JP2021169648A - Oriented electromagnetic steel sheet and method for producing oriented electromagnetic steel sheet - Google Patents
Oriented electromagnetic steel sheet and method for producing oriented electromagnetic steel sheet Download PDFInfo
- Publication number
- JP2021169648A JP2021169648A JP2020073031A JP2020073031A JP2021169648A JP 2021169648 A JP2021169648 A JP 2021169648A JP 2020073031 A JP2020073031 A JP 2020073031A JP 2020073031 A JP2020073031 A JP 2020073031A JP 2021169648 A JP2021169648 A JP 2021169648A
- Authority
- JP
- Japan
- Prior art keywords
- group
- steel sheet
- annealing
- total
- elements
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 101
- 239000010959 steel Substances 0.000 title claims abstract description 101
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 229910052738 indium Inorganic materials 0.000 claims abstract description 49
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 48
- 229910052709 silver Inorganic materials 0.000 claims abstract description 44
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 44
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 43
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 43
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 43
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 43
- 239000012535 impurity Substances 0.000 claims abstract description 25
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 21
- 229910052745 lead Inorganic materials 0.000 claims abstract description 19
- 229910052839 forsterite Inorganic materials 0.000 claims abstract description 13
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 238000000137 annealing Methods 0.000 claims description 93
- 239000011248 coating agent Substances 0.000 claims description 53
- 238000000576 coating method Methods 0.000 claims description 53
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 46
- 239000000395 magnesium oxide Substances 0.000 claims description 42
- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 claims description 39
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 38
- 239000000843 powder Substances 0.000 claims description 38
- 229910052684 Cerium Inorganic materials 0.000 claims description 21
- 229910052693 Europium Inorganic materials 0.000 claims description 21
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 21
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 21
- 229910052788 barium Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 229910052791 calcium Inorganic materials 0.000 claims description 20
- 229910052712 strontium Inorganic materials 0.000 claims description 19
- 239000000654 additive Substances 0.000 claims description 18
- 230000000996 additive effect Effects 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 14
- 238000005121 nitriding Methods 0.000 claims description 12
- 229910052711 selenium Inorganic materials 0.000 claims description 11
- 238000010791 quenching Methods 0.000 claims description 10
- 230000000171 quenching effect Effects 0.000 claims description 10
- 229910052733 gallium Inorganic materials 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000003112 inhibitor Substances 0.000 description 41
- 230000000694 effects Effects 0.000 description 38
- 239000002585 base Substances 0.000 description 30
- 230000004907 flux Effects 0.000 description 28
- 239000000203 mixture Substances 0.000 description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 25
- 238000001953 recrystallisation Methods 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 21
- 239000000126 substance Substances 0.000 description 20
- 239000011575 calcium Substances 0.000 description 19
- 238000005261 decarburization Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 16
- 238000005097 cold rolling Methods 0.000 description 14
- 239000012467 final product Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 238000005096 rolling process Methods 0.000 description 11
- 238000000746 purification Methods 0.000 description 10
- 230000009471 action Effects 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 238000005098 hot rolling Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910000976 Electrical steel Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000001745 non-dispersive infrared spectroscopy Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Manufacturing Of Steel Electrode Plates (AREA)
- Soft Magnetic Materials (AREA)
Abstract
Description
本発明は、磁気特性の良好な方向性電磁鋼板および方向性電磁鋼板を安定的に製造する方法に関する。 The present invention relates to a grain-oriented electrical steel sheet having good magnetic characteristics and a method for stably producing grain-oriented electrical steel sheet.
方向性電磁鋼板は、Ｓｉを２〜５％程度含有し、結晶粒の方位が｛１１０｝＜００１＞方位に高度に集積した鋼板であり、主に変圧器等の静止誘導器の鉄心材料として使用されている。結晶粒方位の高度な集積は、二次再結晶というカタストロフィックな粒成長現象を制御して達成される。 The grain-oriented electrical steel sheet contains about 2 to 5% of Si and is highly integrated in the direction of {110} <001> of crystal grains, and is mainly used as an iron core material for a static inducer such as a transformer. in use. A high degree of accumulation of grain orientation is achieved by controlling the catastrophic grain growth phenomenon of secondary recrystallization.
二次再結晶を制御する方法として、二次再結晶時にインヒビターとして機能する化合物を、熱間圧延前に十分に固溶させ、その後、熱間圧延、及び、後の焼鈍で、微細析出させる方法がある。特許文献１の方法では、ＭｎＳとＡｌＮをインヒビターとして用い、特許文献２及び３の方法では、ＭｎＳとＭｎＳｅをインヒビターとして用いている。 As a method for controlling secondary recrystallization, a compound that functions as an inhibitor during secondary recrystallization is sufficiently dissolved before hot rolling, and then finely precipitated by hot rolling and subsequent annealing. There is. In the method of Patent Document 1, MnS and AlN are used as inhibitors, and in the methods of Patent Documents 2 and 3, MnS and MnSe are used as inhibitors.
また、二次再結晶を制御する方法として、熱間圧延前の鋼片を１２８０℃未満に加熱し、冷間圧延後の窒化処理でＡｌＮを形成し、インヒビターとして用いる方法が例えば、特許文献４及び５に開示されている。 Further, as a method for controlling secondary recrystallization, for example, Patent Document 4 is a method in which a steel piece before hot rolling is heated to less than 1280 ° C., AlN is formed by nitriding treatment after cold rolling, and the steel piece is used as an inhibitor. And 5 are disclosed.
以上の二次再結晶制御を基本として優れた磁気特性を有する方向性電磁鋼板が開発されてきたが、近年、省エネルギーの機運が高まり、さらなる磁気特性の向上が求められている。 A grain-oriented electrical steel sheet having excellent magnetic properties has been developed based on the above secondary recrystallization control, but in recent years, the momentum for energy saving has increased, and further improvement in magnetic properties is required.
方向性電磁鋼板の磁気特性の代表的な指標としては磁束密度が挙げられる。磁束密度を高くするには、結晶粒方位を、｛１１０｝＜００１＞方位に、より高度に集積させることが必要であるが、その方法の一つは、インヒビターの作用を強化する補助的な添加元素を利用することである。特許文献６及び７には、Ｂｉを利用する方法が、特許文献８には、Ｐｂを利用する方法が開示され、特許文献９〜１４には、Ｔｅを利用することに加え、Ｉｎ、Ａｇ、Ｚｎなどの補助元素が有効に作用することが開示されている。 Magnetic flux density is a typical index of the magnetic properties of grain-oriented electrical steel sheets. In order to increase the magnetic flux density, it is necessary to integrate the grain orientation in the {110} <001> orientation to a higher degree, and one of the methods is an auxiliary method for enhancing the action of the inhibitor. It is to utilize additive elements. Patent Documents 6 and 7 disclose a method using Bi, Patent Document 8 discloses a method using Pb, and Patent Documents 9 to 14 disclose In, Ag, in addition to using Te. It is disclosed that auxiliary elements such as Zn act effectively.
また、Ａｇは、電磁鋼板の二次再結晶工程で一次粒の成長を抑制し、二次再結晶を促進する作用を有することが特許文献１５に開示されている。 Further, Patent Document 15 discloses that Ag has an action of suppressing the growth of primary grains in the secondary recrystallization step of an electromagnetic steel sheet and promoting the secondary recrystallization.
本発明者らは、Ｂｉ，Ｐｂ，Ｉｎ，Ｔｅ等のインヒビター補強元素を活用した方向性電磁鋼板のさらなる磁束密度向上を目的とし、様々な元素の複合添加について検討した。その結果、方向性電磁鋼板用スラブにＢｉ，Ｐｂ，Ｉｎ，Ｔｅ等を添加しても最終製品での磁束密度が十分に向上しない場合があることに気付いた。この原因を調査したところ、特性向上が不十分な場合は、二次再結晶で細粒が発生しやすく、特性のばらつきが大きくなっていた。また、Ｂｉ，Ｐｂ，Ｉｎ，Ｔｅ等の添加により熱延性が低下し、熱延板エッジのトリムが必要になる場合が生じるなど、生産性や歩留りを低下させる傾向があることが判明した。さらに検討を進め、添加元素をいくつかの群に分け、各群に分類される元素を適切に組み合わせて含有させることで、熱延性を改善し、二次再結晶での細粒発生を抑制し、最終製品で高い磁束密度を安定的に得られる技術に到達した。具体的には、Ｂｉ及び／又はＰｂを含む方向性電磁鋼板用スラブに、Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇを単独で添加した場合、熱間圧延性が極めて劣位となるが、所要量のＴｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇを複数種類添加すると、熱延性を改善できるとともに、二次再結晶での細粒発生が抑制され、最終製品で高い磁束密度を安定的に得ることができた。しかし、これにより得られる鋼板は、厳しい加工条件において被膜密着性が不足する場合があり、被膜密着性のさらなる改善の余地があった。 The present inventors have studied the composite addition of various elements for the purpose of further improving the magnetic flux density of grain-oriented electrical steel sheets utilizing inhibitor reinforcing elements such as Bi, Pb, In, and Te. As a result, it was noticed that the magnetic flux density in the final product may not be sufficiently improved even if Bi, Pb, In, Te, etc. are added to the slab for grain-oriented electrical steel sheets. As a result of investigating the cause of this, when the improvement of the characteristics was insufficient, fine particles were likely to be generated in the secondary recrystallization, and the variation in the characteristics was large. Further, it has been found that the addition of Bi, Pb, In, Te, etc. reduces the heat ductility, and the trimming of the edge of the hot-rolled plate may be required, which tends to reduce the productivity and the yield. Further studies were carried out, and the additive elements were divided into several groups, and the elements classified in each group were appropriately combined and contained to improve the heat ductility and suppress the generation of fine particles in the secondary recrystallization. We have reached a technology that can stably obtain a high magnetic flux density in the final product. Specifically, when Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg are added alone to a slab for a directional electromagnetic steel plate containing Bi and / or Pb, hot rollability However, by adding a plurality of types of required amounts of Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg, the heat ductility can be improved and fine granules in secondary recrystallization can be obtained. The generation was suppressed, and a high magnetic flux density could be stably obtained in the final product. However, the steel sheet obtained by this may lack the film adhesion under severe processing conditions, and there is room for further improvement of the film adhesion.
本発明は、前述した、Ｂｉ，Ｐｂ，Ｉｎ，Ｔｅ等のインヒビター補強元素の活用に係る技術的課題に鑑み、該課題を解決し、良好な磁気特性と被膜密着性を備える方向性電磁鋼板と、該方向性電磁鋼板の製造方法を提供することを目的とする。 In view of the above-mentioned technical problems related to the utilization of inhibitor reinforcing elements such as Bi, Pb, In, and Te, the present invention solves the problems and provides a grain-oriented electrical steel sheet having good magnetic properties and film adhesion. , An object of the present invention is to provide a method for manufacturing the grain-oriented electrical steel sheet.
本発明者らは、Ｂｉ，Ｐｂ，Ｉｎ，Ｔｅ等のインヒビター補強元素を活用する場合の被膜密着性向上について鋭意検討した。その結果、Ｂｉ及び／又はＰｂを含む方向性電磁鋼板用スラブに、所要量のＴｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇを複数種類添加することで、熱延性を改善できるとともに、最終製品で高く安定した磁束密度が得られ、さらに、仕上焼鈍前に塗布・乾燥する焼鈍分離剤についてＣａ，Ｓｒ，Ｂａ，Ｃｅ，Ｐｒ，Ｅｕ，及びＧｄの添加量を制御することで良好な被膜密着性を確保できることが判明した。 The present inventors have diligently studied the improvement of film adhesion when using inhibitor reinforcing elements such as Bi, Pb, In, and Te. As a result, by adding a plurality of types of required amounts of Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg to the slab for directional electromagnetic steel plate containing Bi and / or Pb, thermal ductility In addition, a high and stable magnetic flux density can be obtained in the final product, and the amount of Ca, Sr, Ba, Ce, Pr, Eu, and Gd added to the annealing separator that is applied and dried before finish annealing is controlled. It was found that good film adhesion can be ensured by doing so.
