WO2016035345A1 - 方向性電磁鋼板の製造方法および窒化処理設備 - Google Patents
方向性電磁鋼板の製造方法および窒化処理設備 Download PDFInfo
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- WO2016035345A1 WO2016035345A1 PCT/JP2015/004503 JP2015004503W WO2016035345A1 WO 2016035345 A1 WO2016035345 A1 WO 2016035345A1 JP 2015004503 W JP2015004503 W JP 2015004503W WO 2016035345 A1 WO2016035345 A1 WO 2016035345A1
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- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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Definitions
- the present invention relates to a method for producing a grain-oriented electrical steel sheet capable of obtaining a grain-oriented electrical steel sheet having excellent magnetic properties at low cost, and a nitriding treatment facility used therefor.
- a grain-oriented electrical steel sheet is a soft magnetic material mainly used as a core material of a transformer and has a crystal structure in which the ⁇ 001> orientation, which is the easy axis of iron, is highly aligned in the rolling direction of the steel sheet.
- Such a texture preferentially causes grains of the [110] ⁇ 001> orientation, which is so-called Goss orientation, during secondary recrystallization annealing during the production process of grain-oriented electrical steel sheets. It is formed through secondary recrystallization that grows hugely.
- such grain-oriented electrical steel sheets have been manufactured by the following procedure. That is, a slab containing about 4.5 mass% or less of Si and an inhibitor component such as MnS, MnSe, and AlN is heated to 1300 ° C. or higher to temporarily dissolve the inhibitor component. Next, the slab in which the inhibitor component is dissolved is hot-rolled, and if necessary, hot-rolled sheet annealing is performed to obtain a final sheet thickness by one or more cold rollings sandwiching intermediate annealing. Further, the cold-rolled sheet having the final thickness is subjected to primary recrystallization tempering in a wet hydrogen atmosphere to perform primary recrystallization and decarburization.
- an inhibitor component such as MnS, MnSe, and AlN
- an annealing separator containing magnesia (MgO) as the main agent is applied to the cold-rolled plate after the primary recrystallization and decarburization, and then the secondary recrystallization and the inhibitor components are purified.
- the final finishing annealing is performed at 1200 ° C. for about 5 hours (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3).
- This (Al, Si) N is finely dispersed in the steel and functions effectively as an inhibitor.
- Non-Patent Document 1 it is explained as follows. That is, in the above-described conventional method for producing a grain-oriented electrical steel sheet, a precipitate (Si 3 N 4 or (Si, Mn) N) mainly composed of silicon nitride is present in the vicinity of the surface of the steel sheet after nitriding treatment. Forming. In the subsequent secondary recrystallization annealing, the precipitate mainly composed of silicon nitride changes to Al-containing nitride ((Al, Si) N or AlN) which is more thermodynamically stable.
- Patent Document 5 proposes a method of performing nitriding at a higher temperature after recrystallization at a slightly lower temperature in a nitriding atmosphere. This method is aimed at suppressing the growth of primary recrystallized grains in the material before nitriding, and by this, the primary recrystallized grain size can be controlled appropriately and a structure suitable for secondary recrystallization can be realized. I can do it.
- Patent Document 6 proposes a method in which only primary recrystallization is performed at a slightly high temperature and then nitriding is performed at a lower temperature. By adopting this method, nitrogen can be uniformly distributed in the thickness direction.
- Patent Documents 5 and 6 both contain Ti and Cu as essential elements, but are added for the purpose of obtaining good characteristics by uniformly depositing nitride after nitriding.
- the texture inherits the characteristics of the structure from the previous process. That is, the columnar crystals that are crystal forms at the time of slabs and the textures that start with equiaxed crystals are in the thickness direction, such as the vicinity of the surface that undergoes shear deformation due to roll friction and the center that undergoes simple compression deformation during hot rolling. It tends to be a different texture.
- the steel sheet surface is rubbed with the roll in the hot rolling and cold rolling processes, and receives a strong shear stress, so that a randomized structure may be formed. For this reason, when secondary recrystallization occurs from the surface of the steel sheet, good magnetic properties may not be obtained because the characteristics of the structure subjected to shear deformation due to roll friction are inherited.
- the present invention has been developed in view of the above-described present situation. That is, by controlling the precipitation of AlN in the steel, forming a uniform texture in the plate thickness direction, and developing secondary recrystallization with a good orientation in the steel plate, the directionality with excellent magnetic properties It aims at providing the manufacturing method of the grain-oriented electrical steel plate from which an electrical steel plate is obtained, and a suitable nitriding equipment used for the method.
- nitride is not uniformly deposited in the thickness direction of the steel plate to exhibit the inhibition effect, but rather the amount of nitride precipitate on the steel plate surface is increased. And, compared with the central part, we thought that the characteristics of the steel sheet would be stabilized if secondary recrystallization was not generated from the structure of the steel sheet surface by applying a strong grain growth inhibiting force to the steel sheet surface. It is.
- nitride has a temperature suitable for precipitation.
- nitride has a temperature suitable for precipitation.
- AlN is suitable for precipitation near 900 ° C
- Si 3 N 4 is near 700 ° C
- iron nitride is suitable for precipitation near 500 ° C. It has been.
- Non-Patent Document 1 nitriding of grain-oriented electrical steel sheets is often performed at around 750 ° C. This is because a temperature suitable for deposition of Si 3 N 4, the Si 3 N 4 is deposited on the steel sheet after nitriding treatment is described in Non-Patent Document 1.
