environmentally friendly method for physically immersing the device and process. In addition, the present invention enables the injection of silicon even under a low purity hydrogen atmosphere, thereby providing a more economic process. In particular, in manufacturing a high silicon steel sheet, by inserting a ceramic fabric or ceramic paper as a shield between the silicon injection source and the steel sheet, it is possible to provide a method for manufacturing a high silicon steel sheet which can maintain a good surface roughness of the steel sheet after immersion.

도 1은 SiO2 - 금속불화물 혼합체를 이용한 침규방법을 나타낸 도면이다.1 is a view showing a precipitation method using a SiO 2 -metal fluoride mixture.

도 2는 SiO2 - 금속불화물 혼합체 내부 및 표면에 각각 저규소강판을 위치시켜 침규하는 방법을 나타낸 도면이다.2 is a view showing a method of immersing by placing a low silicon steel sheet in and inside the SiO 2 -metal fluoride mixture, respectively.

도 3는 규소주입원(1)을 강판(2) 사이에 실드(3)와 함께 적층시킨 모습을 나타낸다.3 shows a state in which the silicon injection source 1 is laminated together with the shield 3 between the steel sheets 2.

도 4는 SiO2+Si+MgF2 계, SiO2+Si+MgF2 계(실드 없음) 및 SiO2+AlF3 계 조건에서 고규소강판 제조공정에 따른 강판 상태를 표면 조도 측정기로 측정한 결과를 나타내는 그래프이다.4 is a surface roughness measurement result of the state of the steel sheet according to the manufacturing process of high silicon steel sheet under the conditions of SiO 2 + Si + MgF 2 system, SiO 2 + Si + MgF 2 system (without shield) and SiO 2 + AlF 3 system A graph representing.

도 5는 시편 부근에 금속불화물로서 NaF 분말을 배치한 후 침규한 결과, NaF가 없는 경우에 비해 규소 함량이 더 증대되는 결과를 나타내는 그래프이다.FIG. 5 is a graph showing the result of increasing the silicon content as compared with the case where NaF powder was disposed after the deposition of NaF powder as a metal fluoride in the vicinity of the specimen.

*도면의 주요부분에 대한 부호의 명칭** Names of symbols for main parts of drawings *

1 : 규소주입원 2 : 저규소 강판1: silicon injection source 2: low silicon steel plate

3 : 실드(Shield) 11 : 혼합분말 3: shield 11: mixed powder

12 : 알루미나 도가니 13 : 저규소강판 12: alumina crucible 13: low silicon steel sheet

21 : SiO2-AlF3 혼합분말 22 : 알루미나 도가니 21: SiO 2 -AlF 3 mixed powder 22: alumina crucible

23a, 23b : 저규소강판 23a, 23b: low silicon steel sheet

본 발명은 다양한 변환을 가할 수 있고 여러 가지 실시예를 가질 수 있는 바, 특정 실시예들을 도면에 예시하고 상세한 설명에 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변환, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 본 발명을 설명함에 있어서 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우 그 상세한 설명을 생략한다.As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all transformations, equivalents, and substitutes included in the spirit and scope of the present invention. In the following description of the present invention, if it is determined that the detailed description of the related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.

본 발명의 고규소강판의 제조방법은, SiO2 분말과 금속불화물 분말을 혼합하여 혼합분말을 생성하는 단계; 상기 혼합분말에 규소 함량이 4중량% 미만인 저규소강판을 접촉시키는 단계; 및 상기 혼합분말에 접촉된 상태의 저규소강판을 수소분위기에서 열처리하는 단계를 거친다. 한편, 본 발명에 따르면, 상기 금속불화물 분말은 MgF2 또는 AlF3 분말이 바람직하다. 상기 이산화규소(SiO2)는 규소산화물로서, 종래 공기 중의 수분이나 산소와 쉽게 반응하는 사염화규소(SiCl4)를 대신하여 규소원으로 사용된다. 순수한 이산화규소를 사용하더라도 침규가 가능하지만, 이 경우는 99.9999% 이상의 초고순도 수소를 사용하여야 하고 1200℃ 정도의 고온이 필요한 단점이 있다. 따라서, 본 발명에서는 침규과정에서 소량의 금속불화물(MgF2 또는 AlF3)을 첨가함으로써 보다 저온에서도 침규가 가능해지고 특히 깨끗한 강판 표면을 얻을 수 있다. Method for producing a high silicon steel sheet of the present invention, SiO2 Mixing the powder with the metal fluoride powder to produce a mixed powder; Contacting the mixed powder with a low silicon steel sheet having a silicon content of less than 4% by weight; And heat-treating the low silicon steel sheet in contact with the mixed powder in a hydrogen atmosphere. Meanwhile, According to the present invention, the metal fluoride powder is MgF2 Or AlF3 Powder is preferred. The silicon dioxide (SiO2) Is a silicon oxide, silicon tetrachloride (SiCl) that easily reacts with moisture and oxygen in the air.4It is used as a silicon source instead of). Even if pure silicon dioxide is used, it is possible to settle, but in this case, it is necessary to use ultra high purity hydrogen of 99.9999% or more and a high temperature of about 1200 ℃ is required. Therefore, in the present invention, a small amount of metal fluoride (MgF)2 Or AlF3) Can be deposited at lower temperatures and a particularly clean steel surface can be obtained.

첨가된 불화마그네슘(MgF2)은 수소 분위기에서 이산화규소와 반응하여 규소와 불소원소를 포함하는 사불화규소(Silicon tetra-fluoride; SiF4), 삼불화규소(Silicon tri-fluoride; SiF3), 이불화규소(Silicon di-fluoride; SiF2), 일불화규소(Silicon fluoride; SiF), 수소화규소들(SiHF3, SiH2F2, SiH3F, SiH4) 등의 다양한 화학종을 형성시킨다. 이러한 다양한 화학종은 이산화규소 분말 및 불화마그네슘 분말 혼합체 내에 존재하는 기공을 통해 저규소강 표면으로 이동하게 되고 그 표면에서 분해반응이나 수소에 의한 환원에 의해 규소가 증착되게 된다. 고온에서 환원된 규소는 저규소강 내부로 확산하여 들어가게 되어 고규소강이 제조되는 것이다. 분말 혼합체를 알루미나 등의 용기에 담고 혼합분말 내부에 저규소강을 접촉시키고, 수소 분위기 하에서 고온으로 상승시키면, 전술한 바와 같이 Si와 불소원소를 포함하는 SiF4, SiF3, SiF2, SiF, SiHF3, SiH2F2, SiH3F, SiH4 등의 다양한 화학종이 형성되고, 이는 혼합분말 내에 존재하는 기공을 통해 저규소강 표면으로 이동하게 되며 그 표면에서 분해반응이나 수소에 의한 환원에 의해 규소가 증착되게 되는 것이다.The added magnesium fluoride (MgF 2 ) reacts with silicon dioxide in a hydrogen atmosphere to contain silicon tetra-fluoride (SiF 4 ), silicon tri-fluoride (SiF 3 ), containing silicon and fluorine elements, Form various chemical species such as silicon di-fluoride (SiF 2 ), silicon fluoride (SiF), and silicon hydrides (SiHF 3 , SiH 2 F 2 , SiH 3 F, SiH 4 ) . These various species migrate to the low silicon steel surface through pores present in the silicon dioxide powder and magnesium fluoride powder mixture, and silicon is deposited on the surface by decomposition reaction or reduction by hydrogen. Silicon reduced at high temperature is diffused into the low silicon steel to produce high silicon steel. When the powder mixture is placed in a container such as alumina, the low silicon steel is brought into contact with the inside of the mixed powder, and elevated to a high temperature in a hydrogen atmosphere. As described above, SiF 4 , SiF 3 , SiF 2 , SiF, Various species such as SiHF 3 , SiH 2 F 2 , SiH 3 F, and SiH 4 are formed, which migrate to the surface of the low silicon steel through the pores present in the mixed powder, and are used for decomposition reaction or reduction by hydrogen at the surface. Silicon will be deposited by.

한편, 본 발명의 실시예에 따르면, 상기 열처리는 1000℃ 내지 1200℃로 행해지는 것이 바람직하다. 반응온도는 침규온도가 너무 낮아지면 침규속도가 기하급수적으로 감소하므로 1000℃ 이상이어야 하고, 1200℃를 초과하면 공업적으로 온도 조절이 어렵기 때문이다. 또한, 본 발명의 실시예에 따르면, 상기 혼합분말 중 금속불화물 분말의 함량은 상기 혼합분말 중 0.05중량% 내지 4.0 중량%인 것이 바람직하다. 금속불화물의 첨가량이 0.05중량%보다 적으면 침규속도가 너무 늦어지고, 불화마그네슘 함량이 증가하면 침규속도가 증가하다가 그 양이 4중량%를 넘어서면 일정하게 되기 때문이다.On the other hand, according to an embodiment of the present invention, the heat treatment is preferably performed at 1000 ℃ to 1200 ℃. The reaction temperature should be 1000 ° C or higher because the deposition rate decreases exponentially if the precipitation temperature is too low, and it is difficult to control the temperature industrially if it exceeds 1200 ° C. In addition, according to an embodiment of the present invention, the content of the metal fluoride powder in the mixed powder is preferably 0.05% to 4.0% by weight of the mixed powder. If the addition amount of the metal fluoride is less than 0.05% by weight, the sintering speed is too slow. If the magnesium fluoride content is increased, the sintering speed is increased, but the amount becomes constant when the amount exceeds 4% by weight.

