JP2012158772A - Method of manufacturing high-silicon steel sheet - Google Patents
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- JP2012158772A JP2012158772A JP2011016980A JP2011016980A JP2012158772A JP 2012158772 A JP2012158772 A JP 2012158772A JP 2011016980 A JP2011016980 A JP 2011016980A JP 2011016980 A JP2011016980 A JP 2011016980A JP 2012158772 A JP2012158772 A JP 2012158772A
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- 229910000976 Electrical steel Inorganic materials 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 87
- 239000010959 steel Substances 0.000 claims abstract description 87
- 239000002344 surface layer Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 48
- 229910052742 iron Inorganic materials 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 15
- 230000006866 deterioration Effects 0.000 abstract description 10
- 230000032683 aging Effects 0.000 abstract description 9
- 238000005475 siliconizing Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 239000012298 atmosphere Substances 0.000 description 13
- 229910003902 SiCl 4 Inorganic materials 0.000 description 12
- 238000009792 diffusion process Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- 238000002791 soaking Methods 0.000 description 8
- 238000005261 decarburization Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、浸珪処理法による高珪素鋼板の製造方法に関する。 The present invention relates to a method for producing a high silicon steel sheet by a siliconization treatment method.
トランスやモーター等の鉄心には、鉄損が低く透磁率が高い等の優れた高周波磁気特性を有することから、高珪素鋼板が多用されている。特にＳｉ濃度が６．５mass％では磁歪が０となり、最大透磁率のピークとなる等のより優れた高周波磁気特性を示すことが知られている。従来、このような高珪素鋼板の製造方法として、低珪素鋼を圧延により薄板とした後、鋼板表面からＳｉを浸透拡散させる、いわゆる浸珪処理法が知られている（例えば、特許文献１）。
一般に、鋼板の浸珪処理ではＳｉ供給用の原料ガスとしてＳｉＣｌ４が使用され、このＳｉＣｌ４は鋼板と反応（ＳｉＣｌ４＋５Ｆｅ→Ｆｅ３Ｓｉ＋２ＦｅＣｌ２）してＳｉが鋼板表層に浸透する。このようにして鋼板表層に浸透したＳｉは、ＳｉＣｌ４を含まない無酸化性ガス雰囲気中で鋼板を均熱処理することにより板厚方向に拡散される。
High-silicon steel plates are frequently used for iron cores such as transformers and motors because they have excellent high-frequency magnetic properties such as low iron loss and high magnetic permeability. In particular, it is known that when the Si concentration is 6.5 mass%, the magnetostriction is 0, and the high-frequency magnetic characteristics such as a peak of maximum permeability are exhibited. Conventionally, as a method for producing such a high silicon steel sheet, a so-called siliconization treatment method is known in which Si is permeated and diffused from the steel sheet surface after the low silicon steel is rolled into a thin sheet (for example, Patent Document 1). .
In general, SiCl 4 is used as a raw material gas for supplying Si in the siliconizing treatment of the steel sheet, and this SiCl 4 reacts with the steel sheet (SiCl 4 + 5Fe → Fe 3 Si + 2FeCl 2 ) and Si permeates the steel sheet surface layer. Thus Si penetrated into the steel sheet surface layer is diffused in the thickness direction by soaking the steel sheet in a non-oxidizing gas atmosphere containing no SiCl 4.
ＳｉＣｌ４を原料ガスとして鋼板を連続的に浸珪処理する場合、浸珪処理雰囲気中に含まれる酸素分（水分及び酸素）がＳｉＣｌ４ガスと反応してシリカが生成され、このシリカが炉内ハースロール等の鋼板に接触する部分に付着し、鋼板に押し疵を発生させるという問題がある。また、浸珪処理により製造される高珪素鋼板は、浸珪処理雰囲気中の水分や酸素によって鋼板表面や粒界が酸化され、この酸化により鋼板の加工性が著しく劣化するという問題もある。
このような浸珪処理雰囲気中に含まれる水分や酸素による問題を回避するため、素材鋼板に予め適量のＣを添加しておき、このＣを雰囲気中の酸素分と反応させること（すなわち、鋼板の脱炭反応を利用すること）により、浸珪反応が起こる鋼板表面付近に存在する水分及び酸素濃度を極限まで下げるという方法が考えられ、この方法を利用した高珪素鋼板の製造方法が特許文献２で提案されている。
When continuously siliciding a steel sheet using SiCl 4 as a raw material gas, the oxygen content (water and oxygen) contained in the silicidation atmosphere reacts with the SiCl 4 gas to produce silica, and this silica is generated in the furnace. There exists a problem of adhering to the part which contacts steel plates, such as a hearth roll, and generating a pushing rod in a steel plate. In addition, the high silicon steel sheet produced by the siliconization treatment has a problem that the surface and grain boundaries of the steel sheet are oxidized by moisture and oxygen in the atmosphere of the siliconization treatment, and the workability of the steel sheet is significantly deteriorated by this oxidation.