- the precipitation of Si 3 N 4 at this time is not uniform in the plate thickness direction, but is the most in the vicinity of the steel plate surface, and almost exists between the surface and 1/4 thickness.
- Si 3 N 4 starts to precipitate. You can't go around.
- the inventors first recalled that the steel sheet was nitrided at a temperature suitable for AlN precipitation. However, when AlN precipitation occurs only in the vicinity of the surface of the steel sheet, nitrogen does not diffuse to the center layer of the steel sheet, and there is no nitride at the center of the sheet thickness. And since the grain growth inhibitory force cannot be obtained in a steel plate center part, it was assumed that it was not a state suitable for a grain-oriented electrical steel plate.
- the inventors first performed nitriding of the steel sheet at a temperature suitable for AlN precipitation, and once promoted AlN precipitation near the surface of the steel sheet, the temperature was suitable for Si 3 N 4 precipitation. Recalling that the temperature was lowered and further nitriding was performed, an experiment was attempted.
- the gist configuration of the present invention is as follows. 1. In mass%, C: 0.10% or less, Si: 1.0 to 5.0%, Mn: 0.01 to 0.5%, one or two selected from S and Se: 0.002 to 0.040% in total, sol.Al: 0.01
- the component composition is further mass%, Ni: 0.005 to 1.50%, Sn: 0.01 to 0.50%, Sb: 0.005-0.50%, Cu: 0.01-0.50%, Cr: 0.01 to 1.50%, P: 0.0050 to 0.50% Nb: 0.0005-0.0100%, Mo: 0.01-0.50% Ti: 0.0005-0.0100%, B: 0.0001-0.0100% and Bi: 0.0005-0.0100% 2.
- the present invention by first depositing a large amount of AlN precipitates in the vicinity of the surface of the steel sheet, it is possible to suppress deterioration of the steel sheet characteristics due to the occurrence of secondary recrystallization from the structure near the surface.
- precipitation of AlN near the center of the steel plate thickness can be increased by depositing a large amount of AlN precipitates in the vicinity of the steel plate surface. Therefore, it is possible to produce a grain-oriented electrical steel sheet that exhibits suitable secondary recrystallization even in the vicinity of the center of the steel sheet thickness and that has industrially stable and good characteristics.
- FIG. 1 is a photograph showing an SEM observation image of a cross section in the direction perpendicular to the rolling direction of a steel sheet after nitriding formed under condition 3 of the example.
- (b) and (c) are graphs showing the results of analyzing the structure of the designated portion of the SEM observation image by EDX (energy dispersive X-ray analysis).
- C 0.10% or less C is an element useful for improving the primary recrystallized texture. However, if the content exceeds 0.10%, the primary recrystallized texture is deteriorated. Was limited to 0.10% or less. From the viewpoint of magnetic properties, the desirable content of C is in the range of 0.01 to 0.08%. If the required magnetic property level is not so high, C may be set to 0.01% or less and 0.0005% or more in order to omit or simplify decarburization in the primary recrystallization annealing.
- Si 1.0-5.0% Si is a useful element that improves iron loss by increasing electrical resistance. However, if the content exceeds 5.0%, the cold rolling property deteriorates significantly, so Si was limited to 5.0% or less. Further, since Si needs to function as a nitride forming element, it is necessary to contain 1.0% or more. Further, from the viewpoint of achieving both iron loss characteristics and cold rollability, the desirable Si content is in the range of 1.5 to 4.5%.
- Mn 0.01-0.5% Mn has the effect of improving the hot workability at the time of production, but the effect is poor at 0.01% or less.
- the content exceeds 0.5%, the primary recrystallization texture deteriorates and the magnetic properties are deteriorated, so the content is limited to 0.5% or less.
- Total of one or two selected from S and Se 0.002 to 0.040%
- S and Se are useful components that combine with Mn and Cu to form MnSe, MnS, Cu 2-x Se, and Cu 2-x S, and exhibit the action of an inhibitor as a dispersed second phase in steel. If the total content of S and Se is less than 0.002%, the effect of addition is poor. On the other hand, if the total content of S and Se exceeds 0.040%, not only is the solid solution during slab heating incomplete, but it also causes defects on the product surface. Therefore, S and Se are limited to a total range of 0.002 to 0.040% in the case of single addition or combined addition.
- Al is a useful component that forms an AlN in the steel and acts as an inhibitor as a dispersed second phase.
- the content is less than 0.01%, a sufficient precipitation amount cannot be secured.
- the Al content exceeds 0.08%, the amount of AlN precipitated after nitriding of the steel sheet becomes excessive, so that the ability to suppress grain growth becomes too high and secondary recrystallization does not occur even when annealed to a high temperature.
- N 0.0010-0.020%
- N is a component necessary for forming AlN as well as Al. Nitrogen necessary as an inhibitor during secondary recrystallization can be supplied by nitriding in a later step. However, if the content is less than 0.0010%, crystal grain growth in the annealing process up to the nitriding process becomes excessive, which may cause grain boundary cracking in the cold rolling process. On the other hand, if N is added in excess of 0.020%, the steel sheet bulges during slab heating. Therefore, the addition of N is limited to the range of 0.0010 to 0.020%.