본 발명에 따르면, 상기 수소 분위기에서 열처리하는 단계는 99.9% 이상의 순도를 갖는 수소 분위기에서 행해지는 것이 바람직하다. 불화마그네슘이 첨가되지 않은 순수한 SiO2만 사용하여 규소를 주입하는 경우에는 순도가 99.9999% 이상의 고순도의 고가인 수소를 사용하여야 한다. SiO2만을 사용할 경우 아래 식 (1)에서 우측으로의 진행 가능성을 열역학적인 측면에서 검토해 본다.According to the invention, the step of heat treatment in the hydrogen atmosphere is preferably carried out in a hydrogen atmosphere having a purity of 99.9% or more. In case of injecting silicon using pure SiO 2 without magnesium fluoride, expensive hydrogen having a high purity of 99.9999% or more should be used. In case of using only SiO 2 , the possibility of moving to the right side in Equation (1) below will be examined in terms of thermodynamics.

SiO2 + 2H2 = Si + 2H2O (1)SiO 2 + 2H 2 = Si + 2H 2 O (1)

Barin의 자료집에 (I. Barin, Thermochemical Data of Pure Substances Part I, VCH, Germany, 1989) 근거하면 1200-1700K 범위에서 이산화규소와 수증기의 형성 자유에너지는 다음 식으로 표현된다.Based on Barin's data sheet (I. Barin, Thermochemical Data of Pure Substances Part I, VCH, Germany, 1989), the free energy of silicon dioxide and water vapor formation in the 1200-1700K range is expressed by

Si + O2 = SiO2, ΔG0 SiO2 = -900.74 + 0.171 T (kJ) (2)Si + O 2 = SiO 2 , ΔG 0 SiO 2 = -900.74 + 0.171 T (kJ) (2)

H2 + 0.5O2 = H2O, ΔG0 H2O = -250.0 + 0.057 T (kJ) (3) H 2 + 0.5O 2 = H 2 O, ΔG 0 H2O = -250.0 + 0.057 T (kJ) (3)

식 (1)의 형성 자유에너지 변화는 400.74-0.057T(kJ)로 표현된다. 결국 식 (1)이 우측으로 반응이 진행되기 위한 조건식은 다음과 같음을 알 수 있다.The change in free energy of formation of equation (1) is expressed as 400.74-0.057T (kJ). As a result, it can be seen that the conditional expression for the reaction (1) to proceed to the right is as follows.

0 = 400,740 - 57 T + 2.303 * R * T log [PH2O/PH2]2 (4)0 = 400,740-57 T + 2.303 * R * T log [P H2O / P H2 ] 2 (4)

식 (4)를 정리하면,Summarizing Equation (4),

PH2O/PH2 = 10 1.49-10,465/T (5)P H2O / P H2 = 10 1.49-10,465 / T (5)

식 (5)로부터 PH2O/PH2의 값이 10-5이면, 즉, 수소가스의 순도가 약 5N 정도면, 1612K 이상이 되면 SiO2의 수소환원에 의해 Si를 생성시킬 수 있음을 알 수 있다. PH2O/PH2의 값이 10-6이면 1397K 이상, PH2O/PH2의 값이 10-7이면 1233K 이상, PH2O/PH2의 값이 10-8이면 1103K 이상으로 온도를 유지하면 Si의 생성이 가능하고 생성된 Si은 그 온도에서 저규소강판으로 확산하여 들어가게 되는 것이다.It can be seen from Equation (5) that Si can be formed by hydrogen reduction of SiO 2 when P H 2 O / P H 2 is 10 −5 , that is, when the purity of hydrogen gas is about 5N, or more than 1612 K. have. If the value of P H2O / P H2 is 10 -6 , 1397K or more; if the value of P H2O / P H2 is 10 -7 , 1233K or more; if the value of P H2O / P H2 is 10 -8, It is possible to produce and the resulting Si is diffused into the low silicon steel sheet at that temperature.

생성된 Si는 Fe와 반응하거나 Fe 기지 내로 확산하여 들어가게 되므로 Si의 활동도는 식(1)과 같이 순수한 상태의 1이 아니라 보다 저하되게 된다. 수소 환원에 의해 생성된 Si가 Fe와 반응하여 FeSi를 형성하는 중간 과정을 거친다고 가정한다면, FeSi의 형성 자유에너지는 -85,754 + 9.75 T (Joule)로 표현된다. 이를 고려하면 식 (5)는 식 (6)으로 표현된다.Since the generated Si reacts with Fe or diffuses into the Fe matrix, the activity of Si is lowered rather than 1 in a pure state as shown in Equation (1). Assuming that Si generated by hydrogen reduction goes through an intermediate process of reacting with Fe to form FeSi, the free energy of formation of FeSi is expressed as -85,754 + 9.75 T (Joule). In view of this, equation (5) is expressed by equation (6).

PH2O/PH2 = 10 1.234-8,225/T (6)P H2O / P H2 = 10 1.234-8,225 / T (6)

이 경우에 PH2O/PH2의 값이 10-5이면 1320K 이상이면 Si의 증착이 가능하게 된다. 즉, 순수한 Si이 생성될 때보다 조업 온도를 약 290℃이상 감소시킬 수 있다는 의미이다. PH2O/PH2의 값이 10-6이면 1137K(약 260℃ 온도 강하) 이상, PH2O/PH2의 값이 10-7이면 1000K 이상으로 온도를 유지하면 Si 원소의 생성이 가능하고 생성된 Si은 그 온도에서 저규소강판으로 확산하여 들어가게 된다.In this case, if the value of P H2O / P H2 is 10 -5, the deposition of Si becomes possible at 1320K or more. This means that the operating temperature can be reduced by about 290 ° C or more than when pure Si is produced. If the value of P H2O / P H2 is 10 -6 or more, 1137K (approximately 260 ° C temperature drop), and if the value of P H2O / P H2 is 10 -7 , the temperature can be maintained at 1000K or more, it is possible to generate Si element. Si diffuses into the low silicon steel sheet at that temperature.

SiO2에 금속불화물(MgF2)을 첨가하면, Si과 수소, 불소 원소를 포함하는 SiF4, SiF3, SiF2, SiF, SiHF3, SiH2F2, SiH3F, SiH4 등의 다양한 가스 형태의 화학종이 형성되고, 이들이 분말 혼합체 내에 존재하는 기공을 통해 저규소강판 표면으로 이동하여 그 표면에서 분해 반응이나 수소에 의한 환원에 의해 규소가 증착된다(윤진국, 변지영, 김재수, 최종술, “Mo의 pack siliconizing에 관한 열역학과 속도론적 연구”, 대한금속학회지, vol.36, No.1 (1998) pp. 59-69). 증착된 규소는 좀 더 긴 시간의 열처리 과정에서 확산 반응에 의해 강판 내부로까지 침투하여 고규소강판이 제조된다. 이 방법은 취급이 용이한 고체 분말을 사용하면서 Si을 포함한 가스종의 이동을 통해 보다 표면이 양호한 강판을 제조할 수 있는 큰 이점을 제공한다.When metal fluoride (MgF 2 ) is added to SiO 2 , SiF 4 , SiF 3 , SiF 2 , SiF, SiHF 3 , SiH 2 F 2 , SiH 3 F, SiH 4, etc. Gas species are formed, and they move to the surface of the low silicon steel sheet through the pores present in the powder mixture, and silicon is deposited on the surface by decomposition reaction or reduction by hydrogen (Yun Jin-kuk, Ji-young Byun, Jae-soo Kim, Choi Sul-sul, “ Thermodynamics and Kinetic Studies on Pack Siliconizing of Mo ”, Journal of the Korean Metal Society, vol.36, No.1 (1998) pp. 59-69). The deposited silicon penetrates into the inside of the steel sheet by the diffusion reaction in the heat treatment process for a longer time to produce a high silicon steel sheet. This method provides the great advantage of producing a better surface steel sheet through the movement of gas species including Si while using solid powders that are easy to handle.