In order to avoid such problems due to moisture and oxygen contained in the siliconizing atmosphere, an appropriate amount of C is added to the raw steel plate in advance, and this C is allowed to react with the oxygen content in the atmosphere (ie, steel plate). By using this decarburization reaction), a method of reducing the moisture and oxygen concentration existing near the steel plate surface where the silicification reaction occurs to the limit is considered, and a method for producing a high silicon steel plate using this method is disclosed in Patent Literature 2 proposed.
しかし、特許文献２の方法のように、適量のＣを添加した素材鋼板に浸珪処理を施した場合、鋼板の脱炭反応が予想どおりには進行せず、浸珪処理後の鋼板（製品）にＣが高濃度に残留し、この高濃度のＣが鋼板（製品）の磁気特性に悪影響を及ぼすという問題があることが判った。具体的には、浸珪処理後の鋼板のＣ濃度が高いと磁気時効が発生し、経時的に鉄損が劣化してしまう。特に高珪素鋼板は、高周波用途に使用されるため、経時的な磁気特性の劣化は高周波機器の破損や異常温度上昇などの弊害を発生させ、実用上大きな問題となる。 However, when the raw steel plate to which an appropriate amount of C is added as in the method of Patent Document 2, the decarburization reaction of the steel plate does not proceed as expected, and the steel plate after the siliconization treatment (product) C) remains in a high concentration, and this high concentration of C has a problem of adversely affecting the magnetic properties of the steel sheet (product). Specifically, when the C concentration of the steel plate after the siliconization treatment is high, magnetic aging occurs and the iron loss deteriorates with time. In particular, a high silicon steel sheet is used for high frequency applications, so that deterioration of magnetic characteristics over time causes problems such as breakage of high frequency equipment and abnormal temperature rise, which is a serious problem in practice.
このような高珪素鋼板の磁気時効の問題は、本質的には、特許文献２の方法を実施するかどうかに関わりなく、浸珪処理後の鋼板（製品）のＣ濃度が或るレベルを超えると生じる恐れがある。
したがって本発明の目的は、浸珪処理法により、磁気時効による鉄損の経時劣化を生じない高珪素鋼板を安定して製造することができる製造方法を提供することにある。
The problem of magnetic aging of such a high silicon steel sheet is essentially that the C concentration of the steel sheet (product) after siliconization exceeds a certain level regardless of whether or not the method of Patent Document 2 is performed. There is a risk that it will occur.
Accordingly, an object of the present invention is to provide a production method capable of stably producing a high silicon steel sheet that does not cause deterioration with time of iron loss due to magnetic aging by a siliconization method.
本発明者らは、上記課題を解決するため、浸珪処理における鋼板中のＣと雰囲気中の酸素分との反応（鋼板の脱炭反応）が阻害される要因とその対策について検討を重ねた結果、（i）浸珪処理時に鋼板中のＳ（硫黄）がＣの移動を妨げ、鋼板の脱炭反応を阻害しており（すなわち、鋼板からＣがうまく抜けない）、鋼板中のＳ濃度が高いほど脱炭反応を阻害する度合いが大きくなること、（ii）したがって、素材鋼板のＳ濃度とＣ濃度との関係を最適化することにより、浸珪処理後の鋼板のＣ濃度を問題ないレベルにすることができ、磁気時効による鉄損の経時劣化を生じない高珪素鋼板を安定的に製造できること、を見出した。 In order to solve the above-mentioned problems, the present inventors have repeatedly studied the factors that hinder the reaction (decarburization reaction of the steel sheet) between C in the steel sheet and the oxygen content in the atmosphere in the siliconization treatment, and countermeasures thereof. As a result, (i) S (sulfur) in the steel sheet hinders the movement of C during silicidation treatment and inhibits the decarburization reaction of the steel sheet (that is, C does not escape well from the steel sheet), and the S concentration in the steel sheet (Ii) Therefore, by optimizing the relationship between the S concentration and the C concentration of the material steel plate, there is no problem with the C concentration of the steel plate after the siliconization treatment. It has been found that a high silicon steel sheet can be stably produced without causing deterioration with time of iron loss due to magnetic aging.