- sol.Al and N are used for nitriding, and additionally using the additionally formed AlN as an inhibitor, 0.01% or more of sol.Al is contained, and N is 14/14 of sol.Al. It is preferable to control the amount to less than 26.98. This is because AlN can be newly deposited by nitriding.
- the essential component in a slab was demonstrated, in the present invention, the following elements can be appropriately contained as a component that improves the magnetic properties more stably industrially.
- the balance of the steel slab component is Fe and inevitable impurities.
- the rolling process is hindered due to inclusions such as coarse oxides, and the primary recrystallized structure becomes uneven or formed. It is desirable to suppress the inclusions to less than 50 ppm because the inclusions themselves deteriorate the magnetic properties.
- Ni 0.005 to 1.50%
- Ni has a function of improving magnetic properties by increasing the uniformity of the hot-rolled sheet structure. Therefore, it is preferable to contain 0.005% or more.
- Ni content exceeds 1.50%, secondary recrystallization becomes difficult and the magnetic properties deteriorate. Therefore, Ni is desirably contained in the range of 0.005 to 1.50%.
- Sn 0.01-0.50%
- Sn is a useful element that suppresses nitriding and oxidation of a steel sheet during secondary recrystallization annealing, promotes secondary recrystallization of crystal grains having a good crystal orientation, and improves magnetic properties. Therefore, Sn is preferably contained in an amount of 0.01% or more, but if it exceeds 0.50%, the cold rolling property is deteriorated. Therefore, it is desirable to contain Sn in the range of 0.01 to 0.50%.
- Sb 0.005-0.50%
- Sb is a useful element that effectively suppresses nitriding and oxidation of a steel sheet during secondary recrystallization annealing, promotes secondary recrystallization of crystal grains having a good crystal orientation, and effectively improves magnetic properties.
- Sb is preferably contained in an amount of 0.005% or more, but if it exceeds 0.50%, the cold rolling property deteriorates. Accordingly, Sb is preferably contained in the range of 0.005 to 0.50%.
- Cu 0.01-0.50%
- Cu functions to suppress the oxidation of the steel sheet during the secondary recrystallization annealing, promote the secondary recrystallization of crystal grains having a good crystal orientation, and effectively improve the magnetic properties.
- the content exceeds 0.50% the hot rolling property is deteriorated, so it is desirable to contain Cu in the range of 0.01 to 0.50%.
- Cr 0.01 to 1.50% Cr has a function of stabilizing the formation of the forsterite film, and for that purpose, it is preferable to contain 0.01% or more. On the other hand, if the content exceeds 1.50%, secondary recrystallization becomes difficult and the magnetic properties deteriorate, so Cr is desirably contained in the range of 0.01 to 1.50%.
- P 0.0050-0.50%
- P has a function of stabilizing the formation of the forsterite film.
- P is preferably contained in an amount of 0.0050% or more.
- P is preferably contained in the range of 0.0050 to 0.50%.
- Nb: 0.0005-0.0100%, Mo: 0.01-0.50% Nb and Mo have an effect of suppressing sag after hot rolling through suppression of cracking due to temperature change during slab heating.
- Nb and Mo are not contained in the above lower limit or more, the effect of suppressing hege is small.
- the above upper limit is exceeded, iron loss is deteriorated when a carbide or nitride is formed to remain in the final product. Therefore, it is desirable to add Nb and Mo within the above range.
- the steel slab adjusted to the above preferable component composition range is subjected to hot rolling without being reheated or after being reheated.
- the reheating temperature is preferably about 1000 ° C. or higher and 1300 ° C. or lower.
- the nitriding treatment is performed before the secondary recrystallization annealing and the inhibitor is reinforced, fine dispersion of precipitates by complete solid solution is not necessarily required in the hot rolling process. Therefore, implementation of ultra-high temperature slab heating exceeding 1300 ° C. is not suitable for the present invention.
- the reheating temperature is desirably 1000 ° C. or higher.
- the hot-rolled sheet after hot rolling is subjected to hot-rolled sheet annealing as necessary, and then subjected to one cold rolling or two or more cold rollings sandwiching the intermediate annealing, and the final cold A rolled plate is used.
- This cold rolling may be performed at normal temperature, or may be warm rolling in which the steel sheet temperature is raised to a temperature higher than normal temperature, for example, about 250 ° C.
- the primary cold-rolled sheet is subjected to primary recrystallization annealing.
- the purpose of this primary recrystallization annealing is to adjust the primary recrystallization grain size optimal for secondary recrystallization by primary recrystallization of a cold rolled sheet having a rolled structure.
- the annealing atmosphere at this time is preferably a wet hydrogen nitrogen or wet hydrogen argon atmosphere.
- the heating rate between 500 ° C. and 700 ° C. to 50 ° C./s or more from the viewpoint of improving the texture of the steel sheet.
- the upper limit of the heating rate between 500 and 700 ° C. is not particularly limited, but is about 400 ° C./s from the viewpoint of equipment.
- the target temperature range during the primary recrystallization annealing is for the purpose of rapidly heating the steel sheet within the temperature range corresponding to the recovery of the structure after cold rolling, and recrystallizing the steel sheet structure. Therefore, the temperature range corresponds to tissue recovery.
- the rate of temperature increase in the temperature range is preferably 50 ° C./s or more, because if the rate of temperature increase is less than 50 ° C./s, tissue recovery at the temperature cannot be sufficiently suppressed. is there.