本発明は、上記知見に基づいてなされたもので、その要旨は以下のとおりである。 The present invention has been made based on the above findings, and the gist thereof is as follows.
[１]
質量％で、Ｓｉ：２．５〜４．５％、Ｃ：０．０２〜０．１０％、酸可溶性Ａｌ：０．０１〜０．０５％、Ｎ：０．００３〜０．０２％、Ｓ＋０．４・Ｓｅ：０．００３〜０．０４％、Ｍｎ：０．０４〜０．２０％、Ｂｉ及びＰｂの一種以上の合計：０．０００５〜０．０５％、さらに、Ｔｅ、Ｉｎ、Ｃｄ、Ｚｎ、Ｇａ、Ａｕ、Ａｇ、Ｐｄ、Ｐｔ、及びＨｇからなる群から選択される少なくとも二種以上の合計：０．００１〜０．５００％を含有し、残部がＦｅ及び不純物からなるスラブを、１０００〜１４５０℃に加熱し、熱間圧延で熱延板とし、該熱延板に焼鈍を施し、次いで、酸洗の後、一回又は焼鈍を挟む二回の冷間圧延で冷延板とし、該冷延板に脱炭焼鈍を施し、必要に応じて該焼鈍中又は焼鈍後に窒化処理を施し、続いて、
酸化マグネシウム粉末を主成分とする焼鈍分離剤であって、
該焼鈍分離剤の酸化マグネシウム粉末は、不純物元素としてＣａ，Ｓｒ，Ｂａ，Ｃｅ，Ｐｒ，Ｅｕ，及びＧｄからなる群から選択される少なくとも一種以上の元素の合計存在量が，該酸化マグネシウム粉末中のＭｇの存在量に対して０．０２〜０．８％の存在比で含有し，
さらに前記焼鈍分離剤は酸化マグネシウム粉末以外にＣａ，Ｓｒ，Ｂａ，Ｃｅ，Ｐｒ，Ｅｕ，及びＧｄからなる群から選択される少なくとも一種以上の元素を含む添加剤を、それぞれの元素の合計存在量が、焼鈍分離剤の中に含まれるＭｇの存在量に対して０．２〜５．０％の存在比となるように含有し，
さらに、前記焼鈍分離剤中のＣａ，Ｓｒ，Ｂａ，Ｃｅ，Ｐｒ，Ｅｕ，及びＧｄの総量に対する、前記焼鈍分離剤中の酸化マグネシウム粉末中の不純物元素としてのＣａ，Ｓｒ，Ｂａ，Ｃｅ，Ｐｒ，Ｅｕ，及びＧｄの総量の割合が、０．０２〜０．６６である焼鈍分離剤を鋼板表裏面に塗布・乾燥したのち、
最終仕上焼鈍を施すことを特徴とする方向性電磁鋼板の製造方法。
[２]
前記スラブは、Ｔｅ、Ｉｎ、Ｃｄ、Ｚｎ、及びＧａからなる群から選択される少なくとも一種以上の合計：０．０００５％以上、かつ、Ａｕ、Ａｇ、Ｐｄ、Ｐｔ、及びＨｇからなる群から選択される少なくとも一種以上の合計：０．０００５％以上を含有する、[１]に記載の方向性電磁鋼板の製造方法。
[３]
質量％で、Ｓｉ：２．５〜４．５％、Ｍｎ：０．０４〜０．２０％、を含有し、残部がＦｅ及び不可避的不純物からなる母材鋼板と、前記母材鋼板の表面に、質量％で、Ｔｅ、Ｉｎ、Ｃｄ、Ｚｎ、Ｇａ、Ａｕ、Ａｇ、Ｐｄ、Ｐｔ、及びＨｇからなる群から選択される少なくとも二種以上の合計：０．０２〜０．５０％、Ｃａ、Ｓｒ、Ｂａ、Ｃｅ、Ｐｒ、Ｅｕ、及びＧｄからなる群から選択される少なくとも一種以上の合計：０．０２〜０．５０％、Ｂｉ及びＰｂの一種以上の合計：０．００５％以下を含有し、フォルステライトを主体とする被膜が存在する、方向性電磁鋼板。
[４]
母材鋼板表面に、
Ｔｅ、Ｉｎ、Ｃｄ、Ｚｎ、及びＧａからなる群から選択される少なくとも一種以上の合計：０．０１％以上、かつＡｕ、Ａｇ、Ｐｄ、Ｐｔ、及びＨｇからなる群から選択される少なくとも一種以上の合計：０．０１％以上、を含有するフォルステライトを主体とする被膜が存在し、[３]に記載の方向性電磁鋼板。
[５]
母材鋼板表面に、
Ｃａ、Ｓｒ、Ｂａ、Ｃｅ、Ｐｒ、Ｅｕ、及びＧｄからなる群のうち、最大の含有量の元素の板厚方向深さと、ＳおよびＳｅからなる群から選択される元素のうち、最大の含有量の元素の板厚方向深さの差が±１．５μｍ以内の範囲である，フォルステライトを主体とする被膜が存在し、[３]または[４]に記載の方向性電磁鋼板。
[1]
By mass%, Si: 2.5 to 4.5%, C: 0.02 to 0.10%, acid-soluble Al: 0.01 to 0.05%, N: 0.003 to 0.02%, S + 0.4 · Se: 0.003 to 0.04%, Mn: 0.04 to 0.20%, total of one or more types of Bi and Pb: 0.0005 to 0.05%, and Te, In, A slab containing at least two or more selected from the group consisting of Cd, Zn, Ga, Au, Ag, Pd, Pt, and Hg: 0.001 to 0.500%, with the balance being Fe and impurities. Is heated to 1000 to 1450 ° C., hot-rolled to obtain a hot-rolled plate, the hot-rolled plate is annealed, and then pickled and then cold-rolled once or twice with annealing. A plate is prepared, and the cold-rolled plate is decarburized and annealed, and if necessary, nitriding is performed during or after the annealing, and then,
An annealing separator containing magnesium oxide powder as the main component.
The magnesium oxide powder of the quenching separator has a total abundance of at least one or more elements selected from the group consisting of Ca, Sr, Ba, Ce, Pr, Eu, and Gd as impurity elements in the magnesium oxide powder. It is contained in an abundance ratio of 0.02 to 0.8% with respect to the abundance of Mg in
Further, the quenching separator contains an additive containing at least one element selected from the group consisting of Ca, Sr, Ba, Ce, Pr, Eu, and Gd in addition to magnesium oxide powder, and the total abundance of each element. Is contained so as to have an abundance ratio of 0.2 to 5.0% with respect to the abundance of Mg contained in the quenching separator.
Further, Ca, Sr, Ba, Ce, Pr as an impurity element in the magnesium oxide powder in the annealing separator with respect to the total amount of Ca, Sr, Ba, Ce, Pr, Eu, and Gd in the annealing separator. , Eu, and Gd are 0.02 to 0.66. After applying and drying the annealing separator on the front and back surfaces of the steel plate,
A method for manufacturing grain-oriented electrical steel sheets, which is characterized by subjecting final finish annealing.
[2]
The slab is a total of at least one selected from the group consisting of Te, In, Cd, Zn, and Ga: 0.0005% or more, and selected from the group consisting of Au, Ag, Pd, Pt, and Hg. The method for producing a directional electromagnetic steel sheet according to [1], which contains at least one or more totals: 0.0005% or more.
[3]
A base steel sheet containing Si: 2.5 to 4.5% and Mn: 0.04 to 0.20% in mass%, and the balance is Fe and unavoidable impurities, and the surface of the base steel sheet. In addition, in mass%, the sum of at least two or more selected from the group consisting of Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt, and Hg: 0.02 to 0.50%, Ca , Sr, Ba, Ce, Pr, Eu, and Gd, the total of at least one selected from the group: 0.02 to 0.50%, and the total of one or more of Bi and Pb: 0.005% or less. A directional electromagnetic steel sheet containing a coating mainly composed of forsterite.
[4]
On the surface of the base steel plate,
Total of at least one selected from the group consisting of Te, In, Cd, Zn, and Ga: 0.01% or more, and at least one selected from the group consisting of Au, Ag, Pd, Pt, and Hg. The directional electromagnetic steel plate according to [3], wherein a film mainly containing forsterite containing 0.01% or more of the above is present.
[5]
On the surface of the base steel plate,
The depth in the plate thickness direction of the element having the maximum content in the group consisting of Ca, Sr, Ba, Ce, Pr, Eu, and Gd, and the maximum content of the element selected from the group consisting of S and Se. The directional electromagnetic steel plate according to [3] or [4], wherein a film mainly composed of forsterite is present, in which the difference in depth in the plate thickness direction of the amount of elements is within ± 1.5 μm.
本発明によれば、安定した高い磁束密度と優れた被膜密着性を備える方向性電磁鋼板を、良好な熱延性で安定的に製造することができる。 According to the present invention, a grain-oriented electrical steel sheet having a stable high magnetic flux density and excellent film adhesion can be stably manufactured with good heat ductility.
以降の説明において、化学組成についての％はすべて質量％を意味する。 In the following description,% for chemical composition means% by mass.
本発明は、インヒビター機能を補強する補助元素としてＢｉ及び／又はＰｂを０．０００５〜０．０５％含有する方向性電磁鋼板用のスラブに、さらに、Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇからなる群から選択される少なくとも二種以上の合計：０．００１〜０．５００％を含有せしめ、後段で詳述する、所定の製造手順で製造すること、そこで焼鈍分離剤を所定の化学組成に制御することを特徴とする。 The present invention provides a slab for a directional electromagnetic steel plate containing 0.0005 to 0.05% of Bi and / or Pb as an auxiliary element for reinforcing the inhibitor function, and further, Te, In, Cd, Zn, Ga, Au. , Ag, Pd, Pt and Hg, a total of at least two selected from the group: 0.001 to 0.500%, and produced by a predetermined production procedure, which will be described in detail later. It is characterized in that the quenching separator is controlled to a predetermined chemical composition.
そして最終製品である方向性電磁鋼板においては、母材鋼板の表面に、Ｔｅ、Ｉｎ、Ｃｄ、Ｚｎ、Ｇａ、Ａｕ、Ａｇ、Ｐｄ、Ｐｔ、及びＨｇからなる群から選択される少なくとも二種以上の合計：０．０２〜０．５０％と、Ｃａ、Ｓｒ、Ｂａ、Ｃｅ、Ｐｒ、Ｅｕ、及びＧｄからなる群から選択される少なくとも一種以上の合計：０．０２〜０．５０％、Ｂｉ及びＰｂの一種以上の合計：０．００５％以下を含有するフォルステライトを主体とする被膜が形成されていることを特徴とする。 In the final product, the directional electromagnetic steel sheet, at least two or more kinds selected from the group consisting of Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt, and Hg are formed on the surface of the base steel sheet. Total: 0.02 to 0.50% and at least one selected from the group consisting of Ca, Sr, Ba, Ce, Pr, Eu, and Gd: 0.02 to 0.50%, Bi And a total of one or more of Pb: a film mainly containing forsterite containing 0.005% or less is formed.