本発明はこのような知見に基づきなされたもので、以下を要旨とするものである。
［1］素材鋼板を浸珪処理することにより、板厚方向の平均Ｓｉ濃度が４．０〜７．０mass％であって、板表層部のＳｉ濃度（mass％）と板厚中心部のＳｉ濃度（mass％）との偏差△Ｓｉ（mass％）が板厚ｔ（ｍｍ）との関係で、△Ｓｉ／ｔ＜２．０を満足する高珪素鋼板を製造する方法において、
素材鋼板として、Ｃ濃度［Ｃ］（mass ppm）とＳ濃度［Ｓ］（mass ppm）が下記（a）〜（c）のいずれかを満足する鋼板を用いることを特徴とする高珪素鋼板の製造方法。
（a）［Ｓ］≦３０、［Ｃ］≦１２０
（b）３０＜［Ｓ］＜１２０、［Ｃ］≦−０．７２２［Ｓ］＋１４１．６６
（c）１２０≦［Ｓ］、［Ｃ］≦５５
［2］上記［1］の製造方法において、浸珪処理後の高珪素鋼板のＣ濃度が５５mass ppm以下であることを特徴とする高珪素鋼板の製造方法。
The present invention has been made on the basis of such findings and has the following gist.
[1] By subjecting the material steel plate to a siliconization treatment, the average Si concentration in the plate thickness direction is 4.0 to 7.0 mass%, and the Si concentration (mass%) in the plate surface layer portion and Si in the plate thickness center portion In a method for producing a high silicon steel plate satisfying ΔSi / t <2.0, the deviation ΔSi (mass%) from the concentration (mass%) is related to the plate thickness t (mm).
A high silicon steel sheet characterized by using a steel sheet having a C concentration [C] (mass ppm) and an S concentration [S] (mass ppm) satisfying any of the following (a) to (c) as a raw steel plate: Production method.
(A) [S] ≦ 30, [C] ≦ 120
(B) 30 <[S] <120, [C] ≦ −0.722 [S] +141.66
(C) 120 ≦ [S], [C] ≦ 55
[2] The method for producing a high silicon steel sheet according to the above [1], wherein the C concentration of the high silicon steel sheet after the siliconization treatment is 55 mass ppm or less.
本発明の製造方法によれば、浸珪処理法により、磁気時効による鉄損の経時劣化を生じない高珪素鋼板を安定して製造することができる。 According to the manufacturing method of the present invention, a high silicon steel plate that does not cause deterioration with time of iron loss due to magnetic aging can be stably manufactured by a siliconization method.
本発明は、素材鋼板を浸珪処理することにより、板厚方向の平均Ｓｉ濃度が４．０〜７．０mass％であって、板表層部のＳｉ濃度（mass％）と板厚中心部のＳｉ濃度（mass％）との偏差△Ｓｉ（mass％）が鋼板の板厚ｔ（ｍｍ）との関係で、△Ｓｉ／ｔ＜２．０を満足する高珪素鋼板を製造する方法である。
ここで、製造される鋼板の板厚方向の平均Ｓｉ濃度が４．０mass％未満では、高珪素鋼板としての十分な高周波磁気特性が得られず、一方、７．０mass％を超えると脆化傾向が認められ、加工性が低下し、切板加工等の加工が困難となる場合がある。
In the present invention, by subjecting the raw steel plate to a siliconization treatment, the average Si concentration in the plate thickness direction is 4.0 to 7.0 mass%, and the Si concentration (mass%) of the plate surface layer portion and the plate thickness center portion This is a method for producing a high silicon steel sheet satisfying ΔSi / t <2.0 in relation to the deviation ΔSi (mass%) from the Si concentration (mass%) and the plate thickness t (mm) of the steel sheet.
Here, if the average Si concentration in the plate thickness direction of the steel plate to be produced is less than 4.0 mass%, sufficient high-frequency magnetic properties as a high silicon steel plate cannot be obtained, while if it exceeds 7.0 mass%, the embrittlement tendency tends to occur. May be recognized, workability may be reduced, and processing such as cut plate processing may be difficult.