- nitriding is performed during the primary recrystallization annealing, after the primary recrystallization annealing, or after the primary recrystallization annealing.
- a temperature suitable for AlN precipitation specifically, 850 ° C. or higher
- the temperature is lowered to a temperature lower than 850 ° C. suitable for Si 3 N 4 precipitation or iron nitride precipitation. It is most important to perform nitriding treatment.
- high temperature nitriding is performed at a temperature suitable for precipitation of AlN.
- nitrogen supplied by nitriding penetrates into the steel and simultaneously precipitates as AlN.
- nitrogen precipitates immediately after nitrogen enters the steel precipitation occurs only near the surface of the plate thickness.
- AlN is a thermodynamically stable nitride, the precipitation state is maintained even during secondary recrystallization annealing, and grain growth near the surface is suppressed.
- low temperature nitridation is performed at a temperature suitable for precipitation of Si 3 N 4 and iron nitride.
- nitriding when nitriding is performed at a temperature suitable for precipitation of Si 3 N 4 or iron nitride below 850 ° C., nitrogen supplied by nitriding enters the steel and precipitates in the form of Si 3 N 4 and the like. These nitrides are also formed near the surface immediately after nitriding, but are not thermodynamically stable as compared with AlN. For this purpose, nitride substitutes for AlN during the temperature increase of the secondary recrystallization annealing. As a result, a state in which AlN is dispersed to the center of the plate thickness is obtained.
- the present invention by performing nitriding with a temperature history of two or more stages of high temperature nitriding and low temperature nitriding, a state in which the precipitation amount of AlN is intentionally increased in the vicinity of the surface of the steel sheet is created. By suppressing the occurrence of secondary recrystallization, magnetic characteristics can be stably improved.
- the upper limit of the temperature of high temperature nitriding is not particularly limited, but is about 1050 ° C. from the technical viewpoint.
- the lower limit of the low-temperature nitriding temperature is not particularly limited, but is about 450 ° C. from the viewpoint of productivity.
- the same effect can be obtained even if the nitriding treatment at each temperature is divided into two or more times and performed in separate steps. It is easier to control the precipitation state by performing soaking in each temperature range, but the effect of the present invention is not required if soaking time is satisfied (even if there is no temperature change). Is obtained.
- nitriding in a temperature range of less than 850 ° C. is performed in order to obtain the grain growth inhibiting force of the entire plate thickness, and it is necessary to take a residence time until a necessary nitriding amount is obtained.
- the amount of nitriding during the nitriding treatment is preferably in the range of 100 massppm to 500 massppm, which is common in the nitriding technology of grain-oriented electrical steel sheets. This is because if it is less than 100 massppm, it is not sufficient for precipitation of AlN, and if it exceeds 500 massppm, excessive nitrogen supply may result in secondary recrystallization failure.
- the reaction efficiency decreases as the temperature is lowered, so that the required residence time varies greatly depending on the temperature. For example, if processing is performed at a temperature of about 750 ° C. at which Si 3 N 4 precipitates, the necessary nitriding amount can be obtained with a residence time of 1 minute or less, but if processing is performed at a low temperature of 450 ° C. at which iron nitride precipitates, Since the reaction rate is extremely low, a time of several hours or more may be required to obtain the necessary nitridation amount.
- the nitriding treatment is efficient because it is performed subsequent to the primary recrystallization annealing, so that the energy required for raising the temperature of the steel sheet becomes unnecessary. Moreover, even if it implements by several annealing from a high temperature side, an equivalent effect can be acquired, but energy efficiency can be improved further by implementing at once.
- FIG. 1 shows a nitriding equipment suitable for use in the present invention.
- 1 is a nitriding equipment
- 2 is a steel strip
- 3 is a nitriding gas supply pipe provided with cooling equipment
- 4 is a cooling equipment
- 5 is a cooling gas supply pipe
- 6 is a nitriding gas supply pipe
- 7 is high-temperature nitriding
- a processing unit 8 is a gas cooling zone
- 9 is a low-temperature nitriding unit
- 10 is an exhaust port.
- the nitriding treatment facility 1 does not require a complicated structure of the facility itself, and may have a facility length corresponding to the sheet feeding speed of the steel strip 2, and has a heater that can be temperature controlled separately before and after. What is necessary is just to provide the predetermined exhaust port 10 with heat processing equipment.
- a gas introduction part having a nitriding gas supply pipe (3 and 6) for introducing a gas containing at least ammonia or nitrogen so that a nitriding atmosphere can be maintained, and high-temperature nitriding and low-temperature nitriding during nitriding can be performed. What is necessary is just to provide the nitriding part (7 and 9).
- the high-temperature treatment section 7 (first half of the nitriding facility) that performs high-temperature nitriding is provided with a nitriding gas supply pipe 3 having a cooling device 4 having a cooling function in order to prevent gas deterioration.
- the cooling device may be any device that is generally used for gas cooling, such as having a nozzle that blows an inert gas of 400 ° C. or less or a nitriding gas onto the steel plate.
- the nitriding process according to this invention can be more effectively performed by taking the following structures.
- the low-temperature treatment section 9 low-stage equipment
- the control level of nitriding is significantly reduced when isothermal holding is not possible at an isothermal temperature, it is preferable to have a heater having a capability of soaking the steel sheet temperature or suppressing the temperature drop at a slightly low temperature.