예를 들어, SiO2-AlF3 혼합체가 저규소강판의 표면에 존재하도록 하고 주위를 수소 분위기로 유지하는 상황을 고려하면, AlF3의 존재 하에 SiO2의 수소에 의한 환원반응은 다음 식 (7)로 표현할 수 있다.For example, considering the situation where the SiO 2 -AlF 3 mixture is present on the surface of the low silicon steel sheet and maintains the surroundings in a hydrogen atmosphere, the reduction reaction of SiO 2 with hydrogen in the presence of AlF 3 is represented by the following equation (7). Can be expressed as

4SiO2(s) + 4AlF3(s) + 2H2(g) = Si(in Si Steel) + 2Al2O3(s) + 3SiF4(g) +2H2O(g) (7)4SiO 2 (s) + 4AlF 3 (s) + 2H 2 (g) = Si ( in Si Steel ) + 2Al 2 O 3 (s) + 3SiF 4 (g) + 2H 2 O (g) (7)

한편, 불화알루미늄(AlF3)은 1548K(1275℃)까지 고체상으로 존재하므로, 본 발명 실시시의 온도인 1273~1473K구간에서도 고체상으로 존재하나 그 증기압은 1300K에서는 14.4mbar, 1400K에서는 91mbar, 1500K에서는 441mbar로 제법 큰 값을 갖는다(I. Barin, Thermochemical Data of Pure Substances Part I, VCH, Germany, 1989). 여기서 식 (7)은 SiO2와 AlF3가 고체상-고체상 반응이 일어나는 것을 고려한 것이나, 그 온도에서 AlF3의 증기압이 커 고체상의 SiO2와 기상의 AlF3가 반응에 참여한다고 볼 수 있다. 고체상-고체상 반응은 두 물질이 접촉하는 지점에서만 반응이 일어기 때문에 반응속도가 느리게 되기 때문이다. 이에 근거하면 식 (7)은 식(8)로 표현될 수 있다.On the other hand, since aluminum fluoride (AlF 3 ) is present in the solid phase up to 1548 K (1275 ° C.), it is present in the solid phase even at a temperature of 1273 to 1473 K at the time of carrying out the present invention. It is quite large at 441 mbar (I. Barin, Thermochemical Data of Pure Substances Part I, VCH, Germany, 1989). Equation (7) considers that the solid phase-solid phase reaction between SiO 2 and AlF 3 takes place, but the vapor pressure of AlF 3 is high at that temperature, and it can be seen that the solid phase SiO 2 and AlF 3 in the gas phase participate in the reaction. Solid-solid reactions are slow because the reaction occurs only at the point of contact between the two materials. Based on this, equation (7) can be expressed by equation (8).

4SiO2(s) + 4AlF3(g) + 2H2(g) = Si(in Si Steel)+2Al2O3(s)+3SiF4(g)+2H2O(g) (8)4SiO 2 (s) + 4AlF 3 (g) + 2H 2 (g) = Si ( in Si Steel ) + 2Al 2 O 3 (s) + 3SiF 4 (g) + 2H 2 O (g) (8)

상기 식의 1400K에서의 표준상태에서의 Gibbs 자유에너지 변화는 +77,263 Joules로 계산된다(I. Barin, Thermochemical Data of Pure Substances Part I and Part II, VCH, Germany, 1989). 상기의 반응이 우측으로 진행될 조건을, 1400K에서는 AlF3의 증기압이 91mbar이고 수소 1 몰이 소모되면 SiF4 1.5 몰 및 H2O 1 몰이 생성된다는 전제하에 계산하면, 식 (8)은 수소농도가 96.8% 이상만 되면 된다는 것을 알 수 있다.The Gibbs free energy change at standard conditions at 1400K is calculated as +77,263 Joules (I. Barin, Thermochemical Data of Pure Substances Part I and Part II, VCH, Germany, 1989). The conditions under which the reaction proceeds to the right are calculated on the assumption that the vapor pressure of AlF 3 is 91 mbar at 1400 K and 1.5 mol of SiF 4 and 1 mol of H 2 O are produced when 1 mol of hydrogen is consumed. It can be seen that it is necessary to have more than%.

이상과 같이, 순수한 SiO2를 1400K에서 수소로 직접 환원하고자 하는 경우에는 99.9999% 정도의 고순도 수소가 필요하나, 금속불화물인 AlF3를 첨가하면 수소의 순도를 약 97%까지 하강시켜도 무방함을 알 수 있어, 금속불화물의 첨가가 공업적으로 매우 효과적임을 알 수 있는 것이다.As described above, when pure SiO 2 is directly reduced from 1400K to hydrogen, high purity hydrogen of about 99.9999% is required, but the addition of metal fluoride AlF 3 may reduce the purity of hydrogen to about 97%. It can be seen that the addition of metal fluoride is very effective industrially.

본 발명의 바람직한 실시예에 따르면, 상기 혼합분말은 Si 분말을 더 포함할 수 있으며, Si 분말의 함량은 상기 혼합분말 중 0.02 중량% 내지 2.0 중량%일 수 있다. 즉, Si 주입원으로 산화물 SiO2와 Si를 동시에 이용하는 SiO2-Si-금속불화물 분말 혼합체를 사용할 수 있는데, 이는 순수한 Si의 활동도는 1로, SiO2 내의 Si의 활동도 보다 커, Si을 함유한 다양한 화학종들의 분압이 단순히 SiO2만 사용했을 때 보다 SiO2-Si-MgF2 분말 혼합체를 사용했을 때 높아지기 때문이다. 이에 의해 Si을 함유한 가스종들의 저규소 강판 표면으로의 공급이 증대되어 침규속도가 증대되는 효과가 나타나게 된다. 순수한 Si를 사용하더라도 침규가 가능하나 고상의 규소 분말이 철판에 부착하여 표면의 조도가 거칠어지며, 순수한 Si에 소량의 MgF2를 첨가하는 방법으로 침규하여도 무방하나 이때에도 표면의 조도가 거칠어지는 문제점이 있으므로 SiO2-Si-금속불화물 분말 혼합체를 사용할 수 있는 것이다.According to a preferred embodiment of the present invention, the mixed powder may further include a Si powder, the content of the Si powder may be from 0.02% to 2.0% by weight of the mixed powder. That is, a SiO 2 -Si-metal fluoride powder mixture using oxides SiO 2 and Si at the same time as a Si source can be used. The pure Si has an activity of 1, which is greater than that of Si in SiO 2 This is because the partial pressures of the various species contained are higher when using SiO 2 -Si-MgF 2 powder mixtures than when only SiO 2 is used. This increases the supply of Si-containing gas species to the low silicon steel sheet surface, resulting in an increase in the deposition rate. Even if pure Si is used, it can be precipitated, but the solid silicon powder adheres to the iron plate, resulting in roughness of the surface, and it may be impregnated by adding a small amount of MgF 2 to pure Si. Since there is a problem, SiO 2 -Si-metal fluoride powder mixture can be used.

본 발명에 따른 SiO2-Si-금속불화물 혼합분말은 SiO2분말과 Si분말, 금속불화물 분말을 혼합하여 만든다. 다음으로, 혼합분말을 알루미나 등의 용기에 담고 혼합분말 내부에 저규소강을 접촉시킨다. 이를 수소분위기하에서 고온으로 상승시키면, 전술한 바와 같이 Si와 불소원소를 포함하는 SiF4, SiF3, SiF2, SiF, SiHF3, SiH2F2, SiH3F, SiH4 등의 다양한 화학종이 형성되고, 이는 혼합분말 내에 존재하는 기공을 통해 저규소강 표면으로 이동하게 되고 그 표면에서 분해반응이나 수소에 의한 환원에 의해 규소가 증착된다. The SiO 2 -Si-metal fluoride mixed powder according to the present invention is made by mixing SiO 2 powder, Si powder, and metal fluoride powder. Next, the mixed powder is placed in a container such as alumina and low silicon steel is brought into contact with the inside of the mixed powder. When it is raised to a high temperature under a hydrogen atmosphere, various chemical species such as SiF 4 , SiF 3 , SiF 2 , SiF, SiHF 3 , SiH 2 F 2 , SiH 3 F, and SiH 4 , which contain Si and fluorine, are described as described above. It is formed, which moves through the pores present in the mixed powder to the surface of the low silicon steel, and silicon is deposited on the surface by decomposition reaction or reduction by hydrogen.

본 발명에 따른 침규조성물인 SiO2-Si-MgF2 혼합체에서 Si의 함유량은 0.02중량%~2.0중량%가 바람직하다. Si를 2.0중량%를 초과하여 첨가하면 혼합분말 내의 Si분말과 저규소 강판과의 직접적인 접촉에 의해 제조되는 규소강판의 표면이 거칠어지는 문제가 있고, 0.02중량% 미만일 경우 침규속도의 증가효과가 없기 때문이다.The content of Si in the SiO 2 -Si-MgF 2 mixture, which is a siliceous composition according to the present invention, is preferably 0.02% by weight to 2.0% by weight. When Si is added in excess of 2.0% by weight, there is a problem that the surface of the silicon steel sheet produced by the direct contact between the Si powder and the low silicon steel sheet in the mixed powder has a problem, and when it is less than 0.02% by weight, there is no effect of increasing the deposition rate. Because.