鋼板を連続的に浸珪処理して高珪素鋼板を製造するために、通常、図１に示されるような、入側から加熱帯、浸珪処理帯、拡散均熱処理帯および冷却帯を備えた連続浸珪処理ラインが用いられる。
素材鋼板のＳｉ濃度は４mass％未満（通常２．８〜３．８mass％程度）であり、この素材鋼板を加熱帯において処理温度まで連続的に加熱した後、浸珪処理帯でＳｉＣｌ4と反応させることによりＳｉを鋼板表層部に浸透させ、次いで、拡散均熱処理帯でＳｉを板厚方向に拡散させるための熱処理を連続的に施した後、冷却帯で冷却することでコイル状の高珪素鋼板が製造される。通常、浸珪処理帯では、ＳｉＣｌ４濃度が約５〜３５ｍｏｌ％程度の処理ガスが供給され、鋼板は概ね露点−３０℃以下、酸素濃度１０ppm以下の雰囲気中で、１０２３〜１２００℃程度の処理温度で浸珪処理される。また、拡散均熱処理帯では、ＳｉＣｌ4を含まない無酸化性ガス雰囲気中で７００〜１２５０℃程度で熱処理される。浸珪処理直後の鋼板は、鋼板表層部が最大で１４．５mass％のＳｉ濃度であるのに対し、板厚中心部では素材鋼板とほぼ同じＳｉ濃度であるという極端なＳｉ濃度勾配を有しているが、拡散熱処理によりこのＳｉ濃度勾配が徐々に均一な方向に変化する。
In order to produce a high silicon steel sheet by continuously siliconizing the steel sheet, it is usually equipped with a heating zone, a siliconized treatment zone, a diffusion soaking zone, and a cooling zone as shown in FIG. A continuous siliconization line is used.
The material steel sheet has a Si concentration of less than 4 mass% (usually about 2.8 to 3.8 mass%), and after this material steel sheet is continuously heated to the treatment temperature in the heating zone, it reacts with SiCl 4 in the siliconization treatment zone. Si is infiltrated into the surface layer of the steel sheet, and then a continuous heat treatment for diffusing Si in the thickness direction in the diffusion soaking zone is followed by cooling in the cooling zone to form coiled high silicon. A steel plate is produced. Usually, in the siliconized zone, a processing gas having a SiCl 4 concentration of about 5 to 35 mol% is supplied, and the steel sheet is processed at a temperature of about 1023 to 1200 ° C. in an atmosphere having a dew point of −30 ° C. or lower and an oxygen concentration of 10 ppm or lower. It is siliconized at temperature. In the diffusion soaking zone, heat treatment is performed at about 700 to 1250 ° C. in a non-oxidizing gas atmosphere containing no SiCl 4 . The steel sheet immediately after the siliconization treatment has an extreme Si concentration gradient in which the steel sheet surface layer portion has a maximum Si concentration of 14.5 mass%, whereas the center thickness of the steel plate has substantially the same Si concentration as the material steel plate. However, this Si concentration gradient gradually changes in a uniform direction by diffusion heat treatment.
上記のように拡散均熱処理帯では、浸珪処理帯での浸珪処理により鋼板表層部に浸透させたＳｉを板厚方向に拡散させるが、この拡散熱処理の時間により、Ｓｉの拡散の度合い、すなわち板表層部のＳｉ濃度（mass％）と板厚中心部のＳｉ濃度（mass％）との偏差△Ｓｉ（mass％）が違ってくる。拡散熱処理によって鋼板表層部のＳｉを板厚方向で略均一に拡散させるには比較的長い時間を要するが、本発明が製造の対象とする△Ｓｉ／ｔ＜２．０を満足する高珪素鋼板は、拡散熱処理時間を概ね０．５〜１０分程度と比較的長くとり、板厚方向でのＳｉ濃度勾配を小さくした高珪素鋼板である。本発明は、このような△Ｓｉ／ｔ＜２．０を満足する高珪素鋼板に関する知見に基づきなされたものである。なお、本発明が製造の対象とする高珪素鋼板は、△Ｓｉ／ｔ＝０の場合を含むが、拡散熱処理時間の制約から通常は△Ｓｉ／ｔ＞０．１程度となる。 As described above, in the diffusion soaking zone, Si permeated into the steel sheet surface layer by the siliconization treatment in the siliconization zone is diffused in the thickness direction, but depending on the time of this diffusion heat treatment, the degree of diffusion of Si, That is, the deviation ΔSi (mass%) between the Si concentration (mass%) in the surface portion of the plate and the Si concentration (mass%) in the central portion of the thickness differs. Although a relatively long time is required for diffusing heat treatment to diffuse Si in the surface portion of the steel sheet substantially uniformly in the thickness direction, the high silicon steel sheet satisfying ΔSi / t <2.0, which is an object of the present invention. Is a high silicon steel sheet in which the diffusion heat treatment time is relatively long, approximately 0.5 to 10 minutes, and the Si concentration gradient in the sheet thickness direction is reduced. The present invention has been made on the basis of knowledge about such a high silicon steel sheet that satisfies ΔSi / t <2.0. The high silicon steel sheet to be manufactured by the present invention includes the case of ΔSi / t = 0, but usually ΔSi / t> 0.1 due to the limitation of the diffusion heat treatment time.