- a cooling zone that cools the steel strip 2 by introducing a cooling gas from the cooling gas supply pipe 5 between the high temperature processing section and the low temperature processing section. 8 is preferable. This is because the temperature can be lowered to an appropriate temperature in a short time while separately adjusting the temperature before and after the furnace.
- the gas introduced from the gas introduction portion in the present invention is not limited as long as it is used in the NH 3 or the like gas nitriding, a slight O 2 to NH 3 in other
- An added oxynitriding atmosphere, a soft nitriding atmosphere containing a small amount of C, or the like can also be used.
- the gas used in the cooling zone include the use of inert gases such as N 2 and Ar and the aforementioned nitriding gas.
- FIG. 2 shows an SEM image obtained by SEM observation of a cross-section in the direction perpendicular to the rolling direction of the steel sheet after nitriding, which was formed under condition 3 of an example described later.
- AlN and Si 3 N 4 are precipitated in the vicinity of the surface after the nitriding treatment.
- iron nitride is formed in the vicinity of the surface instead of Si 3 N 4 .
- An annealing separator is applied to the steel sheet surface after the primary recrystallization annealing and nitriding treatment.
- MgO magnesia
- an appropriate oxide having a melting point higher than the secondary recrystallization annealing temperature such as alumina (Al 2 O 3 ) or calcia (CaO) is used as the main component of the annealing separator.
- alumina Al 2 O 3
- CaO calcia
- the sulfate and sulfide in the annealing separator Ag, Al, Ba, Ca, Co, Cr, Cu, Fe, In, K, Li, Mg, Mn, Na, Ni, Sn, Sb, Sr , Zn or Zr sulfates or sulfides selected from one or more may be added.
- the content of sulfate and sulfide in the annealing separator is preferably about 0.2% to 15%.
- the content of sulfates and sulfides is less than 0.2%, the amount of sulfur increase in the railway will be small. On the other hand, if the content of sulfates and sulfides exceeds 15%, the amount of sulfur increase in the base iron is too large. Therefore, in any case, the effect of improving magnetic characteristics is reduced.
- the grain-oriented electrical steel sheet produced by applying the above-described process to such a grain-oriented electrical steel sheet slab has the following characteristics. That is, in the temperature raising process of secondary recrystallization annealing and at the stage until the start of secondary recrystallization, the amount of nitride is increased in the vicinity of the surface of the steel sheet, and the nitride is precipitated to the center of the plate thickness. It becomes possible. As a result, it is possible to effectively suppress secondary recrystallization from the surface, which is often inferior to the texture, and obtain good magnetic properties.