본 발명의 다른 일 측면에 따른 고규소강판을 제조하는 방법은 분말형태의 SiO2, SiC 및 Si으로 이루어지는 군으로부터 선택되는 하나 이상의 규소주입원과, 규소함량이 4% 미만인 저규소강판을 준비하는 단계; 상기 규소주입원과 저규소강판 사이에 실드(shield)를 삽입하여 적층구조를 형성하는 단계; 및 상기 적층구조를 수소 분위기에서 열처리하는 단계로 구성된다. 상기와 같이 본 발명은 종래 기술의 문제점을 해결하기 위해 강판과의 반응성이 적은 매체를 강판과 분말 혼합체 사이에 삽입하여 서로 격리시키는 방법을 고안하였다. 이러한 매체를 본 명세서 내에서 실드(shield)라고 칭하였다. 일반적으로 세라믹은 철과의 반응성이 미약하므로 이들을 실드로써 사용하였다. 세라믹 직물(textile) 혹은 세라믹 페이퍼(paper)는 산화물을 섬유(fiber)나 위스커(whisker, 단결정으로 이루어진 섬유) 형태로 제조하여 직물 형태로 짜거나 종이 형태로 제조한 것이다. 이들은 기체가 통과할 수 있는 공간을 갖고 있고, 강판과의 반응성이 약한 특징이 있다. 따라서, 이러한 세라믹 직물 또는 세라믹 페이퍼는 Si을 포함한 가스 상(phase)의 이동을 이용하는 침규 방법에 있어서 원활한 통로 역할을 함과 동시에, 규소주입원과 강판을 격리시킴으로써 양호한 강판 상태를 유지할 수 있게 하는 역할을 한다. 이러한 실드로서의 역할을 하는 매체는 굳이 세라믹 직물 혹은 페이퍼가 아니라 기체가 통과할 수 있는 공간을 가지면서 강판 혹은 규소주입원과 반응성이 약한 매체이면 어느 것이나 사용이 가능하다.Method for producing a high silicon steel sheet according to another aspect of the present invention is to prepare a low silicon steel sheet having at least one silicon injection source selected from the group consisting of SiO 2 , SiC and Si in the form of powder, and silicon content less than 4% step; Inserting a shield between the silicon injection source and a low silicon steel sheet to form a laminated structure; And heat treating the laminated structure in a hydrogen atmosphere. As described above, the present invention has devised a method of isolating each other by inserting a medium having a low reactivity with the steel sheet between the steel sheet and the powder mixture to solve the problems of the prior art. Such media are referred to herein as shields. In general, ceramics have a weak reactivity with iron, so they were used as shields. Ceramics or ceramic papers are made of oxides in the form of fibers or whiskers, or woven into paper or paper. They have a space through which gas can pass and have a weak reactivity with steel sheets. Therefore, such a ceramic fabric or ceramic paper serves as a smooth passage in the immersion method using a gas phase movement including Si, and at the same time, isolates the silicon injection source and the steel sheet to maintain a good steel sheet state. Do it. The medium serving as a shield can be used as long as the medium is not ceramic cloth or paper, but has a space through which gas can pass, and is weak in reactivity with a steel sheet or a silicon injection source.

본 발명의 또 다른 일 측면은 도 3에서 볼 수 있는 바와 같이 규소주입원(1)을 저규소강판(2) 사이에 실드(shield)(3)와 함께 위치시켜 이를 수소 분위기 하에서 열처리하는 방법이다. 상황에 따라 도 3의 반복적 적층 이외에도 하나의 저규소강판과 양면 혹은 단면에 실드와 규소주입원을 위치시켜 단판 형태 혹은 긴 코일 형태의 연속적 공정으로 침규시키는 방법도 가능하다.Another aspect of the present invention is a method of heat-treating the silicon injection source 1 with the shield (3) between the low silicon steel sheet (2) as shown in FIG. . Depending on the situation, in addition to the repetitive lamination of FIG. 3, a method of placing a shield and a silicon injection source on one low silicon steel sheet and on both sides or a cross section may be used to infiltrate a continuous process in the form of a single plate or a long coil.

또한 본 발명의 바람직한 실시예에 따르면, 상기 실드는 SiO2를 포함하는 세라믹 직물 또는 세라믹 페이퍼이고, 상기 세라믹 직물 또는 세라믹 페이퍼에 분말 형태의 금속불화물이 살포 또는 슬러리 형태로 도포될 수 있다. 이 경우, 규소주입원은 불필요하다. 실드로서 SiO2를 포함한 세라믹 직물을 사용할 경우에는 그 자체가 규소주입원 역할을 하기 때문에 별도의 분말 형태의 규소주입원 없이도 침규가 가능한 것이다. 하지만, 이 경우에는 금속불화물을 함께 사용하여 공업적으로 신속하고 경제적으로 제조하는 것이 바람직하다. 또한, 금속불화물은 분말 형태인 경우 상기 실드에 적당량 뿌리거나 슬러리 형태로 도포하는 방법이 바람직하고, 금속불화물은 MgF2, AlF3 및 NaF로 이루어지는 군으로부터 선택된 어느 하나인 것이 바람직하다. 상술한 바와 같은 이유로, 적층구조를 수소 분위기에서 열처리하는 단계는 97% 이상의 순도를 갖는 수소 분위기에서 행해질 수 있다.In addition, according to a preferred embodiment of the present invention, the shield is a ceramic fabric or ceramic paper containing SiO 2 , the metal fluoride in powder form may be applied in the form of spray or slurry to the ceramic fabric or ceramic paper. In this case, the silicon injection source is unnecessary. In the case of using a ceramic fabric containing SiO 2 as the shield, since the silicon itself serves as a source of silicon, it is possible to settle without a separate powder source of silicon. In this case, however, it is desirable to manufacture the metal fluoride together in an industrially fast and economical manner. In addition, when the metal fluoride is in the form of powder, it is preferable to spray the shield in an appropriate amount or to apply it in the form of a slurry, and the metal fluoride is preferably any one selected from the group consisting of MgF 2 , AlF 3 and NaF. For the above reasons, the heat treatment of the laminated structure in a hydrogen atmosphere may be performed in a hydrogen atmosphere having a purity of 97% or more.

이하, 본 발명의 바람직한 실시예를 첨부도면을 참조하여 상세히 설명하기로 한다.Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

실시예 1 Example 1

순수한 SiO2 및 SiO2와 AlF3 1.0중량%(SiO2-AlF3 혼합분말 전체 중량 기준)를 혼합한 SiO2-AlF3 혼합분말 2종류를 규소원으로 사용하여 규소강판을 제조하였다. 99.9% 순도의 수소분위기 하에서 도 1에 나타낸 바와 같이 혼합분말(11)을 30ml 부피의 알루미나 도가니(12)에 담그고, 상기 분말 혼합체 속에 1cm x 1cm x 0.15mm 크기의 규소 함량이 3중량%인 규소강판(13)을 넣었다. 그 후, 도 1과 같은 상태로 상기 규소강판(13)을 인코넬 튜브 내에 위치시킨 뒤 가열하였다. 1100℃까지 승온 시킨 상태에서 10시간 동안 유지시킨 후, 노냉하여 시편의 무게변화를 측정하였다. 그 결과 AlF3가 첨가되지 않은 순수한 SiO2분말을 사용하였을 때에는 규소강판의 무게변화를 관찰할 수 없었으나, AlF3가 첨가된 SiO2-AlF3 혼합체를 사용하였을 때에는 규소강판의 무게변화가 있는 것을 관찰할 수 있었다. SiO2와 AlF3 1.0중량%의 혼합분말을 사용한 경우 규소강판의 무게가 2.7% 증가하였으며, 전자탐침 미세분석기(EPMA, Electron Probe Micro Analyzer)로 분석한 결과 제조된 규소강판에 포함된 규소 함량이 5.60중량% 임을 확인할 수 있었다. 즉, 99.9% 순도의 수소 분위기 하에서 AlF3를 첨가하지 않고 순수한 SiO2만을 규소원으로 사용하면 침규가 불가능하나, AlF3를 소량 첨가하면 침규가 가능한 것을 확인할 수 있었다.The pure SiO 2 and SiO 2 and AlF 3 1.0 wt% (SiO 2 -AlF 3 powder mixture total weight) to a mixture SiO 2 -AlF 3 powder mixture of two kinds of silicon steel sheet by using a silicon source was produced. As shown in FIG. 1 under a 99.9% purity hydrogen atmosphere, the mixed powder 11 was immersed in a 30 ml volume alumina crucible 12, and the silicon mixture having a size of 1 cm x 1 cm x 0.15 mm in silicon was 3% by weight. The steel plate 13 was put in. Thereafter, the silicon steel sheet 13 was placed in an Inconel tube and heated in the same state as shown in FIG. 1. After maintaining for 10 hours at a temperature up to 1100 ℃, the furnace was cooled to measure the weight change of the specimen. The result is when AlF 3 was used to pure SiO 2 powder is not added were not able to observe the weight changes of the silicon steel sheet, when the SiO 2 was used -AlF 3 mixture of the AlF 3 is added with a change in weight of the silicon steel sheet Could be observed. In case of using 1.0% by weight of SiO 2 and AlF 3 mixed powder, the weight of silicon steel sheet increased by 2.7%, and the silicon content contained in the manufactured silicon steel sheet was analyzed by the Electron Probe Micro Analyzer (EPMA). 5.60% by weight was confirmed. In other words, when pure SiO 2 was used as a silicon source without adding AlF 3 in a hydrogen atmosphere of 99.9% purity, it was confirmed that agitation was not possible, but a small amount of AlF 3 was added.