本発明では、素材鋼板として、Ｃ濃度［Ｃ］（mass ppm）とＳ濃度［Ｓ］（mass ppm）が下記（a）〜（c）のいずれかを満足する鋼板を用いる。
（a）［Ｓ］≦３０、［Ｃ］≦１２０
（b）３０＜［Ｓ］＜１２０、［Ｃ］≦−０．７２２［Ｓ］＋１４１．６６
（c）１２０≦［Ｓ］、［Ｃ］≦５５
鋼板中のＳ（硫黄）は、鋼板の浸珪処理時におけるＣの移動を妨げることで鋼板の脱炭反応を阻害し、鋼板中のＳ濃度が高いほど脱炭反応を阻害する度合いが大きくなる。ここで、本発明が製造の対象とする△Ｓｉ／ｔ＜２．０を満足する高珪素鋼板の場合には、浸珪処理後の鋼板（製品）のＣ濃度が５５mass ppmを超えると、磁気時効による鉄損の劣化が生じる恐れがある。後述する実施例（図２、図３）の結果が示すように、素材鋼板のＣ濃度とＳ濃度を、上記（a）〜（c）のいずれかを満足する関係に最適化することにより、浸珪処理後の鋼板（製品）のＣ濃度が５５mass ppm以下となり、磁気時効による鉄損の劣化を抑えることができる。すなわち、磁気時効による鉄損の経時劣化を生じない高珪素鋼板を製造することができる。
ここで、素材鋼板のＣ濃度が１２０mass ppmを超えると、通常の浸珪処理において、鋼板のＣ濃度を５５mass ppm以下とすることが困難となるので、素材鋼板のＣ濃度は１２０mass ppm以下であることが好ましい。また、上述したように本発明の方法は、素材鋼板中のＣの脱炭反応を利用するものであるため、素材鋼板中のＣ濃度は１０mass ppm以上、さらに望ましくは４０mass ppm超であることが好ましい。
In the present invention, a steel plate having a C concentration [C] (mass ppm) and an S concentration [S] (mass ppm) satisfying any of the following (a) to (c) is used as the material steel plate.
(A) [S] ≦ 30, [C] ≦ 120
(B) 30 <[S] <120, [C] ≦ −0.722 [S] +141.66
(C) 120 ≦ [S], [C] ≦ 55
S (sulfur) in the steel sheet inhibits the decarburization reaction of the steel sheet by hindering the movement of C during the siliconizing treatment of the steel sheet, and the degree of inhibiting the decarburization reaction increases as the S concentration in the steel sheet increases. . Here, in the case of a high silicon steel plate satisfying ΔSi / t <2.0, which is the object of manufacture of the present invention, if the C concentration of the steel plate (product) after the siliconization treatment exceeds 55 mass ppm, Deterioration of iron loss due to aging may occur. As shown in the results of Examples (FIGS. 2 and 3) to be described later, by optimizing the C concentration and S concentration of the material steel plate to a relationship satisfying any of the above (a) to (c), The C concentration of the steel plate (product) after the siliconization treatment is 55 mass ppm or less, and deterioration of iron loss due to magnetic aging can be suppressed. That is, it is possible to manufacture a high silicon steel sheet that does not cause deterioration of iron loss with time due to magnetic aging.
Here, when the C concentration of the material steel plate exceeds 120 mass ppm, it becomes difficult to set the C concentration of the steel plate to 55 mass ppm or less in a normal silicidation treatment, so the C concentration of the material steel plate is 120 mass ppm or less. It is preferable. Further, as described above, since the method of the present invention uses the decarburization reaction of C in the raw steel plate, the C concentration in the raw steel plate is preferably 10 mass ppm or more, more preferably more than 40 mass ppm. preferable.