（方向性電磁鋼板用スラブ）
まず、スラブ組成について説明する。
なお、この説明においては、Ｂｉ、Ｐｂ、さらに、Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇ以外の元素については、一般的な事項であり、公知の範囲で適宜調整が可能である。
(Slab for grain-oriented electrical steel sheet)
First, the slab composition will be described.
In this description, elements other than Bi, Pb, and Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt, and Hg are general matters and are appropriately used within a known range. It can be adjusted.
Ｓｉは、電気抵抗を高め，鉄損を下げる作用をなす重要な元素である。２．５％未満の添加では、鉄損低下効果が発現しない。一方、４．５％を超えると、冷間圧延時に、圧延材が割れ易くなり、圧延不能となることがある。鉄損特性の向上、及び、圧延時の割れ回避の点で、２．８〜３．８％が好ましい。 Si is an important element that has the effect of increasing electrical resistance and reducing iron loss. If the addition is less than 2.5%, the iron loss lowering effect is not exhibited. On the other hand, if it exceeds 4.5%, the rolled material is liable to crack during cold rolling, and rolling may not be possible. From the viewpoint of improving iron loss characteristics and avoiding cracks during rolling, 2.8 to 3.8% is preferable.
Ｃは、強度向上および結晶方位制御に有効な元素であり、所要量添加する。後工程の脱炭焼鈍で脱炭するので、少ないほど、焼鈍時間は短くてすみ、生産性の点で好ましいが、０．０２％未満であると、スラブ加熱時に、結晶粒が粗大化して、磁気特性が低下する。一方、０．１０％を超えると、脱炭焼鈍時間が長くなり、生産性が低下するだけでなく、脱炭が不充分になり易い。強度維持、結晶方位制御及び、脱炭促進の点から、０．０４〜０．０８％が好ましい。 C is an element effective for improving the strength and controlling the crystal orientation, and is added in a required amount. Since decarburization is performed by decarburization annealing in the subsequent step, the smaller the amount, the shorter the annealing time is, which is preferable in terms of productivity. However, if it is less than 0.02%, the crystal grains become coarse during slab heating. The magnetic properties are reduced. On the other hand, if it exceeds 0.10%, the decarburization annealing time becomes long, not only the productivity decreases, but also the decarburization tends to be insufficient. From the viewpoint of maintaining strength, controlling crystal orientation, and promoting decarburization, 0.04 to 0.08% is preferable.
酸可溶性ＡｌとＮは、インヒビターとして機能するＡｌＮ、又は、（Ａｌ、Ｓｉ）Ｎを形成するのに必要な元素である。 Acid-soluble Al and N are elements necessary for forming AlN or (Al, Si) N that functions as an inhibitor.
酸可溶性Ａｌが０．０１％未満、又は、Ｎが０．００３％未満であると、ＡｌＮ、又は、（Ａｌ、Ｓｉ）Ｎの生成量が少なく、充分なインヒビター機能を確保することができなく、所期の二次再結晶が発現しない。一方、酸可溶性Ａｌが０．０５％を超えるか、又は、Ｎが０．０２％を超えると、過剰なインヒビターのため二次再結晶温度が高くなり過ぎて、二次再結晶不良が生じる。適正量のインヒビター確保の点で、酸可溶性Ａｌは、０．０２〜０．０３５％が好ましく、Ｎは、０．００６〜０．０１％が好ましい。製造法との関連で後述するが、製造過程で窒化を行いインヒビター効果を制御する製造法を適用する場合は、Ｎの上限はより低く設定し、上限を０．０１５％、好ましい上限を０．００８％とすることもできる。 When the acid-soluble Al is less than 0.01% or N is less than 0.003%, the amount of AlN or (Al, Si) N produced is small, and a sufficient inhibitor function cannot be ensured. , The expected secondary recrystallization does not occur. On the other hand, when the acid-soluble Al exceeds 0.05% or N exceeds 0.02%, the secondary recrystallization temperature becomes too high due to the excessive inhibitor, and secondary recrystallization failure occurs. In terms of securing an appropriate amount of inhibitor, acid-soluble Al is preferably 0.02 to 0.035%, and N is preferably 0.006 to 0.01%. As will be described later in relation to the manufacturing method, when applying a manufacturing method in which nitriding is performed in the manufacturing process to control the inhibitory effect, the upper limit of N is set lower, the upper limit is 0.015%, and the preferable upper limit is 0. It can also be 008%.
Ｍｎは、Ｍｎ化合物（一般的にはＭｎＳ又はＭｎＳｅ）を主たるインヒビターとして活用する、スラブを比較的高温で加熱する製造方法において、インヒビターを形成するのに必要な元素である。 Mn is an element required to form an inhibitor in a production method in which a slab is heated at a relatively high temperature, utilizing a Mn compound (generally MnS or MnSe) as a main inhibitor.
Ｍｎが０．０４％未満であると、Ｍｎ化合物の生成量が少なく、充分なインヒビター機能が得られなく、所期の二次再結晶が発現しない。一方、Ｍｎが０．２０％を超えると、Ｍｎ化合物を溶体化するスラブ加熱の加熱温度を高くするか、又は、加熱時間を長くせざるを得ず、操業上の負荷が増大する。完全な溶体化処理、及び、適正量のインヒビター確保の点で、Ｍｎは、０．０６〜０．０９％が好ましい。 When Mn is less than 0.04%, the amount of Mn compound produced is small, a sufficient inhibitor function cannot be obtained, and the desired secondary recrystallization does not occur. On the other hand, if Mn exceeds 0.20%, the heating temperature of the slab heating for dissolving the Mn compound must be increased or the heating time must be lengthened, which increases the operational load. Mn is preferably 0.06 to 0.09% in terms of complete solution treatment and securing an appropriate amount of inhibitor.
なお、インヒビターを熱間圧延後の窒化により形成されるＡｌＮで補強し、スラブを比較的低温で加熱する製造方法においては、Ｍｎ化合物のインヒビター機能を担保するための溶体化状況にも尤度が生じて多少の溶け残りが許容されるので、好ましいＭｎ範囲は０．０６〜０．２０％とでき、さらに好ましくは０．０８〜０．１５％となる。 In the production method in which the inhibitor is reinforced with AlN formed by nitriding after hot rolling and the slab is heated at a relatively low temperature, the likelihood of solution formation for ensuring the inhibitor function of the Mn compound is also high. The preferred Mn range can be 0.06 to 0.20%, more preferably 0.08 to 0.15%, since some undissolved residue is allowed to occur.
ＳおよびＳｅは、Ｍｎ化合物（一般的にはＭｎＳ又はＭｎＳｅ）を主たるインヒビターとして活用する、スラブを比較的高温で加熱する製造方法において、インヒビターを形成するのに必要な元素である。 S and Se are elements required to form an inhibitor in a production method in which a slab is heated at a relatively high temperature, utilizing a Mn compound (generally MnS or MnSe) as a main inhibitor.
この場合、ＳとＳｅは単独または複合して添加できるが、添加量は合計含有量で規定すれば事足り、（Ｓ＋０．４・Ｓｅ）で、０．００３〜０．０４％添加する。ここで、式中の０．４は、Ｓの原子量／Ｓｅの原子量で、Ｓｅの作用効果をＳの作用効果に換算する係数である。Ｍｎ化合物のインヒビターとしてＭｎＳのみを活用する場合を考えれば、Ｓ：０．００３〜０．０４％に相当する。また、Ｍｎ化合物のインヒビターとしてＭｎＳｅのみを活用する場合を考えれば、Ｓｅ：０．００７５〜０．１％に相当する。 In this case, S and Se can be added individually or in combination, but it is sufficient if the addition amount is specified by the total content, and 0.003 to 0.04% is added at (S + 0.4 · Se). Here, 0.4 in the formula is the atomic weight of S / the atomic weight of Se, and is a coefficient for converting the action effect of Se into the action effect of S. Considering the case where only MnS is used as an inhibitor of the Mn compound, it corresponds to S: 0.003 to 0.04%. Further, considering the case where only MnSe is used as an inhibitor of the Mn compound, it corresponds to Se: 0.0075 to 0.1%.
（Ｓ＋０．４・Ｓｅ）が０．００３％未満であると、充分なインヒビター機能を確保することができず、所期の二次再結晶が発現しない。一方、（Ｓ＋０．４・Ｓｅ）が０．０４％を超えると、Ｍｎ量にもよるが、Ｍｎ化合物を溶体化するスラブ加熱の加熱温度を高くするか、又は、加熱時間を長くする必要があり、操業上の負荷が増大する。適正量のインヒビター確保の点で、（Ｓ＋０．４・Ｓｅ）は、０．００７〜０．０１２％が好ましい。 If (S + 0.4 · Se) is less than 0.003%, a sufficient inhibitor function cannot be ensured and the desired secondary recrystallization does not occur. On the other hand, when (S + 0.4 · Se) exceeds 0.04%, it is necessary to raise the heating temperature of the slab heating for dissolving the Mn compound or to lengthen the heating time, depending on the amount of Mn. Yes, the operational load increases. In terms of securing an appropriate amount of inhibitor, (S + 0.4 · Se) is preferably 0.007 to 0.012%.
なお、インヒビターを熱間圧延後の窒化により形成されるＡｌＮで補強し、スラブを比較的低温で加熱する製造方法においては、Ｍｎ化合物のインヒビター機能は強くなくてもよいので、（Ｓ＋０．４・Ｓｅ）は０．００３〜０．０２％とでき、好ましい範囲は０．００３〜０．０１０％となる。 In the production method in which the inhibitor is reinforced with AlN formed by nitriding after hot rolling and the slab is heated at a relatively low temperature, the inhibitor function of the Mn compound does not have to be strong, so (S + 0.4. Se) can be 0.003 to 0.02%, and the preferred range is 0.003 to 0.010%.
本発明の製造法で使用するスラブにおいては、磁束密度を高めるためのインヒビター補強元素として、Ｂｉ及び／又はＰｂを含有する。以降、本明細書では、Ｂｉ及びＰｂをまとめて「Ｂ群元素」と記述することがある。Ｂ群元素は、いずれかを単独で含有してもよいし、複合して含有してもよく、本発明ではＢ群元素の合計含有量で規定し、Ｂｉ及びＰｂの一種以上の合計：０．０００５〜０．０５％である。 The slab used in the production method of the present invention contains Bi and / or Pb as an inhibitor reinforcing element for increasing the magnetic flux density. Hereinafter, in the present specification, Bi and Pb may be collectively referred to as "Group B element". Any of the group B elements may be contained alone or in combination. In the present invention, the total content of the group B elements is defined, and the total of one or more Bi and Pb: 0. It is 0005 to 0.05%.
Ｂ群元素の合計が０．０００５％未満であると、磁束密度向上効果が得られない。一方、０．０５％を超えると、磁束密度向上効果は飽和するとともに、熱延性を低下させる。Ｂ群元素の添加効果を確実に得るには、０．００１〜０．００２％の添加が好ましい。 If the total of the elements in Group B is less than 0.0005%, the effect of improving the magnetic flux density cannot be obtained. On the other hand, if it exceeds 0.05%, the effect of improving the magnetic flux density is saturated and the heat ductility is lowered. In order to surely obtain the effect of adding the group B element, the addition of 0.001 to 0.002% is preferable.