실시예 2 Example 2

규소함량이 3중량%인 규소강판 두 개를 도 2와 같이 위치를 변화시켜 실시예 1과 동일한 방법으로 규소강판을 제조하였다. 1cm x 1cm x 0.15mm 크기의 규소강판 중 하나(23a)를 SiO2와 AlF3 1.0중량%(SiO2-AlF3 혼합분말 전체 중량 기준)를 혼합한 혼합분말(21) 표면에 위치시켰다. 보다 상세하게는 AlF3와 규소강판이 직접 접촉할 수 없도록 SiO2와 AlF3 1.0중량%의 혼합분말 표면을 순수한 SiO2 분말로 한 층 덮은 뒤, 3중량% 규소강판을 SiO2 분말 위에 올려놓았다. 그리고 규소강판 중 다른 하나(23b)는 실시예 1과 같이 SiO2-AlF3 혼합분말(21)의 내부에 위치시킨 후, 99.9% 순도의 수소를 사용하여 1100℃에서 8시간 동안 침규 처리하였다. SiO2-AlF3 혼합분말 표면에 위치한 규소강판의 무게는 2.05% 증가하였으며, SiO2-AlF3 혼합분말 내부에 위치한 규소강판의 무게는 2.09% 증가한 것을 관찰할 수 있었다. 각각의 전자탐침미세분석기(EPMA) 분석결과 전자의 규소 농도는 5.10중량%, 후자의 규소 농도는 5.12중량% 였다. 상기 결과를 분석하면 SiO2-AlF3 혼합분말의 표면에 존재하는 규소강판에도 침규가 된다는 것을 알 수 있었으며, 규소강판이 혼합분말의 표면에 존재하는 경우와 내부에 존재하는 경우의 침규량에 차이가 거의 없다는 점에 비추어 볼 때, 침규반응은 기상의 AlF3를 통하여 일어난다는 것을 확인할 수 있었다.Two silicon steel sheets having a silicon content of 3% by weight were changed as shown in FIG. 2 to prepare silicon steel sheets in the same manner as in Example 1. One of the 1 cm x 1 cm x 0.15 mm silicon steel sheets (23a) was placed on the surface of the mixed powder 21 in which SiO 2 and 1.0% by weight of AlF 3 (based on the total weight of the SiO 2 -AlF 3 mixed powder) were mixed. More specifically, 1.0 wt% of the mixed powder of SiO 2 and AlF 3 was covered with pure SiO 2 powder so that the AlF 3 and the silicon steel sheet could not be directly contacted, and then the 3 wt% silicon steel sheet was placed on the SiO 2 powder. . The other one of the silicon steel sheets 23b was placed inside the SiO 2 -AlF 3 mixed powder 21 as in Example 1, and then subjected to a precipitation treatment for 8 hours at 1100 ° C. using 99.9% hydrogen. SiO 2 -AlF 3 increased weight is 2.05% of the silicon steel sheet in a mixed powder surface, the weight of the silicon steel sheet in the SiO 2 -AlF 3 powder mixture inside was able to observe that the increase of 2.09%. The results of the electron probe microanalysis (EPMA) analysis showed that the former silicon concentration was 5.10 wt% and the latter silicon concentration was 5.12 wt%. Analysis of the results showed that the silicon steel sheets present on the surface of the SiO 2 -AlF 3 mixed powder were also agglomerated, and the difference in the amount of precipitates when the silicon steel sheet was present on the surface of the mixed powder and when present inside. In view of the lack of, it can be seen that the agitation reaction occurs through AlF 3 in the gas phase.

실시예 3 Example 3

SiO2와 AlF3 1.0중량%(SiO2-AlF3 혼합분말 전체 중량 기준)를 혼합한 SiO2-AlF3 혼합분말을 이용하여 침규온도를 각각 1000℃, 1200℃로 하여 8시간 동안 침규하였다.Chimgyu to a temperature of 1000 ℃, 1200 ℃ respectively, using the SiO 2 and AlF 3 1.0 wt.% SiO 2 -AlF 3 powder mixture by mixing (SiO 2 -AlF 3 powder mixture total weight) were chimgyu for 8 hours.

침규온도를 1000℃로 한 경우에는 규소강판의 무게가 0.98% 증가하였으며, 1200℃로 한 경우에는 규소강판의 무게가 3.65% 증가한 것을 관찰할 수 있었다. 또한, 규소함량은 전자탐침미세분석기(EPMA)에 의한 분석결과 각각 4.03중량%, 6.55중량%임을 확인할 수 있었다.The weight of the silicon steel sheet increased 0.98% when the immersion temperature was set to 1000 ° C, and the weight of the silicon steel sheet increased by 3.65% when the temperature was set to 1200 ° C. In addition, the silicon content was found to be 4.03% by weight and 6.55% by weight, respectively, as a result of analysis by the electron probe microanalyzer (EPMA).

실시예 4 Example 4

SiO2-AlF3 혼합체에서 AlF3의 농도를 0.05 중량%, 0.25 중량%, 0.50 중량%, 1.00 중량%, 2.00 중량%, 3.00 중량%, 4.00 중량%로 변화시키면서 99.9% 순도의 수소를 이용하여 1100℃에서 8시간 동안 침규하였다. AlF3의 농도가 0.05 중량%, 0.25 중량%, 0.50 중량%, 1.00 중량%, 2.00 중량%, 3.00 중량%, 4.00 중량%일 때, 각각 규소강판의 무게가 0.80%, 1.31%, 1.52%, 2.09%, 2.54%, 3.45%, 3.40% 증가함을 관찰할 수 있었으며, 전자탐침미세분석기(EPMA)로 분석한 결과 각각의 규소함량은 3.87중량%, 4.42중량%, 4.58중량%, 5.12중량%, 5.65중량%, 6.48중량%, 6.46중량%임을 확인할 수 있었다.The concentration of AlF 3 in the SiO 2 -AlF 3 mixture was changed to 0.05%, 0.25%, 0.50%, 1.00%, 2.00%, 3.00%, 4.00% by weight with 99.9% purity hydrogen. It was settled for 8 hours at 1100 ° C. When the concentration of AlF 3 is 0.05 wt%, 0.25 wt%, 0.50 wt%, 1.00 wt%, 2.00 wt%, 3.00 wt%, 4.00 wt%, the weight of the silicon steel sheet is 0.80%, 1.31%, 1.52%, 2.09%, 2.54%, 3.45%, 3.40% increased, and the results of the analysis by the electron probe microanalyzer (EPMA) showed that the silicon content was 3.87%, 4.42%, 4.58%, 5.12% by weight. , 5.65% by weight, 6.48% by weight, it could be confirmed that the 6.46% by weight.

실시예 5 Example 5

이산화규소(SiO2)-불화마그네슘(MgF2) 혼합체가 규소원으로 작용하는지를 검증하기 위해 다음의 시험을 수행하였다. 순수한 SiO2와, SiO2 + 1.0중량% MgF2 혼합체 2종류를 규소원으로 사용하였다. 분말 혼합체를 부피 30ml 정도의 알루미나 도가니에 담그고 그 분말 속에 1㎝×1㎝×0.15㎜ 크기의 3% 규소강판을 넣는다. 그 상태로 인코넬 튜브(inconel tube) 내에 위치시키고 가열시켜 1100℃까지 승온시킨다. 분위기는 99.9% 순도의 수소를 사용하였다. 1100℃에서 6시간 유지시킨 후 노냉하여 시편의 무게변화를 측정하였다. 그 결과 MgF2가 첨가되지 않은 순수한 SiO2 분말을 사용하였을 때는 규소강판의 무게변화를 관찰할 수 없었다. 반면 MgF2가 첨가된 SiO2-MgF2 혼합체를 이용하였을 때는 무게변화를 관찰할 수 있었는데 SiO2 + 1.0중량% MgF2 혼합체에서는 규소강판의 1.2% 무게증가가 관찰되었다. 전자탐침미소분석기(EPMA; Electron Probe Micro Analyzer) 분석결과 4.3%의 규소를 함유한 규소강판이 얻어졌다.The following tests were conducted to verify that the silicon dioxide (SiO 2 ) -magnesium fluoride (MgF 2 ) mixture acts as a silicon source. Pure SiO 2 and two kinds of SiO 2 + 1.0 wt% MgF 2 mixtures were used as silicon sources. The powder mixture is immersed in an alumina crucible having a volume of about 30 ml, and 3% silicon steel sheet having a size of 1 cm × 1 cm × 0.15 mm is placed in the powder. In that state, it is placed in an inconel tube and heated to 1100 ° C. The atmosphere used hydrogen of 99.9% purity. After maintaining at 1100 ° C. for 6 hours, the furnace was cooled and the weight of the specimen was measured. As a result, when pure SiO 2 powder without MgF 2 was used, the weight change of the silicon steel sheet could not be observed. On the other hand, when the SiO 2 -MgF 2 mixture containing MgF 2 was used, the weight change was observed. In the SiO 2 + 1.0 wt% MgF 2 mixture, a 1.2% weight increase of the silicon steel sheet was observed. Electron Probe Micro Analyzer (EPMA) analysis showed a silicon steel sheet containing 4.3% silicon.