素材鋼板の他の成分について、好ましい条件は以下のとおりである。
Ｍｎの含有量が０．０１mass％未満では固溶Ｓによる熱間脆性、冷間脆性の問題を生じるおそれがあり、一方、０．５mass％を超えるとＭｎによる固溶強化により鋼板が硬質化するおそれがあるので、Ｍｎの含有量は０．０１〜０．５mass％が好ましい。
Ａｌの含有量が１．０mass％を超えると冷間圧延性が劣化するおそれがあるので、１．０mass％以下とすることが好ましい。
Ｎは磁気特性を劣化させる元素であるが、０．０１mass％であれば実質的な影響は殆んどないため、０．０１mass％以下とすることが好ましい。
Ｏは加工性と磁気特性を劣化させる元素であるが、０．０１mass％以下であれば実質的な影響は殆んどないため、０．０１mass％以下とすることが好ましい。
通常、素材鋼板は、熱間圧延、酸洗、冷間圧延を経て得られる薄鋼板であり、磁気特性と加工組み立ての観点から、一般に板厚０．０３〜０．５ｍｍ程度のものが用いられる。
Preferred conditions for the other components of the material steel plate are as follows.
If the content of Mn is less than 0.01 mass%, there is a risk of causing problems of hot brittleness and cold brittleness due to the solid solution S. On the other hand, if it exceeds 0.5 mass%, the steel sheet is hardened due to solid solution strengthening by Mn. Since there exists a possibility, 0.01-0.5 mass% of content of Mn is preferable.
If the Al content exceeds 1.0 mass%, the cold rollability may be deteriorated, so it is preferable to set the content to 1.0 mass% or less.
N is an element that deteriorates the magnetic properties. However, if it is 0.01 mass%, there is almost no influence. Therefore, N is preferably 0.01 mass% or less.
O is an element that deteriorates workability and magnetic properties, but if it is 0.01 mass% or less, there is almost no substantial influence, so it is preferably 0.01 mass% or less.
Usually, a raw steel plate is a thin steel plate obtained through hot rolling, pickling, and cold rolling, and generally has a thickness of about 0.03 to 0.5 mm from the viewpoint of magnetic properties and work assembly. .
本発明の製造方法は、素材鋼板のＣ濃度を浸珪処理後の鋼板（高珪素鋼板）の目標Ｃ濃度よりも高くしておき、浸珪処理雰囲気中に含まれる酸素分によって素材鋼板の脱炭反応を生じさせつつ、素材鋼板の浸珪処理を行う方法に限定されるものではないが、この方法を用いる場合に特に有用である。この方法によれば、浸珪反応が起こる鋼板表面付近に存在する水分及び酸素濃度を極限まで下げることができ、その酸素分（水分及び酸素）がＳｉＣｌ４ガスと反応してシリカが生成されることを防止し、且つ水分や酸素によって鋼板表面や粒界が酸化されることも防止でき、これによって表面性状と加工性がともに優れた高珪素鋼板を得ることができる。 In the production method of the present invention, the C concentration of the raw steel plate is made higher than the target C concentration of the steel plate after the siliconization treatment (high silicon steel plate), and the raw steel plate is removed by the oxygen content contained in the siliconization atmosphere. Although it is not limited to the method of performing the silicidation process of a raw steel plate while causing a carbon reaction, it is particularly useful when using this method. According to this method, it is possible to reduce the moisture and oxygen concentrations existing near the steel plate surface where the silicification reaction occurs, and the oxygen content (moisture and oxygen) reacts with the SiCl 4 gas to generate silica. In addition, it is possible to prevent the steel sheet surface and grain boundaries from being oxidized by moisture and oxygen, thereby obtaining a high silicon steel sheet having both excellent surface properties and workability.