- an insulating film can be further applied and baked on the steel sheet surface.
- the type of the insulating coating is not particularly limited, and any conventionally known insulating coating is suitable. For example, there is a method in which a coating solution containing phosphate-chromate-colloidal silica described in JP-A-50-79442 and JP-A-48-39338 is applied to a steel plate and baked at about 800 ° C. Is preferred. Further, the shape of the steel sheet can be adjusted by flattening annealing, and this flattening annealing can be combined with the baking treatment of the insulating coating.
- 21 or 20 steel sheets with the same conditions were produced per condition. Under the conditions of 21 sheets, one of them was used to analyze the sample after nitriding. The remaining 20 sheets were mainly composed of MgO, and the annealing separation aid shown in Table 1 was added to water. The annealing separator added after forming a slurry was applied and dried, and baked on the steel plate. Thereafter, final re-annealing with a maximum temperature of 1200 ° C. was performed for secondary recrystallization.
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Abstract
Description
すなわち、4.5mass%以下程度のSiと、MnS,MnSeおよびAlNなどのインヒビター成分を含有するスラブを、1300℃以上に加熱してインヒビター成分を一旦固溶させる。次いで、インヒビター成分が固溶したスラブを、熱間圧延し、必要に応じて熱延板焼鈍を施して、1回または中間焼鈍を挟む2回以上の冷間圧延によって最終板厚とする。
さらに、最終板厚となった冷間圧延板に、湿潤水素雰囲気中で一次再結晶焼純を施して、一次再結晶および脱炭を行う。その後、一次再結晶および脱炭を施した後の冷間圧延板に、マグネシア(MgO)を主剤とする焼鈍分離剤を塗布してから、二次再結晶の発現とインヒビター成分の純化のために、1200℃、5h程度の最終仕上焼鈍を行う、という工程を経ていた(例えば、特許文献1、特許文献2および特許文献3を参照)。
非特許文献1によれば、以下のように説明されている。
すなわち、上記した従来の方向性電磁鋼板の製造方法において、窒化処理後の鋼板には、窒化珪素を主体とした析出物(Si3N4もしくは(Si,Mn)N)が、その表面近傍に形成している。そして、引き続いて行われる二次再結晶焼鈍において、上記窒化珪素を主体とした析出物は、より熱力学的に安定したAl含有窒化物((Al,Si)N、あるいはAlN)に変化する。この際、表面近傍に存在したSi3N4は二次再結晶焼鈍の昇温中に固溶して、窒素は鋼中へ拡散する。そして、二次再結晶焼鈍において、900℃を超える温度になると、板厚方向にほぼ均一なAl含有窒化物が析出し、板全厚で粒成長抑制力(インヒビション効果)を得ることができるとされている。なお、この手法は、スラブ高温加熱を用いた析出物の分散制御に比べて、比較的容易に板厚方向に均一な析出物量と析出物粒径を得ることができるという利点を有している。
方向性電磁鋼板の製造工程において、集合組織は、前工程からの組織の特徴を継承している。すなわち、スラブ時の結晶形態である柱状晶や、等軸晶に始まる集合組織は、熱延時に、ロール摩擦によるせん断変形を受ける表面近傍や、単純圧縮変形を受ける中心部など、板厚方向で異なった集合組織になりやすい。
すなわち、鋼板の板厚方向に、窒化物を均一に析出させてインヒビション効果を発揮させるのではなく、むしろ、鋼板表面の窒化物の析出物量を多くする。そして、中心部に比べて、鋼板表面に強い粒成長抑制力を付与することで、二次再結晶を鋼板表面の組織から発生させなければ、鋼板の特性が安定化するのではないかと考えたのである。
しかしながら、鋼板の表面近傍にのみAlN析出が生じた場合、鋼板の中心層にまで窒素が拡散せずに、板厚の中心に窒化物がない状態となる。そして、鋼板中央部では粒成長抑制力を得ることができないため、方向性電磁鋼板に適した状態でないことが想定された。
発明者らは、上記知見に基づき、さらに検討を加えて本発明を完成させた。
1.mass%で、C:0.10%以下、Si:1.0~5.0%、Mn:0.01~0.5%、SおよびSeのうちから選んだ1種または2種:合計で0.002~0.040%、sol.Al:0.01~0.08%およびN:0.0010~0.020%を含有し、残部はFeおよび不可避的不純物からなる成分組成を有する鋼スラブを熱間圧延して、熱延板を得る工程と、
前記熱延板に必要に応じて熱延板焼鈍を施す工程と、
その後、前記熱延板に1回または中間焼鈍を挟む2回以上の冷間圧延を施して最終板厚を有する冷間圧延板とする工程と、
その後、前記冷間圧延板に一次再結晶焼鈍と窒化処理を施し、その後、焼鈍分離剤を塗布して二次再結晶焼鈍を実施して、方向性電磁鋼板を得る工程と、
を有し、
上記窒化処理を、高温窒化と、それに引き続く低温窒化との少なくとも2段階の温度で実施し、該高温窒化での滞留時間を少なくとも3秒以上600秒以下とする方向性電磁鋼板の製造方法。