실시예 6 Example 6

실시예 5와 실험방법은 동일하나 11㎝×1㎝×0.15㎜ 크기의 3% 규소강판을 사용하였다. 혼합분말 내 MgF2의 함량을 질량백분율로 2%까지 증가시킨 것을 사용하고, 99.9%순도의 수소를 사용하여 1100℃에서 침규 처리하였다. 침규시간을 1시간, 4시간, 6시간, 14시간, 20시간으로 변화시키면서 시험한 결과 분말 내 존재했던 규소강판의 무게변화는 각기 0.8%, 1.6%, 1.9%, 2.8%, 3.2% 였고, 각각의 EPMA 규소분석치는 3.9%, 4.6%, 5.0%, 5.9%, 6.4%였다. 이상에서 침규량은 반응시간의 제곱근에 비례하여 증가함을 알 수 있다. 이는 Si을 함유한 가스종이 혼합분말의 기공을 통해 규소강판 표면으로 이동하는 기상확산이 반응율속임을 시사한다.Example 5 and the experimental method is the same, but 3% silicon steel sheet of 11 cm × 1 cm × 0.15 mm size was used. The content of MgF 2 in the mixed powder was increased to 2% by mass percentage, and 99.9% pure hydrogen was used to immerse at 1100 ° C. The weight change of the silicon steel sheets in the powder was 0.8%, 1.6%, 1.9%, 2.8%, 3.2%, respectively, when the immersion time was changed to 1 hour, 4 hours, 6 hours, 14 hours, 20 hours. Each EPMA silicon analysis was 3.9%, 4.6%, 5.0%, 5.9% and 6.4%. In the above it can be seen that the amount of precipitation increases in proportion to the square root of the reaction time. This suggests that the gas phase diffusion in which Si-containing gas species move to the surface of the silicon steel sheet through the pores of the mixed powder is a reaction rate.

실시예 7 Example 7

SiO2+Si+MgF2 혼합분말이 규소원으로 작용하는가를 검증하기 위해 다음의 시험을 수행하였다. SiO2 + 0.13중량% Si + 2.0중량% MgF2 혼합분말을 침규조성물로 사용하였다. 도 1과 같이 혼합분말(11)을 부피 30ml 정도의 알루미나 도가니(12)에 담그고 그 분말 속에 1㎝×1㎝×0.25㎜ 크기의 3% 규소강판(13)을 넣는다. 상기와 같은 상태로 인코넬 튜브 내에 위치시키고 가열시켜 1100℃까지 승온시키고, 99.9% 순도의 수소를 사용한다. 1100℃에서 6시간 유지시킨 후 노냉하여 시편의 무게변화를 측정한 결과 2.8%의 무게증가가 관찰되었고, EPMA(Electron Probe Micro Analyzer) 분석결과 5.9%의 규소를 함유한 규소강판을 얻을 수 있었다.The following tests were performed to verify that the SiO 2 + Si + MgF 2 mixed powder acts as a silicon source. SiO 2 + 0.13 wt% Si + 2.0 wt% MgF 2 mixed powder was used as the siliceous composition. As shown in FIG. 1, the mixed powder 11 is immersed in an alumina crucible 12 having a volume of about 30 ml, and a 3% silicon steel sheet 13 having a size of 1 cm × 1 cm × 0.25 mm is placed in the powder. Placed in the Inconel tube in the same state as above, heated to 1100 ° C., using 99.9% purity hydrogen. After maintaining for 6 hours at 1100 ℃, the weight change of the specimen was measured by blast furnace and the weight increase of 2.8% was observed. The EPMA (Electron Probe Micro Analyzer) analysis showed that silicon steel sheet containing 5.9% of silicon was obtained.

실시예 8 Example 8

상기 실시예 7과 실험방법은 동일하나 11㎝×1㎝×0.25㎜ 크기의 3% 규소강판을 사용하였다. 혼합분말 내 MgF2의 함량은 질량백분율로 2%로 고정하고, 99.9% 순도의 수소를 사용하여 1100℃에서 시간 침규처리하였다. 이 때, 침규조성물중 규소함량을 0%, 0.05%, 0.25%, 0.52%, 1.0%로 변화시켰다. 그 결과 규소강판의 무게변화는 각기 1.2%, 1.7%, 3.8%, 6.5%, 10.7%였고, 각각의 EPMA 규소 분석치는 4.2%, 4.8%, 6.7%, 9.2%, 12.8%였다. 본 실시예에서는 Si의 첨가량에 비례하여 침규량이 증가함을 알 수 있었다.Example 7 and the experimental method were the same, but a 3% silicon steel sheet having a size of 11 cm × 1 cm × 0.25 mm was used. The content of MgF 2 in the mixed powder was fixed at 2% by mass percentage and subjected to time immersion at 1100 ° C. using 99.9% purity hydrogen. At this time, the silicon content in the siliceous composition was changed to 0%, 0.05%, 0.25%, 0.52%, and 1.0%. As a result, the weight change of silicon steel sheet was 1.2%, 1.7%, 3.8%, 6.5%, and 10.7%, respectively, and the analysis of EPMA silicon was 4.2%, 4.8%, 6.7%, 9.2%, and 12.8%, respectively. In this embodiment, it was found that the amount of precipitates increased in proportion to the amount of Si added.

실시예 9Example 9

상기 실시예 8와 동일한 방법으로 실험을 행하였으며, 혼합분말 내 MgF2의 함량은 2중량%로, Si의 함량은 0.52중량%로 하였다. 99.9%순도의 수소를 사용하여 1100℃에서 침규 처리하였다. 이 때, 침규시간을 4시간, 6시간, 10시간 변화시키면서 시험한 결과 분말 내 존재했던 규소강판의 무게변화는 각기 3.1%, 3.8%, 4.2%였고, 각각의 EPMA 규소 분석치는 6.0%, 6.7%, 7.2%였다.The experiment was carried out in the same manner as in Example 8, the content of MgF 2 in the mixed powder was 2% by weight, the content of Si was 0.52% by weight. 99.5% pure hydrogen was used to immerse at 1100 ° C. At this time, the weight change of the silicon steel sheet in the powder was 3.1%, 3.8%, and 4.2%, respectively. The EPMA silicon analysis values were 6.0% and 6.7, respectively. %, 7.2%.

실시예 10 Example 10

SiO2 + 0.52중량% Si + 2.0중량% MgF2 혼합체를 이용한 침규에서 침규온도를 낮추어 1000℃에서 6시간 99.9%의 수소를 이용하여 침규하면 무게증가는 2.6%로, 순수한 Si가 첨가되지 않은 SiO2 + 2.0중량% MgF2 혼합분말을 이용하여 얻은 무게증가량 0.72%에 비해 약 3.5배 이상의 침규속도 증가가 있었다. SiO2+0.52중량% Si+2.0중량% MgF2 혼합체를 이용한 침규에서 침규온도를 더욱 낮추어 900℃에서 6시간 99.9%의 수소를 이용하여 침규하면 무게증가는 0.87%로 되어 Si의 첨가하지 않은 침규조성물에 비해 동일한 침규속도를 얻는데 100℃ 정도의 온도 저하가 가능함을 알 수 있었다.SiO 2 + 0.52 wt% Si + 2.0 wt% MgF 2 Mixture lowered the sintering temperature, and the weight increase was 2.6% when sintered at 1000 ℃ for 6 hours using 99.9% hydrogen. There was an increase in the settling rate of about 3.5 times more than the weight gain 0.72% obtained using 2 + 2.0 wt% MgF 2 mixed powder. In case of agitation using SiO 2 + 0.52% by weight Si + 2.0% by weight MgF 2 mixture, further lowering the agitation temperature and impregnating with 99.9% hydrogen for 6 hours at 900 ° C resulted in a weight gain of 0.87%. Compared with the composition, it was found that a temperature drop of about 100 ° C. was possible to obtain the same deposition rate.