［実施例１］
図１に示すような連続浸珪処理ラインにおいて、板厚が０．１０ｍｍ、Ｓｉ濃度が３mass％の素材鋼板を連続浸珪処理し、板厚方向の平均Ｓｉ濃度が６．５mass％であって、板表層部のＳｉ濃度（mass％）と板厚中心部のＳｉ濃度（mass％）との偏差△Ｓｉが０．０２mass％（△Ｓｉ／ｔ＝０．２）の高珪素鋼板を製造した。なお、素材鋼板中のＣ濃度（Ｃ含有量）とＳ濃度（Ｓ含有量）は図２に示す値であり、他の成分（Ｍｎ，Ａｌ，Ｎ，Ｏ）の含有量は、さきに述べた好ましい範囲内であった。連続浸珪処理ラインでは、浸珪処理帯において、Ｎ２＋ＳｉＣｌ４雰囲気（露点：−３０℃以下、酸素濃度：１０ppm以下）中で１２００℃で浸珪処理を行い、引き続き拡散均熱処理帯において、Ｎ２雰囲気中で１２３０℃で拡散均熱処理を行った。
[Example 1]
In the continuous siliconization treatment line as shown in FIG. 1, a raw steel plate having a plate thickness of 0.10 mm and a Si concentration of 3 mass% is continuously siliconized, and the average Si concentration in the plate thickness direction is 6.5 mass%. A high silicon steel sheet having a deviation ΔSi of 0.02 mass% (ΔSi / t = 0.2) between the Si concentration (mass%) of the surface layer portion of the plate and the Si concentration (mass%) of the central portion of the thickness was manufactured. . In addition, C density | concentration (C content) and S density | concentration (S content) in a raw steel plate are the values shown in FIG. 2, and content of other components (Mn, Al, N, O) is described above. It was within the preferable range. In the continuous siliconization treatment line, the siliconization treatment is performed at 1200 ° C. in a N 2 + SiCl 4 atmosphere (dew point: −30 ° C. or less, oxygen concentration: 10 ppm or less) in the siliconization treatment zone. Diffusion soaking was performed at 1230 ° C. in an N 2 atmosphere.
製造後の高珪素鋼板を２００℃の雰囲気に１００ｈｒ放置し、その前後の鉄損の増加率を測定することで鉄損の経時変化を調べ、下記の基準で評価した。なお、本実施例での鉄損は、Ｗ10/400（１Ｔ，４００Ｈｚ）の条件とした。この試験結果を、素材鋼板のＣ濃度とＳ濃度との関係で整理したものを図２に示す。
○（良好）：鉄損の経時増加率が８％以下
△（許容）：鉄損の経時増加率が８％超１０％以下
×（不良）：鉄損の経時増加率が１０％超
浸珪処理後の鋼板のＣ濃度は、“○”の結果となったものは全て５５mass ppm以下となっており、また、“△”の結果となったものは全て５５mass
ppm超６０mass ppm以下、“×”の結果となったものは全て６０mass ppm超となっていた。
The manufactured high silicon steel sheet was allowed to stand in an atmosphere of 200 ° C. for 100 hours, and the change rate of iron loss with time was measured by measuring the rate of increase in iron loss before and after that, and evaluated according to the following criteria. The iron loss in this example was W10 / 400 (1T, 400 Hz). FIG. 2 shows the results of the test arranged in relation to the C concentration and S concentration of the steel sheet.
○ (Good): Increase rate of iron loss with time is 8% or less △ (Acceptable): Increase rate of iron loss with time is more than 8% and 10% or less × (Poor): Increase rate with time of iron loss is more than 10% The C concentration of the steel sheet after the treatment was 55 mass ppm or less for all the results of “◯”, and 55 mass for all of the results of “△”.
All of the results exceeding “ppm” exceeding 60 ppm by mass and exceeding “×” were above 60 mass ppm.
［実施例２］
図１に示すような連続浸珪処理ラインにおいて、板厚が０．１５ｍｍ、Ｓｉ濃度が３mass％の素材鋼板を連続浸珪処理し、板厚方向の平均Ｓｉ濃度が６．５mass％であって、板表層部のＳｉ濃度（mass％）と板厚中心部のＳｉ濃度（mass％）との偏差△Ｓｉが０．２０mass％（△Ｓｉ／ｔ＝１．３）の高珪素鋼板を製造した。なお、素材鋼板中のＣ濃度（Ｃ含有量）とＳ濃度（Ｓ含有量）は図３に示す値であり、他の成分（Ｍｎ，Ａｌ，Ｎ，Ｏ）の含有量は、さきに述べた好ましい範囲内であった。連続浸珪処理ラインでは、浸珪処理帯において実施例１と同様のＮ２＋ＳｉＣｌ４雰囲気中で１２００℃で浸珪処理を行い、引き続き拡散均熱処理帯において、Ｎ２雰囲気中で１２３０℃で拡散均熱処理を行った。
[Example 2]
In the continuous siliconization treatment line as shown in FIG. 1, a material steel plate having a thickness of 0.15 mm and a Si concentration of 3 mass% is continuously siliconized, and the average Si concentration in the thickness direction is 6.5 mass%. A high silicon steel sheet having a deviation ΔSi of 0.20 mass% (ΔSi / t = 1.3) between the Si concentration (mass%) of the surface layer portion of the plate and the Si concentration (mass%) of the central portion of the plate thickness was manufactured. . In addition, C density | concentration (C content) and S density | concentration (S content) in a raw steel plate are the values shown in FIG. 3, and content of other components (Mn, Al, N, O) is described above. It was within the preferable range. In the continuous siliconization treatment line, the siliconization treatment is performed at 1200 ° C. in the same N 2 + SiCl 4 atmosphere as in Example 1 in the siliconization treatment zone, followed by diffusion at 1230 ° C. in the N 2 atmosphere in the diffusion soaking zone. Soaking was performed.