本発明のスラブにおいては、以上の成分組成に加え、Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇからなる群から選択される２種以上の元素を合計で０．００１〜０．５００％含有する。以降、本明細書では、Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇをまとめて「Ｘ群元素」と記述することがある。Ｘ群元素はＢ群元素と同時に添加することで格段に磁束密度を高めるが、１種類のみの含有では熱延性がきわめて劣化するとともに、二次再結晶を不安定化にし磁束密度のばらつきを大きくすることにつながる。しかし、２種以上を添加することで熱延性の向上、二次再結晶の安定化による磁束密度のばらつき抑制が可能となる。０．００１％未満の場合では、上記作用が発現しない。一方、０．５００％を超えると、上記磁束密度改善効果は飽和するばかりでなく熱延性を劣化させる場合がある。また添加コストが上昇するため本発明の対象外とする。Ｘ群元素から選択される２種以上の元素の合計は、好ましくは０．００２〜０．２４０％、さらに好ましくは０．００４〜０．１２０％である。 In the slab of the present invention, in addition to the above component compositions, two or more elements selected from the group consisting of Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg are added to a total of 0. Contains 001 to 0.500%. Hereinafter, in the present specification, Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg may be collectively referred to as "Group X element". Group X elements are added at the same time as group B elements to significantly increase the magnetic flux density, but if only one type is contained, the thermal ductility is extremely deteriorated, secondary recrystallization is destabilized, and the variation in magnetic flux density is large. It leads to doing. However, by adding two or more kinds, it is possible to improve the thermal ductility and suppress the variation in the magnetic flux density by stabilizing the secondary recrystallization. If it is less than 0.001%, the above effect does not occur. On the other hand, if it exceeds 0.500%, the effect of improving the magnetic flux density may not only be saturated but also deteriorate the heat ductility. Further, since the addition cost increases, it is excluded from the subject of the present invention. The total of two or more elements selected from the group X elements is preferably 0.002 to 0.240%, more preferably 0.004 to 0.120%.
Ｘ群元素が上記作用を発現させるメカニズムは明確ではないが、以下のように考えられる。Ｂ群元素は、一般的に本発明鋼板およびスラブの組織の主相であるαＦｅ相には固溶しにくい元素であり、インヒビターを強化することで磁束密度向上効果を発現する。そして、Ｂ群元素と親和性の強いＸ群を添加することでインヒビターはより強化され、さらに高い磁束密度の実現が期待できるようになる。一方で、Ｘ群元素は、単独で粒界などに偏析しやすい元素でもある。このため、不用意に添加すると熱延性を低下させるとともに、二次再結晶を不安定にし磁束密度のばらつきを大きくすることにもつながる。Ｘ群元素を単独でなく２種類以上含有させることで、粒界への偏析を抑制しつつ、Ｂ群元素との協働効果を強く発現させ、熱延性の低下を回避しつつ効率的にインヒビター強化機能のみを享受できるようになると考えられる。 The mechanism by which the elements of group X exert the above action is not clear, but it is considered as follows. Group B elements are elements that are generally difficult to dissolve in the αFe phase, which is the main phase of the structure of the steel plate and slab of the present invention, and exhibit the effect of improving the magnetic flux density by strengthening the inhibitor. Then, by adding the X group having a strong affinity with the B group element, the inhibitor is further strengthened, and the realization of a higher magnetic flux density can be expected. On the other hand, the group X element is also an element that is easily segregated at grain boundaries and the like by itself. Therefore, if it is added carelessly, the thermal ductility will be lowered, and the secondary recrystallization will be unstable, leading to a large variation in the magnetic flux density. By containing two or more types of group X elements instead of a single element, segregation to grain boundaries is suppressed, a strong cooperative effect with group B elements is exhibited, and an inhibitor is efficiently suppressed while avoiding a decrease in heat ductility. It is thought that only the enhanced functions will be enjoyed.
また、上記作用を顕著に発現させる観点から、Ｘ群元素を２つに分類し、Ｔｅ，Ｉｎ，Ｃｄ，ＺｎおよびＧａからなる群とＡｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇからなる群からそれぞれ少なくとも１種類ずつ組み合わせて含有することが望ましい。以降、本明細書では、Ｔｅ，Ｉｎ，Ｃｄ，ＺｎおよびＧａをまとめて「Ｃ類元素」、Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇをまとめて「Ｄ類元素」と記述することがある。本発明のスラブにおいては、Ｃ類元素から選択される少なくとも一種以上の合計：０．０００５％以上、Ｄ類元素から選択される少なくとも一種以上の合計：０．０００５％以上を満足することで上記作用がより顕著に発揮される。（ただし、前述のとおり、Ｘ群の合計は０．５００％以下とする。）Ｃ類元素またはＤ類元素のどちらか一方または両方が０．０００５％未満では顕著な効果が得られない。Ｃ類およびＤ類の各々について、０．００１〜０．１２０％が好ましく、０．００２〜０．０６０％がより好ましい。なお、Ｃ類元素の合計とＤ類元素の合計は、同じ量である必要はないが、Ｘ群元素の合計含有量が一定であれば、同程度の含有量とすることで効果はより顕著になる。同程度とは、一方の類の元素の量に対して、他方の類の元素の量が０．５〜１．５倍、より好ましくは０．８〜１．２倍であることを指す。 Further, from the viewpoint of remarkably exhibiting the above action, the X group elements are classified into two groups, and at least from the group consisting of Te, In, Cd, Zn and Ga and the group consisting of Au, Ag, Pd, Pt and Hg, respectively. It is desirable to contain them in combination one by one. Hereinafter, in the present specification, Te, In, Cd, Zn and Ga may be collectively referred to as “C-class element”, and Au, Ag, Pd, Pt and Hg may be collectively referred to as “D-class element”. In the slab of the present invention, the total of at least one selected from the C-class elements: 0.0005% or more and the total of at least one or more selected from the D-class elements: 0.0005% or more are satisfied. The action is more pronounced. (However, as described above, the total of the X group is 0.500% or less.) If either or both of the C-class element and the D-class element is less than 0.0005%, a remarkable effect cannot be obtained. For each of Class C and Class D, 0.001 to 0.120% is preferable, and 0.002 to 0.060% is more preferable. The total amount of the C group elements and the total amount of the D group elements do not have to be the same amount, but if the total content of the group X elements is constant, the effect is more remarkable by setting the total content to the same level. become. The same degree means that the amount of the element of the other class is 0.5 to 1.5 times, more preferably 0.8 to 1.2 times the amount of the element of one class.
このメカニズムは明確ではないが、Ｃ類元素はＤ類元素との親和性が高く、この両方が共存することで、Ｂ群元素を含めた相互作用が複雑化するのみならず、各類元素による安定化合物が形成し、二次再結晶における微細粒の残存や熱延性の低下を回避する効果が増長することに加え、インヒビター効果が安定化すると考えられる。 Although this mechanism is not clear, C-class elements have a high affinity with D-class elements, and the coexistence of both of them not only complicates the interaction including group B elements, but also depends on each class element. It is considered that the stable compound is formed, and the effect of avoiding the residual fine particles and the decrease in heat ductility in the secondary recrystallization is enhanced, and the inhibitory effect is stabilized.
さらに、本発明のスラブには、他のインヒビター構成元素として、Ｃｕ、Ｓｎ、Ｓｂ等の１種又は２種以上を、公知の範囲内で添加してもよい。一般的な合計量は、０．０００５〜０．５％である。 Further, one or more of Cu, Sn, Sb and the like may be added to the slab of the present invention as other inhibitor constituent elements within a known range. A typical total amount is 0.0005-0.5%.
スラブの化学組成の残部は、Ｆｅおよび不純物である。不純物とは、スラブを工業的に製造する際に、原料としての鉱石、スクラップ、または製造環境等から混入する元素を意味する。また、公知の効果を期待して、Ｆｅを公知の元素で本発明効果を消失させない範囲で置き換えて添加することを除外するものではない。 The rest of the chemical composition of the slab is Fe and impurities. Impurities mean elements mixed in from ore, scrap, manufacturing environment, etc. as raw materials when slabs are industrially manufactured. Further, in anticipation of a known effect, it is not excluded to replace Fe with a known element within a range that does not eliminate the effect of the present invention.
（方向性電磁鋼板）
次に方向性電磁鋼板について説明する。
なお、この説明においては、Ｂｉ、Ｐｂ；Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇ；ならびにＣａ、Ｓｒ、Ｂａ、Ｃｅ、Ｐｒ、Ｅｕ、およびＧｄ以外の元素については、一般的な事項であり、公知の範囲で適宜調整が可能である。
(Directional magnetic steel sheet)
Next, the grain-oriented electrical steel sheet will be described.
In this description, elements other than Bi, Pb; Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg; and Ca, Sr, Ba, Ce, Pr, Eu, and Gd are used. Is a general matter and can be appropriately adjusted within a known range.
方向性電磁鋼板の母材鋼板の化学組成は基本的には素材である上述のスラブ組成に準じたものになる。しかし、一般的な方向性電磁鋼板の製造においては製造過程で脱炭焼鈍および純化焼鈍により含有元素の一部が系外に排出されるため、素材であるスラブと最終製品である方向性電磁鋼板の母材鋼板の化学組成は明確に異なるものとなる。以下の説明はこれを念頭にしたものである。 The chemical composition of the base steel sheet of the grain-oriented electrical steel sheet basically conforms to the above-mentioned slab composition which is the material. However, in the production of general grain-oriented electrical steel sheets, some of the contained elements are discharged to the outside of the system by decarburization annealing and purification annealing during the manufacturing process, so the slab as the material and the grain-oriented electrical steel sheet as the final product The chemical composition of the base steel sheet is clearly different. The following explanation is with this in mind.
また、方向性電磁鋼板の製造過程の仕上焼鈍において、母材鋼板の表面には一般的に「グラス被膜」、「一次被膜」と呼ばれるフォルステライトを主体とする被膜が形成される。本発明の方向性電磁鋼板は、この被膜にＸ群元素、Ｂ群元素、さらにＣａ、Ｓｒ、Ｂａ、Ｃｅ、Ｐｒ、Ｅｕ、及びＧｄからなる群から選択される少なくとも一種以上が含有されることを大きな特徴としている。 Further, in the finish annealing in the manufacturing process of the grain-oriented electrical steel sheet, a film mainly composed of forsterite, which is generally called "glass coating" or "primary coating", is formed on the surface of the base steel sheet. In the directional electromagnetic steel plate of the present invention, the coating film contains at least one selected from the group consisting of group X elements, group B elements, and Ca, Sr, Ba, Ce, Pr, Eu, and Gd. Is a major feature.
まず母材鋼板の化学組成について説明する。 First, the chemical composition of the base steel sheet will be described.
Ｓｉは、電気抵抗を高め，鉄損を下げる作用をなす重要な元素である。２．５％未満の添加では、鉄損低下効果が発現しない。一方、４．５％を超えると、冷間圧延時に、圧延材が割れ易くなり、圧延不能となることがある。鉄損特性の向上、及び、圧延時の割れ回避の点で、２．８〜３．８％が好ましい。 Si is an important element that has the effect of increasing electrical resistance and reducing iron loss. If the addition is less than 2.5%, the iron loss lowering effect is not exhibited. On the other hand, if it exceeds 4.5%, the rolled material is liable to crack during cold rolling, and rolling may not be possible. From the viewpoint of improving iron loss characteristics and avoiding cracks during rolling, 2.8 to 3.8% is preferable.