Ni:0.005~1.50%、Sn:0.01~0.50%、
Sb:0.005~0.50%、Cu:0.01~0.50%、
Cr:0.01~1.50%、P:0.0050~0.50%
Nb:0.0005~0.0100%、Mo:0.01~0.50%
Ti:0.0005~0.0100%、B:0.0001~0.0100%およびBi:0.0005~0.0100%
のうちから選んだ1種または2種以上を含有する前記1に記載の方向性電磁鋼板の製造方法。
アンモニアまたは窒素を少なくとも含むガスを導入する窒化ガス供給配管と、窒化処理時の高温窒化と低温窒化を連続で行う窒化処理部とを備え、該窒化処理部は、高温窒化を行う高温処理部と、低温窒化を行う低温処理部とを有し、該高温処理部への窒化ガス供給配管に冷却用機器を備える窒化処理設備。
まず、本発明において、鋼スラブの成分組成の限定理由について説明する。なお、以下に記載する「%」表示は特に断らない限り、mass%を意味するものとする。
C:0.10%以下
Cは、一次再結晶集合組織を改善する上で有用な元素であるが、含有量が0.10%を超えるとかえって一次再結晶集合組織の劣化を招くので、本発明では含有量を0.10%以下に限定した。なお、磁気特性の観点から、Cの望ましい含有量は、0.01~0.08%の範囲である。また、要求される磁気特性のレベルがさほど高くない場合には、一次再結晶焼鈍における脱炭を省略あるいは簡略化するために、あえてCを0.01%以下0.0005%以上としてもよい。
Siは、電気抵抗を高めることによって鉄損を改善する有用元素であるが、含有量が5.0%を超えると冷間圧延性が著しく劣化するので、Siは5.0%以下に限定した。またSiは窒化物形成元素として機能させる必要があるため、1.0%以上含有させることが必要である。また、鉄損特性と冷間圧延性の両立の観点から、望ましいSi含有量は、1.5~4.5%の範囲である。
Mnは、製造時における熱間加工性を向上させる効果があるが、0.01%以下では効果に乏しい。一方、含有量が0.5%を超えた場合には、一次再結晶集合組織が悪化して磁気特性の劣化を招くので0.5%以下に限定した。
SおよびSeは、MnやCuと結合してMnSe、MnS、Cu2-xSe、Cu2-xSを形成し、鋼中の分散第二相としてインヒビターの作用を発揮する有用成分である。これらS、Seの合計の含有量が0.002%に満たないと、その添加効果に乏しい。一方で、S、Seの合計の含有量が0.040%を超えると、スラブ加熱時の固溶が不完全となるだけでなく、製品表面の欠陥の原因ともなる。従って、S、Seは、単独添加または複合添加いずれの場合も合計で0.002~0.040%の範囲に限定した。
Alは、鋼中でAlNを形成して分散第二相としてインヒビターの作用をする有用成分であるが、含有量が0.01%に満たないと十分に析出量が確保できない。一方で、Al含有量が0.08%を超えると、鋼板の窒化後に析出するAlN量が過剰となるため、粒成長の抑制力が高くなりすぎて、高温まで焼鈍しても二次再結晶しない。
NもAlと同様にAlNを形成するために必要な成分である。二次再結晶時にインヒビターとして必要な窒素は、後工程にて窒化により供給することができる。しかしながら、含有量が0.0010%を下回ると、窒化工程までの間の焼鈍工程における結晶粒成長が過剰となって、冷間圧延工程での粒界割れなどの原因となる場合がある。一方、0.020%を超えてNを添加すると、スラブ加熱時に鋼板のふくれ等を生じる。そのため、Nの添加は、0.0010~0.020%の範囲に限定した。
Niは、熱延板組織の均一性を高めることにより、磁気特性を改善する働きがある。そのためには0.005%以上含有させることが好ましい。一方、Ni含有量が1.50%を超えると二次再結晶が困難となって、磁気特性が劣化する。従って、Niは0.005~1.50%の範囲で含有させることが望ましい。
Snは、二次再結晶焼鈍中の鋼板の窒化や酸化を抑制し、良好な結晶方位を有する結晶粒の二次再結晶を促進して磁気特性を向上させる有用元素である。そのために、Snは、0.01%以上含有させることが好ましいが、0.50%を超えて含有されると冷間圧延性が劣化する。従って、Snは0.01~0.50%の範囲で含有させることが望ましい。
Sbは、二次再結晶焼鈍中の鋼板の窒化や酸化を抑制し、良好な結晶方位を有する結晶粒の二次再結晶を促進して磁気特性を効果的に向上させる有用元素である。その目的のためには、Sbを、0.005%以上含有させることが好ましいが、0.50%を超えて含有されると冷間圧延性が劣化する。従って、Sbは0.005~0.50%の範囲で含有させることが望ましい。
Cuは、二次再結晶焼鈍中の鋼板の酸化を抑制し、良好な結晶方位を有する結晶粒の二次再結晶を促進して磁気特性を効果的に向上させる働きがある。そのためには、Cuを、0.01%以上含有させることが好ましい。一方、0.50%を超えて含有されると熱間圧延性の劣化を招くので、Cuは0.01~0.50%の範囲で含有させることが望ましい。
Crは、フォルステライト被膜の形成を安定化させる働きがあり、そのためには0.01%以上含有させることが好ましい。一方で含有量が1.50%を超えると二次再結晶が困難となり、磁気特性が劣化するので、Crは0.01~1.50%の範囲で含有させることが望ましい。
Pは、フォルステライト被膜の形成を安定化させる働きがあり、そのためには0.0050%以上含有させることが好ましい。一方、含有量が0.50%を超えると冷間圧延性が劣化するので、Pは0.0050~0.50%の範囲で含有させることが望ましい。
Nb、Moは、スラブ加熱時の温度変化による割れの抑制等を介して、熱延後のヘゲを抑制する効果を有している。ここで、Nb、Moを、上記下限以上に含有させなければ、ヘゲ抑制の効果は小さい。一方、上記上限を超えると、炭化物や、窒化物を形成するなどして最終製品まで残留した際に、鉄損劣化を引き起こす。従って、Nb、Moは、上記の範囲で添加することが望ましい。
これらの成分は、窒化した際に析出物を形成したり、自身が偏析するなどしたりして、補助的なインヒビターとして機能し、二次再結晶を安定化させる効果を有する場合がある。ここで、これらの成分が、上記下限未満では、補助インヒビターとしての添加効果を得るに乏しい。一方、上記上限を超えると、形成した析出物が純化後にも残留して磁気特性劣化の原因となったり、粒界を脆化させベンド特性を劣化させたりする場合がある。