실시예 11 Example 11

고규소강판의 제조방법에 실드를 적용하였을 경우 강판 표면 상태가 개선됨을 확인하기 위하여 이하와 같은 실험을 행하고, 각 침규 공정에 따른 강판 상태를 표면 조도 측정기로 측정하여 비교하였다. 두께 0.15 mm, 길이 12 cm, 폭 10 cm인 3% 규소강판 시편의 상, 하부를 폭 12 cm, 길이 14 cm, 두께 0.8 mm 실리카(SiO2)를 포함하는 세라믹 직물, 즉 실리카 직물((주)부일세이프텍)로 감싸고, SiO2+Si+MgF2 계, SiO2+AlF3 계 조건과 실리카(SiO2)를 포함하는 세라믹 직물이 없는 SiO2+Si+MgF2 계 조건에서 침규 공정을 진행하였다. 각 시편은 1200℃, 수소 분위기 하에서 열처리 후 노냉(furnace cooling)시켜 규소함량을 확인하였다. 도 4는 SiO2+Si+MgF2 계, SiO2+Si+MgF2 계(실드 없음) 및 SiO2+AlF3 계 조건에서 고규소강판 제조공정에 따른 강판 상태를 표면 조도 측정기로 측정한 결과를 나타내는 그래프이다. 도 4에서 볼 수 있는 바와 같이 규소 함량이 증가함에 따라 모든 경우의 표면 조도가 서서히 증가되는 결과를 확인하였다. 특히, SiO2+Si+MgF2 계로 침규한 경우, 실드를 사용하지 않아 규소주입원과 강판이 직접 맞닿은 경우 규소함량 6.2%인 강판의 표면 조도는 3% 상태에서의 표면 조도 대비 12배로 증가한 반면, 실리카(SiO2)를 포함하는 세라믹 직물을 실드로 사용하여 제조된 규소 함량 6.2%인 강판의 표면 조도는 3% 상태 대비 3배로 증가하여 비교적 양호한 표면 상태를 얻을 수 있었다. SiO2+AlF3 계에서도 실리카(SiO2)를 포함하는 세라믹 직물을 사용하여 규소함량 6%까지 침규시키면 표면 조도가 규소함량 3% 상태 대비 약 4배로 증가하여 상대적으로 강판의 표면상태가 양호함을 알 수 있었다.In order to confirm that the surface condition of the steel sheet is improved when the shield is applied to the manufacturing method of the high silicon steel sheet, the following experiment was performed, and the steel sheet state according to each of the precipitating processes was measured and compared with the surface roughness measuring instrument. The upper and lower portions of a 3% silicon steel specimen having a thickness of 0.15 mm, a length of 12 cm, and a width of 10 cm, the bottom of the ceramic fabric, i.e., a silica fabric comprising 12 cm wide, 14 cm long and 0.8 mm thick silica (SiO 2 ) Immersion process under the conditions of SiO 2 + Si + MgF 2 , SiO 2 + AlF 3 and SiO 2 + Si + MgF 2 without the ceramic fabric containing silica (SiO 2 ) Proceeded. Each specimen was heat treated in a hydrogen atmosphere at 1200 ° C., followed by furnace cooling to confirm silicon content. 4 is a surface roughness measurement result of the state of the steel sheet according to the manufacturing process of high silicon steel sheet under the conditions of SiO 2 + Si + MgF 2 system, SiO 2 + Si + MgF 2 system (without shield) and SiO 2 + AlF 3 system A graph representing. As shown in FIG. 4, the surface roughness of all cases was gradually increased as the silicon content was increased. Particularly, when the silicon dioxide is directly contacted with the steel sheet without the shield when the SiO 2 + Si + MgF 2 system is aerated, the surface roughness of the steel sheet with 6.2% of silicon increased by 12 times compared to the surface roughness at 3%. , The surface roughness of the steel sheet with a silicon content of 6.2% manufactured by using a ceramic fabric containing silica (SiO 2 ) as a shield increased three times compared to a 3% state, thereby obtaining a relatively good surface state. Even in SiO 2 + AlF 3 system, when the ceramic fabric containing silica (SiO 2 ) is used to immerse up to 6% of silicon, the surface roughness increases about 4 times compared to that of 3% of silicon. And it was found.

실시예 12 Example 12

실리카(SiO2)를 포함하는 세라믹 직물에 의한 침규 시 금속불화물의 효과를 확인하기 위해 다음과 같은 실험을 행하였다. 두께 0.15 mm, 길이 12 cm, 폭 10 cm인 3% 규소강판 시편의 양 면을 폭 12 cm, 길이 14 cm, 두께 0.8 mm 실리카(SiO2)를 포함하는 세라믹 직물, 즉 실리카 직물((주)부일세이프텍)로 감싸고 수소 분위기 하에서 1200℃에서 시간 별로 열처리한 후 노냉시켜 규소함량을 확인하였다. 실험결과, 도 5에서 볼 수 있듯이 규소주입원을 별도로 가하지 않고 단순히 실리카(SiO2)를 포함하는 세라믹 직물만 사용하더라도 표면상태가 양호한 고규소강판을 제조할 수가 있음을 알 수 있었다. 규소함량은 무게변화를 Si의 추가만으로 가정하고 계산한 것으로써, 22시간 만에 규소함량은 6.5%에 도달하여 시간당 약 0.16%씩 규소함량이 증가함을 알 수 있었다.In order to confirm the effect of the metal fluoride during the deposition of the ceramic fabric containing silica (SiO 2 ) was carried out as follows. A ceramic fabric, i.e., a silica fabric, comprising silica (SiO 2 ) having a width of 12 cm, a length of 14 cm, and a thickness of 0.8 mm, on both sides of a 3% silicon steel specimen of 0.15 mm thickness, 12 cm length, and 10 cm width. Buil safetech) was wrapped and heat-treated at 1200 ℃ for hours under hydrogen atmosphere to confirm the silicon content by the furnace cooling. As a result, as shown in FIG. 5, it was found that even when only a ceramic fabric including silica (SiO 2 ) was used without adding a silicon injection source, a high silicon steel sheet having a good surface state could be manufactured. The silicon content was calculated by assuming that the weight change was based on the addition of Si, and after 22 hours, the silicon content reached 6.5% and the silicon content increased by about 0.16% per hour.

또한, 상기 실험방법과 동일한 방법으로 실험을 하되, 시편 부근에 NaF 분말을 약 5 g 정도 배치한 후 침규하였다. 도 5는 시편 부근에 금속불화물로서 NaF 분말을 배치한 후 침규한 결과, NaF가 없는 경우에 비해 규소 함량이 더 증대되는 결과를 보여준다. 도 5에서 나타난 바와 같이 금속불화물이 없는 경우에 비해 규소 함량이 상대적으로 더 증대됨을 확인할 수 있었다.In addition, the experiment was carried out in the same manner as in the above experimental method, but after placing about 5 g of NaF powder in the vicinity of the specimen was settled. FIG. 5 shows that after the NaF powder is placed as a metal fluoride in the vicinity of the specimen, the silicon content is increased as compared with the case without NaF. As shown in FIG. 5, it was confirmed that the silicon content was relatively increased as compared with the case without the metal fluoride.

이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시 양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.The specific parts of the present invention have been described in detail above, and it is apparent to those skilled in the art that such specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. something to do. Therefore, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (23)