Ｍｎは、製造過程での系外への排出を考慮したとしても、前述のインヒビター制御の観点からスラブに添加されたものの少なからざる量が最終製品に含有される元素である。最終製品での含有量が、０．０４％未満となるほどの純化焼鈍を実施することはコスト的に不利であり、困難である。スラブに添加されたものの大部分が最終製品に残存する場合として、上限を０．２０％とする。 Mn is an element contained in the final product in a considerable amount of what is added to the slab from the viewpoint of the above-mentioned inhibitor control, even if the discharge to the outside of the system in the manufacturing process is taken into consideration. It is costly and difficult to carry out purification annealing so that the content in the final product is less than 0.04%. The upper limit is 0.20%, assuming that most of what is added to the slab remains in the final product.
スラブ組成において必須元素であったＣ、酸可溶性Ａｌ、Ｎ、ＳおよびＳｅは、製品においては選択元素となる。 C, acid-soluble Al, N, S and Se, which are essential elements in the slab composition, are selective elements in the product.
Ｃは製造過程の脱炭焼鈍で系外に排出され、スラブ組成から明確に低減される。最終製品においては含有される必要はなく、時効により磁気特性を阻害することもあるため、基本的には低減すべき元素であり、ゼロでも構わない。実用的な脱炭焼鈍能力を考慮すれば、０．００５％以下とすべきである。一方で脱炭焼鈍のコストを考慮すると、０．０００１％未満とすることは困難である。 C is discharged out of the system by decarburization annealing in the manufacturing process and is clearly reduced from the slab composition. It is not necessary to be contained in the final product, and the magnetic properties may be impaired by aging. Therefore, it is basically an element to be reduced and may be zero. Considering the practical decarburization annealing capacity, it should be 0.005% or less. On the other hand, considering the cost of decarburization annealing, it is difficult to make it less than 0.0001%.
酸可溶性ＡｌとＮは前述の通り、製造過程においてインヒビターとして活用される元素であるが、最終製品において含有される必要はない。これら元素は製造過程の純化焼鈍において多くの割合が系外に排出される。Ａｌは飽和磁束密度を低下させ、Ｎは磁気時効を引き起こすためゼロでも構わない。実用的な純化焼鈍能力とコストを考慮すると、酸可溶性Ａｌ：０．０００１〜０．００５％、Ｎ：０．０００１〜０．００５％となる。 As described above, acid-soluble Al and N are elements that are utilized as inhibitors in the manufacturing process, but do not need to be contained in the final product. A large proportion of these elements are discharged from the system during purification annealing in the manufacturing process. Al lowers the saturation magnetic flux density, and N causes magnetic aging, so it may be zero. Considering the practical purification annealing ability and cost, the acid-soluble Al: 0.0001 to 0.005% and N: 0.0001 to 0.005%.
ＳおよびＳｅも前述の通り、製造過程においてインヒビターとして活用される元素であるが、最終製品において含有される必要はなくゼロでも構わない。これら元素は製造過程の純化焼鈍において多くの割合が系外に排出される。実用的な純化焼鈍能力とコストを考慮すると、Ｓ、Ｓｅとも０．０００１〜０．００５％となる。 As described above, S and Se are also elements that are utilized as inhibitors in the manufacturing process, but they do not have to be contained in the final product and may be zero. A large proportion of these elements are discharged from the system during purification annealing in the manufacturing process. Considering the practical purification annealing capacity and cost, both S and Se are 0.0001 to 0.005%.
注意を要するのは、スラブで必須元素となっているＢ群元素およびＸ群元素である。これらは高温での純化焼鈍を伴う一般的な方向性電磁鋼板の製造方法においては、母材鋼板からほぼ完全に排除され、製品板において母材鋼板の化学組成として検出することは非常に困難となる。このため本発明では、方向性電磁鋼板の母材鋼板の化学組成としては、Ｂ群元素およびＸ群元素は規定せず、後述の一次被膜の化学組成において規定している。ただし、本発明の方向性電磁鋼板は、Ｂ群元素およびＸ群元素を検出される量で含有する母材鋼板を除外するものではない。 Attention should be paid to the group B and group X elements, which are essential elements in the slab. These are almost completely eliminated from the base steel sheet in the general method for manufacturing grain-oriented electrical steel sheets accompanied by purification annealing at high temperature, and it is very difficult to detect them as the chemical composition of the base steel sheet in the product board. Become. Therefore, in the present invention, the group B element and the group X element are not specified as the chemical composition of the base steel sheet of the directional electromagnetic steel sheet, but are specified in the chemical composition of the primary coating described later. However, the grain-oriented electrical steel sheet of the present invention does not exclude the base steel sheet containing the B group element and the X group element in a detected amount.
方向性電磁鋼板の母材鋼板の化学組成の残部は、Ｆｅおよび不純物である。不純物とは、母材鋼板を工業的に製造する際に、原料としての鉱石、スクラップ、または製造環境等から混入する元素を意味する。また、公知の効果を期待して、Ｆｅを公知の効果を発現させる元素により本発明効果を消失させない範囲で置き換えて添加することを除外するものではない。 The balance of the chemical composition of the base steel sheet of the grain-oriented electrical steel sheet is Fe and impurities. Impurities mean elements mixed from ore, scrap, manufacturing environment, etc. as raw materials when the base steel sheet is industrially manufactured. Further, in anticipation of a known effect, it is not excluded to replace Fe with an element that exhibits the known effect within a range that does not eliminate the effect of the present invention.
次に本発明の方向性電磁鋼板の最大の特徴とも言える被膜の組成について説明する。ここで対象となる「被膜」は、前述のとおり一般的に「グラス被膜」、「一次被膜」と呼ばれる被膜である。その形成機構自体は、方向性電磁鋼板において良く知られたものであり、特別なものではない。つまり、仕上焼鈍前にいわゆる「焼鈍分離剤」として鋼板表面に塗布された酸化物が、仕上焼鈍中に母材鋼板と反応して形成された酸化物が主体となり鋼板表面を覆った酸化物層である。この反応過程では、母材鋼板から様々な元素が系外に排出されるが、その際に鋼板表面の焼鈍分離剤起因の酸化物や雰囲気中の酸素と反応する。仕上焼鈍後、その一部は自然剥落、または水洗や軽酸洗等で除去されるが、一部は母材鋼板表面との複雑な凹凸界面の形成により固着して保持される。反応に際しては、母材鋼板側から仕上焼鈍雰囲気に亘る元素の拡散が起きて厚さ方向に大きな組成変化が生じるため、最終的に母材鋼板表面に固着して残存する「一次被膜」の化学組成は焼鈍分離剤の化学組成とは全く異なったものとなる。一般的にはフォルステライトを主体としており、例えば、フォルステライト（Ｍｇ２ＳｉＯ４）、スピネル（ＭｇＡｌ２Ｏ４）、または、コーディエライト（Ｍｇ２Ａｌ４Ｓｉ５Ｏ１６）などの複合酸化物によって構成されるものである。また、鋼板や焼鈍分離剤から由来する金属の化合物として、比較的少量のＭｎ等の硫化物、Ｔｉ等の窒化物が分散することもある。以降、本発明でＸ群元素を含有すべきフォルステライトを主体とする被膜を単に「一次被膜」と記述することがある。 Next, the composition of the coating film, which can be said to be the greatest feature of the grain-oriented electrical steel sheet of the present invention, will be described. The target "coating" here is a coating generally called a "glass coating" or a "primary coating" as described above. The forming mechanism itself is well known in grain-oriented electrical steel sheets and is not special. That is, an oxide layer in which the oxide applied to the surface of the steel sheet as a so-called "annealing separator" before the finish annealing is mainly composed of the oxide formed by reacting with the base steel sheet during the finish annealing to cover the steel sheet surface. Is. In this reaction process, various elements are discharged from the base steel sheet to the outside of the system, and at that time, they react with oxides caused by the annealing separator on the surface of the steel sheet and oxygen in the atmosphere. After finish annealing, a part of it is naturally peeled off or removed by washing with water or light pickling, but a part is fixed and held by forming a complicated uneven interface with the surface of the base steel sheet. During the reaction, the elements diffuse from the base steel sheet side to the finish annealing atmosphere and a large composition change occurs in the thickness direction, so the chemistry of the "primary coating" that finally adheres to the surface of the base steel sheet and remains. The composition is completely different from the chemical composition of the annealing separator. Generally, it is mainly composed of forsterite, for example, a composite oxide such as forsterite (Mg 2 SiO 4 ), spinel (Mg Al 2 O 4 ), or cordierite (Mg 2 Al 4 Si 5 O 16). It is composed of. Further, as a compound of a metal derived from a steel sheet or an annealing separator, a relatively small amount of a sulfide such as Mn and a nitride such as Ti may be dispersed. Hereinafter, in the present invention, a film mainly containing forsterite, which should contain a group X element, may be simply referred to as a “primary film”.
本発明の方向性電磁鋼板は、純化焼鈍により母材鋼板から排出されたＸ群元素が一次被膜に取り込まれ、製品板の一次被膜の化学組成に特徴が現れる。本発明の方向性電磁鋼板は、母材鋼板の表面にＸ群元素から選択される少なくとも二種以上の合計で０．０２〜０．５０％を含有する被膜が形成されている。これにより、本発明の方向性電磁鋼板は、磁束密度が高く、かつその変動が小さく安定した特性を有する方向性電磁鋼板となる。好ましくは０．０３〜０．４０％、さらに好ましくは０．０５〜０．３０％である。 In the grain-oriented electrical steel sheet of the present invention, the group X elements discharged from the base steel sheet by purification annealing are incorporated into the primary coating, and the chemical composition of the primary coating of the product plate is characterized. In the grain-oriented electrical steel sheet of the present invention, a coating film containing 0.02 to 0.50% in total of at least two or more kinds selected from group X elements is formed on the surface of the base steel sheet. As a result, the grain-oriented electrical steel sheet of the present invention becomes a grain-oriented electrical steel sheet having a high magnetic flux density, small fluctuations thereof, and stable characteristics. It is preferably 0.03 to 0.40%, more preferably 0.05 to 0.30%.
また、スラブ組成で説明したのと同様に、高い磁束密度の安定化効果を顕著に発現させる観点から、本発明の方向性電磁鋼板で規定される上記一次被膜は、Ｃ類元素とＤ類元素からそれぞれ少なくとも１種類ずつを組み合わせて含有することが望ましい。上記一次被膜においては、Ｃ類元素から選択される少なくとも一種以上の合計：０．０１％以上、かつＤ類元素から選択される少なくとも一種以上の合計：０．０１％以上を満足することで上記効果がより顕著に発揮される。（ただし、前述のとおり、Ｘ群の合計は０．５０％以下とする。）Ｃ類元素またはＤ類元素のどちらか一方または両方が０．０１％未満では効果が得られない。Ｃ類およびＤ類の各々について、０．０２〜０．２０％が好ましく、０．０３〜０．１５％がより好ましい。なお、Ｃ類元素の合計とＤ類元素の合計は、同じ量である必要はないが、Ｘ群元素の合計含有量が一定であれば、同程度の含有量とすることで効果はより顕著になる。同程度とは、一方の類の元素の量に対して、他方の類の元素の量が０．５〜１．５倍、より好ましくは０．８〜１．２倍であることを指す。 Further, as described in the slab composition, from the viewpoint of remarkably exhibiting the stabilizing effect of high magnetic flux density, the primary coating defined by the grain-oriented electrical steel sheet of the present invention is a class C element and a class D element. It is desirable to contain at least one of each in combination. In the primary coating, the total of at least one type selected from the C-class elements: 0.01% or more and the total of at least one type or more selected from the D-class elements: 0.01% or more are satisfied. The effect is more pronounced. (However, as described above, the total of the X group is 0.50% or less.) If either or both of the C-class element and the D-class element is less than 0.01%, the effect cannot be obtained. For each of Class C and Class D, 0.02 to 0.20% is preferable, and 0.03 to 0.15% is more preferable. The total amount of the C group elements and the total amount of the D group elements do not have to be the same amount, but if the total content of the group X elements is constant, the effect is more remarkable by setting the total content to the same level. become. The same degree means that the amount of the element of the other class is 0.5 to 1.5 times, more preferably 0.8 to 1.2 times the amount of the element of one class.