上記の好適成分組成範囲に調整した鋼スラブを、再加熱することなくあるいは再加熱したのち、熱間圧延に供する。なお、スラブを再加熱する場合には、再加熱温度は、1000℃以上1300℃以下程度とすることが望ましい。本発明では、二次再結晶焼鈍を実施する前に窒化処理を行ない、インヒビターを補強するため、熱延工程で完全固溶による析出物の微細分散は必ずしも必要ではない。そのため、1300℃を超えるような超高温スラブ加熱の実施は本発明には適していない。しかしながら、窒化までの焼鈍工程で、結晶粒径が粗大化し過ぎることがないように、加熱温度を上げ、熱延時にAl、N、Mn、S、Seをある程度固溶させ、分散させることは有用である。また、加熱温度が低すぎると熱延時の圧延温度までが低下して、圧延荷重が高くなり、圧延が困難となる。そのため、再加熱温度は1000℃以上が望ましい。
この一次再結晶焼鈍の目的は、圧延組織を有する冷間圧延板を一次再結晶させて、二次再結晶に最適な一次再結晶粒径に調整することである。そのためには、一次再結晶焼鈍の焼鈍温度を800℃以上950℃未満程度とすることが望ましい。この時の焼鈍雰囲気は、湿水素窒素あるいは湿水素アルゴン雰囲気とすることが好ましい。またかかる雰囲気とすることで脱炭焼鈍を兼ねても良い。
また、当該温度域の昇温速度は50℃/s以上が好ましいが、これは、昇温速度が50℃/s未満では、当該温度での組織の回復を十分に抑制することができないからである。
なお、これらの技術思想は、特開平7-62436号等に記載されたものと同じである。
図1に、本発明に用いて好適な窒化処理設備を示す。図中、1は窒化処理設備、2は鋼帯、3は冷却用機器を備える窒化ガス供給配管、4は冷却用機器、5は冷却ガス供給配管、6は窒化ガス供給配管、7は高温窒化処理部、8はガス冷却ゾーン、9は低温窒化処理部、10は排気口である。
本発明における窒化処理設備1は、設備の構造自体に複雑なものは必要なく、鋼帯2の通板速度に応じた設備長があれば良く、前後で別々に温度制御が可能なヒーターを有する熱処理設備で、所定の排気口10を備えれば良い。また、窒化雰囲気を保持できるような、アンモニアまたは窒素を少なくとも含むガスを導入する窒化ガス供給配管(3および6)を有するガス導入部と、窒化処理時の高温窒化と低温窒化を行うことができる窒化処理部(7および9)とを備えていればよい。
例えば、低温窒化を行う低温処理部9(設備後半)については、断熱を十分に行っていれば自然冷却を利用しても問題はない。ただし、等温で均熱保持できない場合は、窒化の制御レベルが大幅に低下するため、やや低温で、鋼板温度を均熱ないしは温度低下を抑える程度の能力を有するヒーターを有することが好ましい。また、高温処理部の温度を850℃以上に調整し、さらに低温処理部の温度を850℃未満に調整する機能を有することが望ましい。
また、平坦化焼鈍により、鋼板の形状を整えることも可能であり、さらにこの平坦化焼鈍を絶縁被膜の焼き付け処理と兼備させることもできる。
続けて、アンモニア、水素、窒素の混合雰囲気中で、表1に示した窒化条件で窒化処理を行った。また、一次再結晶焼鈍の昇温速度は500~700℃間の昇温速度を20℃/sと150℃/sの2水準とした。
評価結果を表1に併記する。
2 鋼帯
3 冷却用機器を備える窒化ガス供給配管
4 冷却用機器
5 冷却ガス供給配管
6 窒化ガス供給配管
7 高温窒化処理部
8 ガス冷却ゾーン
9 低温窒化処理部
10 排気口
Claims (7)
- mass%で、C:0.10%以下、Si:1.0~5.0%、Mn:0.01~0.5%、SおよびSeのうちから選んだ1種または2種:合計で0.002~0.040%、sol.Al:0.01~0.08%およびN:0.0010~0.020%を含有し、残部はFeおよび不可避的不純物からなる成分組成を有する鋼スラブを熱間圧延して、熱延板を得る工程と、
前記熱延板に必要に応じて熱延板焼鈍を施す工程と、
その後、前記熱延板に1回または中間焼鈍を挟む2回以上の冷間圧延を施して最終板厚を有する冷間圧延板とする工程と、
その後、前記冷間圧延板に一次再結晶焼鈍と窒化処理を施し、その後、焼鈍分離剤を塗布して二次再結晶焼鈍を実施して、方向性電磁鋼板を得る工程と、
を有し、
上記窒化処理を、高温窒化と、それに引き続く低温窒化との少なくとも2段階の温度で実施し、該高温窒化での滞留時間を少なくとも3秒以上600秒以下とする方向性電磁鋼板の製造方法。 - 前記成分組成がさらに、mass%で、
Ni:0.005~1.50%、Sn:0.01~0.50%、
Sb:0.005~0.50%、Cu:0.01~0.50%、
Cr:0.01~1.50%、P:0.0050~0.50%
Nb:0.0005~0.0100%、Mo:0.01~0.50%
Ti:0.0005~0.0100%、B:0.0001~0.0100%およびBi:0.0005~0.0100%
のうちから選んだ1種または2種以上を含有する請求項1に記載の方向性電磁鋼板の製造方法。 - 前記高温窒化を850℃以上で、また前記低温窒化を850℃未満で行う請求項1または2に記載の方向性電磁鋼板の製造方法。
- 前記一次再結晶焼鈍において、500~700℃間の昇温速度を50℃/s以上とする請求項1~3のいずれか1項に記載の方向性電磁鋼板の製造方法。
- 請求項1~4のいずれか1項に記載の方向性電磁鋼板の製造方法に用いる窒化処理設備であって、
アンモニアまたは窒素を少なくとも含むガスを導入する窒化ガス供給配管と、窒化処理時の高温窒化と低温窒化を連続で行う窒化処理部とを備え、
該窒化処理部は、高温窒化を行う高温処理部と、低温窒化を行う低温処理部とを有し、
該高温処理部への窒化ガス供給配管に冷却用機器を備える窒化処理設備。 - 前記高温処理部と前記低温処理部との間にガス冷却ゾーンを備える請求項5に記載の窒化処理設備。
- 前記高温処理部の温度を850℃以上に調整し、さらに前記低温処理部の温度を850℃未満に調整する機能を有する請求項5または6に記載の窒化処理設備。
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EP3196320A1 (en) | 2017-07-26 |
BR112017003743B1 (pt) | 2021-05-04 |
US10900113B2 (en) | 2021-01-26 |
US20170226622A1 (en) | 2017-08-10 |
CN106661656A (zh) | 2017-05-10 |
KR101988142B1 (ko) | 2019-06-11 |
EP3196320A4 (en) | 2017-08-09 |
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