製造後の高珪素鋼板を２００℃の雰囲気に１００ｈｒ放置し、その前後の鉄損の増加率を測定することで鉄損の経時変化を調べ、下記の基準で評価した。なお、本実施例での鉄損は、Ｗ10/400（１Ｔ，４００Ｈｚ）の条件とした。この試験結果を、素材鋼板のＣ濃度とＳ濃度との関係で整理したものを図３に示す。
○（良好）：鉄損の経時増加率が８％以下
△（許容）：鉄損の経時増加率が８％超１０％以下
×（不良）：鉄損の経時増加率が１０％超
浸珪処理後の鋼板のＣ濃度は、“○”の結果となったものは全て５５mass ppm以下となっており、また、“△”の結果となったものは全て５５mass
ppm超６０mass ppm以下、“×”の結果となったものは全て６０mass ppm超となっていた。
The manufactured high silicon steel sheet was allowed to stand in an atmosphere of 200 ° C. for 100 hours, and the change rate of iron loss with time was measured by measuring the rate of increase in iron loss before and after that, and evaluated according to the following criteria. The iron loss in this example was W10 / 400 (1T, 400 Hz). FIG. 3 shows the results of this test arranged in relation to the C concentration and S concentration of the steel sheet.
○ (Good): Increase rate of iron loss with time is 8% or less △ (Acceptable): Increase rate of iron loss with time is more than 8% and 10% or less × (Poor): Increase rate with time of iron loss is more than 10% The C concentration of the steel sheet after the treatment was 55 mass ppm or less for all the results of “◯”, and 55 mass for all of the results of “△”.
All of the results exceeding “ppm” exceeding 60 ppm by mass and exceeding “×” were above 60 mass ppm.
Claims (2)
素材鋼板として、Ｃ濃度［Ｃ］（mass ppm）とＳ濃度［Ｓ］（mass ppm）が下記（a）〜（c）のいずれかを満足する鋼板を用いることを特徴とする高珪素鋼板の製造方法。
（a）［Ｓ］≦３０、［Ｃ］≦１２０
（b）３０＜［Ｓ］＜１２０、［Ｃ］≦−０．７２２［Ｓ］＋１４１．６６
（c）１２０≦［Ｓ］、［Ｃ］≦５５ By subjecting the material steel plate to a siliconization treatment, the average Si concentration in the plate thickness direction is 4.0 to 7.0 mass%, and the Si concentration (mass%) in the plate surface layer portion and the Si concentration in the plate thickness center portion (mass) %) In relation to the plate thickness t (mm), in the method for producing a high silicon steel sheet satisfying ΔSi / t <2.0,
A high silicon steel sheet characterized by using a steel sheet having a C concentration [C] (mass ppm) and an S concentration [S] (mass ppm) satisfying any of the following (a) to (c) as a raw steel plate: Production method.
(A) [S] ≦ 30, [C] ≦ 120
(B) 30 <[S] <120, [C] ≦ −0.722 [S] +141.66
(C) 120 ≦ [S], [C] ≦ 55
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| JPH04246157A (en) * | 1991-01-29 | 1992-09-02 | Nkk Corp | High silicon steel sheet excellent in soft-magnetic property |
| JPH11286753A (en) * | 1998-04-02 | 1999-10-19 | Nkk Corp | Silicon steel sheet stable and low in residual magnetic flux density |
| JPH11293448A (en) * | 1998-04-10 | 1999-10-26 | Nkk Corp | Production of silicon steel sheet using siliconizing method |
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| JPH04246157A (en) * | 1991-01-29 | 1992-09-02 | Nkk Corp | High silicon steel sheet excellent in soft-magnetic property |
| JPH11286753A (en) * | 1998-04-02 | 1999-10-19 | Nkk Corp | Silicon steel sheet stable and low in residual magnetic flux density |
| JPH11293448A (en) * | 1998-04-10 | 1999-10-26 | Nkk Corp | Production of silicon steel sheet using siliconizing method |
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