さらに上記一次被膜には、Ｂ群元素が含有されても良い。ただしＢ群元素は純化焼鈍における蒸発により、母材鋼板に固着する一次被膜中には残存しにくい。これはＢ群元素の蒸気圧が高いためと考えられる。このため、一次被膜の分析においてＢ群元素の含有量は検出限界以下、すなわちゼロとなることも多いが、わずかに検出されることもある。この場合の検出量は、Ｂ群元素の一種以上の合計で０．００５％以下であるが、この検出は、製造過程でＢ群元素がインヒビター補強元素として活用されていたことの証左とも言え、これを考慮して本発明の特徴の一つとして規定するものである。 Further, the primary coating may contain a group B element. However, the group B elements are unlikely to remain in the primary coating that adheres to the base steel sheet due to evaporation during purification annealing. It is considered that this is because the vapor pressure of the group B elements is high. Therefore, in the analysis of the primary coating, the content of the group B element is often below the detection limit, that is, zero, but it may be slightly detected. The amount detected in this case is 0.005% or less in total for one or more group B elements, but this detection can be said to be proof that the group B elements were utilized as inhibitor reinforcing elements in the manufacturing process. In consideration of this, it is defined as one of the features of the present invention.
さらに上記一次被膜には、Ｃａ，Ｓｒ，Ｂａ，Ｃｅ，Ｐｒ，Ｅｕ及びＧｄからなる群から選択される少なくとも一種以上の合計が０．０２〜０．５０％で含有される。以降、本明細書では、Ｃａ，Ｓｒ，Ｂａ，Ｃｅ，Ｐｒ，Ｅｕ及びＧｄをまとめて「Ｙ群元素」と記述することがある。一次被膜にＹ群元素を上記範囲で含有させることで、方向性電磁鋼板の被膜密着性が向上する。その理由は明確ではないが、以下のように考えられる。 Further, the primary coating contains 0.02 to 0.50% of the total of at least one selected from the group consisting of Ca, Sr, Ba, Ce, Pr, Eu and Gd. Hereinafter, in the present specification, Ca, Sr, Ba, Ce, Pr, Eu and Gd may be collectively referred to as “Y group element”. By including the Y group element in the primary film in the above range, the film adhesion of the grain-oriented electrical steel sheet is improved. The reason is not clear, but it can be considered as follows.
まず、本発明が対象とするＸ群元素を含有する鋼板において被膜密着性が不十分となる原因を説明する。Ｘ群元素が粒界に偏析しやすい元素であることは前述のとおりであるが、このような偏析は方向性電磁鋼板の製造過程において鋼板表面に一次被膜が形成する過程での鋼板と一次被膜の界面においても生じる。Ｘ群元素が単独元素として上記界面に濃化し酸化層に固溶すると酸化物である一次被膜の融点を著しく低下させる。このため、一次被膜の形成過程において界面凹凸が消失し、一般的に母鋼板と被膜の密着性の主因子となっている界面凹凸によるアンカー効果が働くなり、密着性が低下する。 First, the cause of insufficient film adhesion in the steel sheet containing the group X element, which is the subject of the present invention, will be described. As mentioned above, the element X is an element that easily segregates at the grain boundaries. Such segregation is caused by the steel sheet and the primary film in the process of forming the primary film on the surface of the grain steel sheet in the manufacturing process of the grain-oriented electrical steel sheet. It also occurs at the interface of. When the group X element is concentrated as a single element at the interface and dissolved in the oxide layer, the melting point of the primary film, which is an oxide, is significantly lowered. For this reason, the interfacial unevenness disappears in the process of forming the primary coating, and the anchor effect due to the interfacial unevenness, which is generally the main factor of the adhesion between the mother steel plate and the coating, works, and the adhesion is lowered.
このような状況にある鋼板において、Ｙ群元素が存在することにより被膜密着性が向上する原因は以下のように考えられる。Ｙ群元素はＭｎＳよりも安定な硫化物を形成する傾向が強く、Ｍｎが硫化物として化合物を形成することを回避させる。このため、ＭｎはＸ群元素との化合物を形成するようになる。あるいはＹ群元素はＸ群元素との化合物として存在する。このため、Ｘ群元素が母材鋼板と一次被膜の界面に偏析したとしても酸化層に固溶しないため界面凹凸の消失は回避され、被膜密着性への悪影響は抑制される。０．０２％以下であると、その効果は発揮されず、０．５０％以上であると、被膜と地鉄の界面の凹凸が発達しすぎて磁気特性が劣化する。ここで、硫化物がもっとも無害化されている（言い換えると、Ｙ群元素がＭｎＳよりも安定な硫化物を形成して、ＭｎとＸ群元素が化合物を形成することにより、Ｘ群元素による被膜密着性への悪影響が抑制されている）状況の場合、Ｙ群元素はＳ及びＳｅと同じ板厚深さの領域に濃化する。Ｙ群元素の深さとＳ及びＳｅの深さの差が±１．５μｍ以下であれば、Ｙ群元素が鋼中で分解されづらい硫化物を形成しており、被膜密着性の改善効果が十分に発揮されている状態である。
上記の状態を確認する場合、測定を容易に行なう観点から、Ｙ群元素（Ｃａ、Ｓｒ、Ｂａ、Ｃｅ、Ｐｒ、Ｅｕ、及びＧｄ）のうち最大の含有量の元素の板厚方向深さと、ＳおよびＳｅからなる群から選択される元素のうち、最大の含有量の元素の板厚方向深さの差が±１．５μｍ以内の範囲であることを確認してもよい。
In a steel sheet in such a situation, the cause for improving the film adhesion due to the presence of the Y group element is considered as follows. Group Y elements have a stronger tendency to form stable sulfides than MnS, and prevent Mn from forming compounds as sulfides. Therefore, Mn forms a compound with the X group element. Alternatively, the Y group element exists as a compound with the X group element. Therefore, even if the group X element segregates at the interface between the base steel sheet and the primary coating, it does not dissolve in the oxide layer, so that the disappearance of the interface unevenness is avoided and the adverse effect on the coating adhesion is suppressed. If it is 0.02% or less, the effect is not exhibited, and if it is 0.50% or more, the unevenness at the interface between the coating film and the base iron develops too much and the magnetic characteristics deteriorate. Here, the sulfide is most detoxified (in other words, the Y group element forms a sulfide that is more stable than MnS, and the Mn and the X group element form a compound, so that the film is formed by the X group element. In the case of the situation (the adverse effect on the adhesion is suppressed), the Y group elements are concentrated in the region having the same plate thickness and depth as S and Se. If the difference between the depth of the Y group element and the depth of S and Se is ± 1.5 μm or less, the Y group element forms a sulfide that is difficult to decompose in the steel, and the effect of improving the film adhesion is sufficient. It is in a state of being demonstrated.
When confirming the above state, from the viewpoint of facilitating the measurement, the depth in the plate thickness direction of the element having the largest content among the Y group elements (Ca, Sr, Ba, Ce, Pr, Eu, and Gd) and It may be confirmed that the difference in depth in the plate thickness direction of the element having the maximum content among the elements selected from the group consisting of S and Se is within ± 1.5 μm.
ここで注意すべきは、Ｙ群元素の添加方法である。例えば、素材であるスラブにＹ群元素を添加し、製造工程を経て最終的に一次被膜にＹ群元素が含有されるようにすることも考えられる。しかし、本発明鋼板は前述のようにＸ群元素をＢ群元素と協働させて熱延性の低下や磁気特性向上を図るものであるため、鋼材全体でＸ群元素がＭｎまたはＹ群元素と化合物を形成してしまうのは好ましい形態ではない。このため、Ｙ群元素は焼鈍分離剤に添加し、母鋼板と一次被膜の界面近傍領域だけで上記の作用が起きるようにすることが好ましい。これについては製造方法との関連で後述する。 What should be noted here is the method of adding the Y group element. For example, it is conceivable to add the Y group element to the slab which is the material so that the Y group element is finally contained in the primary coating through the manufacturing process. However, as described above, the steel plate of the present invention cooperates with the group B elements to reduce the thermal ductility and improve the magnetic properties. Therefore, the group X elements are Mn or the Y group elements in the entire steel material. Forming a compound is not a preferred form. Therefore, it is preferable that the Y group elements are added to the annealing separator so that the above action occurs only in the region near the interface between the mother steel plate and the primary coating. This will be described later in relation to the manufacturing method.
上記の一次被膜は母材鋼板の表面に形成されている。母材鋼板の両面はもちろん、片面のみに形成されている場合も、本発明の対象とする。また、表面の全面が覆われている必要はなく、部分的な被覆状態であっても本発明の対象とする。 The primary coating is formed on the surface of the base steel sheet. The subject of the present invention is not only the case where the base steel plate is formed on both sides but also on only one side. Further, it is not necessary that the entire surface is covered, and even a partially covered state is the subject of the present invention.
注意を要するのは、一次被膜は仕上焼鈍後に形成していたとしても、その後の処理、例えば研削や酸洗などの化学処理で完全に除去できることである。つまり、本発明のスラブおよび製造方法を利用して製造され、本発明の効果を享受した方向性電磁鋼板であっても、仕上焼鈍後に形成されていた一次被膜が完全に除去されてしまえば、方向性電磁鋼板としては本発明の範囲外の鋼板になってしまう。この点で、方向性電磁鋼板としての本発明は、本発明効果を享受した鋼板への権利行使の備えが十分とは言えない面がある。ただしこれは逆に見ると、母材鋼板の一部にでも本発明が規定する一次被膜が形成（残存）していれば、本発明の効果を享受した本発明の範囲内にある鋼板との判断を可能とすることの根拠にもなっている。 It should be noted that even if the primary coating is formed after finish annealing, it can be completely removed by subsequent treatments, such as chemical treatments such as grinding and pickling. That is, even in a grain-oriented electrical steel sheet manufactured by using the slab and the manufacturing method of the present invention and enjoying the effect of the present invention, if the primary coating formed after finish annealing is completely removed, The grain-oriented electrical steel sheet is outside the scope of the present invention. In this respect, the present invention as a grain-oriented electrical steel sheet is not sufficiently prepared for exercising rights on a steel sheet that enjoys the effects of the present invention. However, when viewed from the opposite side, if the primary coating defined by the present invention is formed (residual) even on a part of the base steel sheet, it is a steel sheet within the scope of the present invention that enjoys the effects of the present invention. It is also the basis for making decisions possible.
（製造法）
次に本発明の製造方法について説明する。
(Manufacturing method)
Next, the production method of the present invention will be described.