규소주입원과 금속불화물 분말을 혼합하여 혼합분말을 생성하는 단계;Mixing the silicon injection source and the metal fluoride powder to produce a mixed powder; 상기 혼합분말에 규소 함량이 4중량% 미만인 저규소강판을 접촉시키는 단계; 및Contacting the mixed powder with a low silicon steel sheet having a silicon content of less than 4% by weight; And 상기 혼합분말에 접촉된 상태의 저규소강판을 수소분위기에서 열처리하는 단계;Heat-treating the low silicon steel sheet in contact with the mixed powder in a hydrogen atmosphere; 를 포함하는 고규소강판의 제조방법.Method for producing a high silicon steel sheet comprising a. 제1항에 있어서,The method of claim 1, 상기 규소주입원은 SiO2 분말인 것을 특징으로 하는 고규소강판의 제조방법.The silicon injection source is a method for producing a high silicon steel sheet, characterized in that the SiO 2 powder. 제1항에 있어서,The method of claim 1, 상기 혼합분말은 Si 분말을 더 포함하는 것을 특징으로 하는 고규소강판의 제조방법.The mixed powder is a manufacturing method of high silicon steel sheet, characterized in that it further comprises a Si powder. 제3항에 있어서,The method of claim 3, 상기 혼합분말 중 Si 분말의 함량은 상기 혼합분말 중 0.02 중량% 내지 2.0 중량%인 것을 특징으로 하는 고규소강판의 제조방법.The content of Si powder in the mixed powder is a method for producing a high silicon steel sheet, characterized in that from 0.02% to 2.0% by weight of the mixed powder. 제1항에 있어서,The method of claim 1, 상기 금속불화물 분말은 MgF2 또는 AlF3 분말인 것을 특징으로 하는 고규소강판의 제조방법.The metal fluoride powder is MgF 2 or AlF 3 powder manufacturing method of high silicon steel, characterized in that the powder. 제1항에 있어서,The method of claim 1, 상기 혼합분말 중 금속불화물 분말의 함량은 상기 혼합분말 중 0.05중량% 내지 4.0 중량%인 것을 특징으로 하는 고규소강판의 제조방법.The content of the metal fluoride powder in the mixed powder is a method for producing a high silicon steel sheet, characterized in that 0.05% to 4.0% by weight of the mixed powder. 제1항에 있어서,The method of claim 1, 상기 열처리는 1000℃ 내지 1200℃로 행해지는 것을 특징으로 고규소강판의 제조방법.The heat treatment is carried out at 1000 ℃ to 1200 ℃ manufacturing method of high silicon steel sheet. 제1항에 있어서,The method of claim 1, 상기 수소 분위기에서 열처리하는 단계는 99.9% 이상의 순도를 갖는 수소 분위기에서 행해지는 것을 특징으로 하는 고규소강판의 제조방법.The step of heat treatment in the hydrogen atmosphere is a method of manufacturing a high silicon steel sheet, characterized in that the hydrogen atmosphere having a purity of 99.9% or more. 규소주입원을 준비하는 단계;Preparing a silicon infusion source; 상기 규소주입원에 실드가 적층된 규소 함량이 4중량% 미만인 저규소강판을 접촉시키는 단계; 및Contacting the silicon injection source with a low silicon steel sheet having a shielded silicon content of less than 4% by weight; And 상기 규소주입원에 접촉된 상태의 저규소강판을 수소분위기에서 열처리하는 단계;Heat-treating the low silicon steel sheet in contact with the silicon injection source in a hydrogen atmosphere; 를 포함하는 고규소강판의 제조방법.Method for producing a high silicon steel sheet comprising a. 제9항에 있어서, The method of claim 9, 상기 규소주입원은 규소주입원에 금속불화물 분말을 혼합한 혼합분말인 것을 특징으로 하는 고규소강판의 제조방법.The silicon injection source is a method for producing a high silicon steel sheet, characterized in that the powder mixed with a metal fluoride powder in the silicon injection source. 제9항에 있어서,The method of claim 9, 상기 규소주입원은 SiO2, SiC 및 Si 분말로 이루어지는 군으로부터 선택되는 하나 이상인 것을 특징으로 하는 고규소강판의 제조방법.The silicon injection source is a method for producing a high silicon steel sheet, characterized in that at least one selected from the group consisting of SiO 2 , SiC and Si powder. 제9항에 있어서,The method of claim 9, 상기 실드는 세라믹 직물 또는 세라믹 페이퍼인 것을 특징으로 하는 고규소강판의 제조방법.The shield is a method of manufacturing a high silicon steel sheet, characterized in that the ceramic fabric or ceramic paper. 제9항에 있어서,The method of claim 9, 상기 금속불화물은 MgF2, AlF3 및 NaF로 이루어지는 군으로부터 선택된 어느 하나인 것을 특징으로 하는 고규소강판의 제조방법.The metal fluoride is a method for producing a high silicon steel sheet, characterized in that any one selected from the group consisting of MgF 2 , AlF 3 and NaF. 제9항에 있어서,The method of claim 9, 상기 수소 분위기에서 열처리하는 단계는 97% 이상의 순도를 갖는 수소 분위기에서 행해지는 것을 특징으로 하는 양호한 표면상태를 가지는 고규소강판의 제조방법.The heat treatment in the hydrogen atmosphere is a method for producing a high silicon steel sheet having a good surface state, characterized in that carried out in a hydrogen atmosphere having a purity of 97% or more. 금속불화물 분말을 준비하는 단계;Preparing a metal fluoride powder; 상기 금속불화물 분말에 SiO2를 포함한 실드가 적층된 규소 함량이 4중량% 미만인 저규소강판을 접촉시키는 단계; 및Contacting the metal fluoride powder with a low silicon steel sheet having a silicon content of less than 4% by weight in which a shield including SiO 2 is laminated; And 상기 혼합분말에 접촉된 상태의 저규소강판을 수소분위기에서 열처리하는 단계;Heat-treating the low silicon steel sheet in contact with the mixed powder in a hydrogen atmosphere; 를 포함하는 고규소강판의 제조방법.Method for producing a high silicon steel sheet comprising a. 제15항에 있어서,The method of claim 15, 상기 실드는 SiO2를 포함한 세라믹 직물 또는 세라믹 페이퍼인 것을 특징으로 하는 고규소강판의 제조방법.The shield is a method of manufacturing a high silicon steel sheet, characterized in that the ceramic fabric or ceramic paper containing SiO 2 . 제15항에 있어서,The method of claim 15, 상기 금속불화물은 MgF2, AlF3 및 NaF로 이루어지는 군으로부터 선택된 어느 하나인 것을 특징으로 하는 고규소강판의 제조방법.The metal fluoride is a method for producing a high silicon steel sheet, characterized in that any one selected from the group consisting of MgF 2 , AlF 3 and NaF. 제15항에 있어서,The method of claim 15, 상기 수소 분위기에서 열처리하는 단계는 97% 이상의 순도를 갖는 수소 분위기에서 행해지는 것을 특징으로 하는 양호한 표면상태를 가지는 고규소강판의 제조방법.The heat treatment in the hydrogen atmosphere is a method for producing a high silicon steel sheet having a good surface state, characterized in that carried out in a hydrogen atmosphere having a purity of 97% or more. 제1항 내지 제18항 중 어느 한 항의 방법으로 제조된 고규소강판.A high silicon steel sheet produced by the method of any one of claims 1 to 18. 규소 함량이 4중량% 미만인 저규소강판을 이용하여 고규소강판을 제조시 적용하는 SiO2 및, AlF3 또는 MgF2 분말의 혼합체로 구성된 침규 조성물.An agglomeration composition composed of a mixture of SiO 2 and AlF 3 or MgF 2 powder applied when manufacturing a high silicon steel sheet using a low silicon steel sheet having a silicon content of less than 4% by weight. 제20항에 있어서,The method of claim 20, 상기 분말 혼합체는 Si 분말을 더 포함하는 것을 특징으로 하는 침규 조성물.Said powder mixture further comprises Si powder. 제20항 또는 제21항에 있어서,The method of claim 20 or 21, 상기 AlF3 또는 MgF2 분말의 함량은 상기 혼합분말 중 0.05중량% 내지 4.0 중량%인 것을 특징으로 하는 침규 조성물.The content of the AlF 3 or MgF 2 powder is an acupuncture composition, characterized in that 0.05% to 4.0% by weight of the mixed powder. 제21항에 있어서, The method of claim 21, 상기 Si 분말의 함량은 상기 혼합분말 중 0.02중량% 내지 2.0 중량%인 것을 특징으로 하는 침규 조성물.The content of the Si powder is a precipitating composition, characterized in that 0.02% to 2.0% by weight of the mixed powder.
PCT/KR2010/001828 2009-10-30 2010-03-25 High-silicon steel sheet production method and high-silicon steel sheet produced using the same Ceased WO2011052858A1 (en)

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KR1020090130395A KR101150336B1 (en) 2009-12-24 2009-12-24 Siliconizing powder of SiO2, Si and MgF2 and method for producing high silicon steel
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5200145A (en) * 1987-06-08 1993-04-06 Exxon Research And Engineering Co. Electrical steels and method for producing same
JPH10147856A (en) * 1996-11-15 1998-06-02 Nkk Corp Continuous siliconizing equipment for steel strip
US6387194B1 (en) * 2001-02-20 2002-05-14 Mcdermott Technology, Inc Process and composition for chromizing 400-series stainless steels
KR20040041774A (en) * 2002-11-11 2004-05-20 주식회사 포스코 Coating composition and, method for manufacturing high silicon grain-oriented electrical steel sheet with superior core loss property using thereof
KR20040046401A (en) * 2002-11-27 2004-06-05 주식회사 포스코 Coating composition with superior powder coating and surface properties

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5200145A (en) * 1987-06-08 1993-04-06 Exxon Research And Engineering Co. Electrical steels and method for producing same
JPH10147856A (en) * 1996-11-15 1998-06-02 Nkk Corp Continuous siliconizing equipment for steel strip
US6387194B1 (en) * 2001-02-20 2002-05-14 Mcdermott Technology, Inc Process and composition for chromizing 400-series stainless steels
KR20040041774A (en) * 2002-11-11 2004-05-20 주식회사 포스코 Coating composition and, method for manufacturing high silicon grain-oriented electrical steel sheet with superior core loss property using thereof
KR20040046401A (en) * 2002-11-27 2004-06-05 주식회사 포스코 Coating composition with superior powder coating and surface properties

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