本発明は、Ｓｉ：２．５〜４．５％、Ｃ：０．０２〜０．１０％、酸可溶性Ａｌ：０．０１〜０．０５％、Ｎ：０．００３〜０．０２％、Ｓ＋０．４・Ｓｅ：０．００３〜０．０４％、Ｍｎ：０．０４〜０．２０％、Ｂｉ及びＰｂの一種以上の合計：０．０００５〜０．０５％、さらに、Ｔｅ、Ｉｎ、Ｃｄ、Ｚｎ、Ｇａ、Ａｕ、Ａｇ、Ｐｄ、Ｐｔ、及びＨｇからなる群から選択される少なくとも二種以上の合計：０．００１〜０．５００％を含有し、残部がＦｅ及び不可避的不純物からなるスラブを、１０００〜１４５０℃に加熱し、熱間圧延で熱延板とし、該熱延板に焼鈍を施し、次いで、酸洗の後、一回又は焼鈍を挟む二回の冷間圧延で冷延板とし、該冷延板に脱炭焼鈍を施し、必要に応じて該焼鈍中又は焼鈍後に窒化処理を施し、続いて、所定の焼鈍分離剤を塗布し、最終仕上焼鈍を施すことを特徴とする。 In the present invention, Si: 2.5 to 4.5%, C: 0.02 to 0.10%, acid-soluble Al: 0.01 to 0.05%, N: 0.003 to 0.02%, S + 0.4 · Se: 0.003 to 0.04%, Mn: 0.04 to 0.20%, total of one or more types of Bi and Pb: 0.0005 to 0.05%, and Te, In, A total of at least two selected from the group consisting of Cd, Zn, Ga, Au, Ag, Pd, Pt, and Hg: 0.001 to 0.500%, with the balance being from Fe and unavoidable impurities. The slab is heated to 1000 to 1450 ° C., hot-rolled to obtain a hot-rolled plate, the hot-rolled plate is annealed, and then pickled and then cold-rolled once or twice with annealing. A cold-rolled plate is prepared, and the cold-rolled plate is decarburized and annealed, and if necessary, nitriding is performed during or after the annealing, and then a predetermined annealing separator is applied and final finish annealing is performed. It is a feature.
この製造法においては、スラブにＢ群元素、Ｘ群元素を所定の条件で含有させること、焼鈍分離剤にＹ群元素を所定の条件で含有させること以外は、公知の条件に準ずるものであり、特別な条件である必要はない。以下、この前提で説明する。 In this production method, the known conditions are followed except that the slab contains the B group element and the X group element under the predetermined conditions, and the annealing separator contains the Y group element under the predetermined conditions. , It does not have to be a special condition. Hereinafter, this premise will be described.
上記化学組成のスラブは、通常の溶解−鋳造方法で製造することができる。 The slab having the above chemical composition can be produced by a usual melting-casting method.
Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇは、Ｆｅに固溶し難い元素であるが、例えば、溶鋼を攪拌しながら、各金属を添加して、Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇ：０．００１〜０．５００％を含むスラブを製造することができる。 Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg are elements that are difficult to dissolve in Fe. For example, while stirring molten steel, each metal is added to Te, In. , Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg: 0.001 to 0.500% can be produced.
インヒビター構成元素を、鋼のマトリックス中に溶体化するため、鋳造したスラブを、１０００〜１４５０℃に加熱する、後の工程で、ＡｌＮ（インヒビター）を導入する窒化処理を行う場合は、スラブの加熱温度を１２５０℃未満とできることは公知の通りである。 In order to dissolve the inhibitor constituent elements in the steel matrix, the cast slab is heated to 1000 to 1450 ° C. In the subsequent step, when the nitriding treatment for introducing AlN (inhibitor) is performed, the slab is heated. It is known that the temperature can be set to less than 1250 ° C.
スラブ加熱に続く工程における条件は、通常の条件でよい。 The conditions in the step following the slab heating may be normal conditions.
加熱されたスラブを熱間圧延して熱延板に仕上る。熱延板の板厚は、特に限定されないが、後の冷間圧延の圧下率との関係で、通常は、１．８〜３．５ｍｍとする。熱延板に、通常、７５０〜１２００℃、３０秒〜１０分の焼鈍を施した後、酸洗に次いで、冷間圧延に供する。 The heated slab is hot-rolled to make a hot-rolled plate. The thickness of the hot-rolled sheet is not particularly limited, but is usually 1.8 to 3.5 mm in relation to the reduction rate of the subsequent cold rolling. The hot-rolled sheet is usually annealed at 750 to 1200 ° C. for 30 seconds to 10 minutes, and then pickled and then subjected to cold rolling.
冷間圧延は、１回行うか、又は、焼鈍を挟んで２回に分けて行う。１回の冷間圧延は、焼鈍を途中に含まず、１回又は複数回の冷間圧延を行うことを意味する。いずれの冷間圧延においても、最終圧下率を８０〜９５％とするのが好ましい。 Cold rolling is performed once or divided into two times with annealing in between. One cold rolling does not include annealing in the middle, and means that one or more cold rollings are performed. In any cold rolling, the final rolling reduction is preferably 80 to 95%.
冷間圧延を、焼鈍を挟んで２回に分けて行う場合、焼鈍は、７５０〜１２００℃で、３０秒〜１０分間、行うのが好ましい。 When the cold rolling is carried out in two steps with annealing in between, the annealing is preferably carried out at 750 to 1200 ° C. for 30 seconds to 10 minutes.
冷間圧延が１回であると、電磁鋼板の幅方向及び長手方向における磁気特性が不均一になり易い。冷間圧延を２回に分けて行うと、磁気特性は均一化するが、到達磁束密度は低下する傾向がある。冷間圧延の回数は、所望の磁気特性と製造コストを勘案して、適宜、選択する。 If the cold rolling is performed once, the magnetic characteristics of the electrical steel sheet in the width direction and the longitudinal direction tend to be non-uniform. When the cold rolling is performed in two steps, the magnetic characteristics become uniform, but the ultimate magnetic flux density tends to decrease. The number of cold rollings is appropriately selected in consideration of desired magnetic properties and manufacturing cost.
冷間圧延の後、冷延板を脱炭焼鈍する。脱炭焼鈍は、通常、水素と窒素を含む湿潤雰囲気中で、８００〜９００℃で行い、Ｃを０．００２％以下に低減する。 After cold rolling, the cold rolled sheet is decarburized and annealed. Decarburization annealing is usually carried out at 800-900 ° C. in a moist atmosphere containing hydrogen and nitrogen to reduce C to 0.002% or less.
脱炭焼鈍における昇温速度は８０℃／ｓ以上とすることが好ましい。この理由は昇温速度８０℃／ｓ以上で鉄損が低減するためである。上限は特に設けないが、２００℃／ｓもあれば十分な効果が発揮される。 The rate of temperature rise in decarburization annealing is preferably 80 ° C./s or higher. The reason for this is that iron loss is reduced at a heating rate of 80 ° C./s or higher. Although no upper limit is set, a sufficient effect can be exhibited at 200 ° C./s.
スラブを１２５０℃未満で加熱し、脱炭焼鈍中又は脱炭焼鈍後、窒化処理を行う場合、窒化処理は、例えば、アンモニア等の窒化能を有するガスを含む雰囲気中で行う。 When the slab is heated at a temperature lower than 1250 ° C. and the nitriding treatment is performed during decarburization annealing or after decarburization annealing, the nitriding treatment is performed in an atmosphere containing a gas having a nitriding ability such as ammonia.
脱炭焼鈍又は窒化処理の後、鋼板に、ＭｇＯを主成分とする焼鈍分離剤を塗布して、仕上焼鈍を施す。本発明において、仕上焼鈍工程で使用される焼鈍分離剤は、酸化マグネシウム粉末と、添加剤とを含有する。酸化マグネシウム粉末は焼鈍分離剤の主成分であり、「主成分」とはある物質（例えば、焼鈍分離剤）に５０％以上含まれている成分のことを言い、好ましくは７０％以上、より好ましくは８０％以上である。焼鈍分離剤の鋼板への付着量は、片面あたり、例えば、２ｇ／ｍ２以上１０ｇ／ｍ２以下が好ましい。焼鈍分離剤の鋼板への付着量が２ｇ／ｍ２未満である場合、仕上焼鈍において、鋼板同士が焼き付いてしまうので好ましくない。焼鈍分離剤の鋼板への付着量が１０ｇ／ｍ２超である場合、製造コストが増大するので好ましくない。焼鈍分離剤の塗布は、水性スラリーによる塗布の代わりに、静電塗布などでも構わない。
酸化マグネシウム粉末とは、ＭｇＯを主成分とする粉末であり、不純物としてＣａ，Ｓｒ，Ｂａ，Ｃｅ，Ｐｒ，Ｅｕ，及びＧｄからなる群から選択される金属（Ｙ群元素）を少なくとも1種以上含有し、その合計含有量は、酸化マグネシウム粉末中のＭｇの存在量に対し、０．０２〜０．８％の範囲である。０．０２％以下となると、被膜の形成が促進されず、被膜密着性が劣位となる。一方、０．８％を超えると、鋼板と被膜の界面で硫化物を形成し、インヒビターの分解を早めるので、磁気特性が劣位となる。
添加剤は、Ｙ群元素を少なくとも1種以上含有する化合物であり、その合計添加量は、焼鈍分離剤中のＭｇの存在量に対し、０．２〜５．０％の存在比となるように含有する。０．２％以下となると、被膜密着性改善効果が得られず、５．０％以上となると、フォルステライト形成反応を促進しすぎて、インヒビターの分解が遅くなり、細粒が発生するなどして磁気特性が安定的に得られなくなる。
また、全焼鈍分離剤中に含まれるＹ群元素の合計存在量に対する，前記酸化マグネシウム粉末中のＹ群元素の合計存在量の割合は０．０５〜０．６６である。０．０５以下であると、ＭｇＯの反応が十分促進されず、インヒビターの分解が遅くなり、細粒が発生するなどして、磁気特性が安定的に得られなくなる。また、０．６６以上であると、被膜が形成しすぎて、磁気特性が劣化する。
After decarburization annealing or nitriding treatment, an annealing separator containing MgO as a main component is applied to the steel sheet to perform finish annealing. In the present invention, the annealing separator used in the finishing annealing step contains magnesium oxide powder and an additive. Magnesium oxide powder is the main component of the annealing separator, and the "main component" refers to a component contained in a substance (for example, an annealing separator) in an amount of 50% or more, preferably 70% or more, more preferably. Is 80% or more. Adhesion amount of the steel sheet in the annealing separating agent, per side, for example, preferably 2 g / m 2 or more 10 g / m 2 or less. If the amount of the annealing separator attached to the steel sheet is less than 2 g / m 2 , the steel sheets will seize with each other during the finish annealing, which is not preferable. If the amount of the annealing separator adhered to the steel sheet exceeds 10 g / m 2 , the manufacturing cost increases, which is not preferable. The annealing separating agent may be applied by electrostatic application or the like instead of application by the aqueous slurry.
Magnesium oxide powder is a powder containing MgO as a main component, and contains at least one metal (Y group element) selected from the group consisting of Ca, Sr, Ba, Ce, Pr, Eu, and Gd as impurities. It is contained, and the total content thereof is in the range of 0.02 to 0.8% with respect to the abundance of Mg in the magnesium oxide powder. If it is 0.02% or less, the formation of the film is not promoted and the film adhesion is inferior. On the other hand, if it exceeds 0.8%, sulfide is formed at the interface between the steel sheet and the coating film, and the decomposition of the inhibitor is accelerated, so that the magnetic properties are inferior.
The additive is a compound containing at least one Y group element, and the total amount of the additive added is 0.2 to 5.0% of the abundance of Mg in the quenching separator. It is contained in. If it is 0.2% or less, the effect of improving the film adhesion cannot be obtained, and if it is 5.0% or more, the forsterite formation reaction is promoted too much, the decomposition of the inhibitor is delayed, and fine particles are generated. Therefore, the magnetic characteristics cannot be obtained stably.
The ratio of the total abundance of the Y group elements in the magnesium oxide powder to the total abundance of the Y group elements contained in the total quenching separator is 0.05 to 0.66. If it is 0.05 or less, the reaction of MgO is not sufficiently promoted, the decomposition of the inhibitor is delayed, fine particles are generated, and the magnetic characteristics cannot be stably obtained. On the other hand, if it is 0.66 or more, the film is formed too much and the magnetic characteristics are deteriorated.
仕上焼鈍は、｛１１０｝＜００１＞方位の結晶粒を二次再結晶させる工程であり、磁束密度を高めるために重要な工程である。通常、窒素と水素の混合雰囲気中、１１００〜１２００℃への昇温過程で、二次再結晶を発現させ、その後、上記雰囲気を水素雰囲気に切り替え、１１００〜１２００℃で２０時間程度の焼鈍を行う。この焼鈍は一般的に純化焼鈍と呼ばれ、Ｎ、Ｓ、Ｓｅ等を、鋼板から排出し、磁気特性を良好なものとする。 Finish annealing is a step of secondary recrystallization of crystal grains in the {110} <001> orientation, and is an important step for increasing the magnetic flux density. Usually, in a mixed atmosphere of nitrogen and hydrogen, secondary recrystallization is expressed in the process of raising the temperature to 1100 to 1200 ° C., then the above atmosphere is switched to a hydrogen atmosphere, and annealing is performed at 1100 to 1200 ° C. for about 20 hours. conduct. This annealing is generally called purified annealing, and N, S, Se and the like are discharged from the steel sheet to improve the magnetic characteristics.
二次再結晶の安定的進行、及び、磁束密度の向上の点で、仕上焼鈍の昇温平均速度は遅いほうがよいが、生産性の点から、３℃／ｈ以上が好ましく、より好ましくは、５〜２０℃／ｈである。 From the viewpoint of stable progress of secondary recrystallization and improvement of magnetic flux density, the average rate of temperature rise of finish annealing should be slow, but from the viewpoint of productivity, 3 ° C./h or more is preferable, and more preferably. It is 5 to 20 ° C./h.
なお、７５０℃までの昇温速度は、特に限定されないが、通常、１５〜１００℃／ｈであり、生産性の点で、速いほうが望ましい。 The rate of temperature rise up to 750 ° C. is not particularly limited, but is usually 15 to 100 ° C./h, and a faster rate is desirable from the viewpoint of productivity.
仕上焼鈍後の鋼板に、例えば、リン酸アルミニウムとコロイダルシリカを主成分とする被膜液を塗布して焼き付け、絶縁被膜を形成する。 For example, a coating liquid containing aluminum phosphate and colloidal silica as main components is applied to the steel sheet after finish annealing and baked to form an insulating film.
（化学組成の測定） (Measurement of chemical composition)
母材鋼板の成分は、熱アルカリおよび酸などに浸漬し、製品鋼板上に形成する絶縁被膜や一次被膜を除去し、ＩＣＰ―ＭＳ、ＮＤＩＲなどの分析方法を適宜用いて測定する。 The components of the base steel sheet are immersed in hot alkali and acid to remove the insulating film and primary film formed on the product steel sheet, and are measured by appropriately using an analytical method such as ICP-MS or NDIR.
また、一次被膜の成分は、熱アルカリに浸漬し、製品鋼板上に形成する絶縁被膜を除去するか、絶縁被膜塗布前の一次被膜付き鋼板に対し、アセチルアセトン系の電解液中で鋼板を電解し、一次被膜を電解残渣として抽出し、ＸＲＦにより測定し、質量％で、一次被膜の重量を１００％としたときの、Ｂｉ、Ｐｂ、Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇならびにＣａ、Ｓｒ、Ｂａ、Ｃｅ、Ｐｒ、Ｅｕ、およびＧｄ量を測定する。 In addition, the components of the primary coating are immersed in hot alkali to remove the insulating coating formed on the product steel sheet, or the steel sheet with the primary coating before the insulating coating is applied is electrolyzed in an acetylacetone-based electrolytic solution. , The primary coating was extracted as an electrolytic residue, measured by XRF, and Bi, Pb, Te, In, Cd, Zn, Ga, Au, Ag, Pd when the weight of the primary coating was 100% by mass%. , Pt and Hg and Ca, Sr, Ba, Ce, Pr, Eu, and Gd amounts are measured.
（特定成分の板厚深さ位置の測定）
母材鋼板被膜中の特定成分の濃化位置の測定は、熱アルカリに浸漬し、製品鋼板上に形成する絶縁被膜を除去するか、絶縁被膜塗布前の一次被膜付き鋼板に対し、ＧＤＳ分析を行い、対象とする特定成分元素の、最も高い発光強度の位置を特定して行う。ただし、表層から０．０５μｍ以内は酸洗で除去できなかった焼鈍分離剤または絶縁被膜の残存物であるため除外し、表層から０．０５μｍより深い位置にあるもっとも高い発光強度の位置を採用する。
(Measurement of plate thickness depth position of specific component)
To measure the concentration position of a specific component in the base steel sheet coating, either immerse it in hot alkali to remove the insulating coating formed on the product steel plate, or perform GDS analysis on the primary coated steel plate before applying the insulating coating. This is performed by identifying the position of the highest emission intensity of the target specific component element. However, the area within 0.05 μm from the surface layer is excluded because it is a residue of the annealing separator or insulating film that could not be removed by pickling, and the position with the highest emission intensity deeper than 0.05 μm from the surface layer is adopted. ..
次に、本発明の実施例について説明するが、実施例の条件は、本発明の実施可能性及び効果を確認するために採用した一条件例であり、本発明は、この一条件例に限定されるものではない。本発明は、本発明の要旨を逸脱せず、本発明の目的を達成する限りにおいて、種々の条件を採用し得るものである。
なお、以下の表において、「−」の記載は、意図的な添加を行っていない元素に関する項目であり、測定を実施していないことを示し、不可避不純物レベルでの含有を除外するものではない。
また、素材において意図的に添加した元素であっても、製造過程の純化により検出限界以下の含有量となったものは、「＜」を用いた数値で示す。
Next, examples of the present invention will be described. The conditions of the examples are one condition example adopted for confirming the feasibility and effect of the present invention, and the present invention is limited to this one condition example. It is not something that is done. In the present invention, various conditions can be adopted as long as the gist of the present invention is not deviated and the object of the present invention is achieved.
In the table below, the description of "-" indicates that the element has not been intentionally added, indicates that the measurement has not been performed, and does not exclude the inclusion at the unavoidable impurity level. ..
In addition, even if the element is intentionally added in the material, the content of the element whose content is below the detection limit due to purification in the manufacturing process is indicated by a numerical value using "<".
（実施例１）
真空溶解炉にて、質量％で、Ｃ：０．０９％、Ｓｉ：３．１％、Ａｌ：０．０３％、Ｎ：０．０１％、Ｓ：０．０３％、Ｍｎ：０．０８％、Ｃｕ，Ｓｎ、Ｓｂ：０．２〜０．３％、Ｂｉ，Ｐｂ添加量および、Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇの添加量を種々変えて含有するスラブを作製した。この化学組成は表１に示す。このスラブに、加熱条件を１３５０℃、１時間とした熱間圧延を施し、板厚２．０ｍｍの熱延板に仕上げた。
(Example 1)
In a vacuum melting furnace, in mass%, C: 0.09%, Si: 3.1%, Al: 0.03%, N: 0.01%, S: 0.03%, Mn: 0.08 %, Cu, Sn, Sb: 0.2 to 0.3%, Bi, Pb addition amount and Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg addition amounts are variously changed. A slab containing it was prepared. This chemical composition is shown in Table 1. This slab was hot-rolled under heating conditions of 1350 ° C. for 1 hour to finish a hot-rolled plate having a plate thickness of 2.0 mm.
上記熱延板に、１０８０℃、１２０秒の焼鈍を施し、次いで、酸洗の後、冷間圧延で板厚０．２３ｍｍの冷延板に仕上げた。この冷延板に、水素を含む湿潤雰囲気中にて、昇温速度３００℃／ｓで８４０℃、１１０秒の脱炭焼鈍を施し、その後、表２に記載の焼鈍分離剤を水スラリーにて塗布し、次いで、１２００℃、２０時間の仕上焼鈍を施した。 The hot-rolled plate was annealed at 1080 ° C. for 120 seconds, then pickled and then cold-rolled to finish a cold-rolled plate having a plate thickness of 0.23 mm. This cold-rolled sheet is subjected to decarburization and annealing at a heating rate of 300 ° C./s at 840 ° C. for 110 seconds in a moist atmosphere containing hydrogen, and then the annealing separator shown in Table 2 is applied in a water slurry. It was applied and then subjected to finish annealing at 1200 ° C. for 20 hours.
仕上焼鈍後の鋼板を水洗した後、磁気測定用の単板サイズに剪断し、リン酸アルミニウムとコロイダルシリカを主成分とする被膜液を塗布して焼き付け、絶縁被膜付き方向性電磁鋼板を作製した。 After the finish annealed steel sheet was washed with water, it was sheared to a single plate size for magnetic measurement, and a coating liquid containing aluminum phosphate and colloidal silica as main components was applied and baked to prepare a grain-oriented electrical steel sheet with an insulating film. ..
作製した方向性電磁鋼板の磁束密度Ｂ８を測定した。Ｂ８は、磁化力８００Ａ／ｍにおける磁束密度であり、Ｗ６０ｍｍ×Ｌ３００ｍｍの単板で評価した。溶解成分毎に、測定用の単板を５枚用意し、Ｂ８を測定した。５枚のＢ８測定値のうち、最高値をＢ８ｍａｘとし、最低値をＢ８ｍｉｎとし、その差をΔＢ８として、磁気特性の変動幅を示す指標とした。 The magnetic flux density B8 of the prepared grain-oriented electrical steel sheet was measured. B8 is the magnetic flux density at a magnetization force of 800 A / m, and was evaluated with a single plate of W60 mm × L300 mm. Five veneers for measurement were prepared for each dissolved component, and B8 was measured. Of the five B8 measured values, the highest value was B8max, the lowest value was B8min, and the difference was ΔB8, which was used as an index showing the fluctuation range of the magnetic characteristics.
また熱延性は、熱延板のエッジ部を目視で観察し、クラックの発生頻度により以下の３段階で評価した。
良好・・・・熱延板のエッジ（板幅端部）を圧延方向に１０００ｍｍにわたり目視観察し、板幅方向の長さが２０ｍｍ以上のクラックの個数が１個以下であること
可・・・・・熱延板のエッジ（板幅端部）を圧延方向に１０００ｍｍにわたり目視観察し、板幅方向の長さが２０ｍｍ以上のクラックの個数が２個以上であること
割れ・・・・熱間圧延中に破断すること
なお、ここでのクラックは鋼板エッジに発生するもののうち、板厚を貫通したものである。また、クラックの板幅方向の長さは板厚を貫通した部位の幅方向の長さである。
The heat ductility was evaluated by visually observing the edge portion of the hot-rolled plate and evaluating it in the following three stages according to the frequency of crack occurrence.
Good ... The edge (plate width end) of the hot-rolled plate is visually observed over 1000 mm in the rolling direction, and the number of cracks with a length of 20 mm or more in the plate width direction can be 1 or less.・ ・ Visually observe the edge (plate width end) of the hot-rolled plate over 1000 mm in the rolling direction, and the number of cracks with a length of 20 mm or more in the plate width direction is 2 or more. Breaking during rolling The cracks here occur at the edges of the steel sheet and penetrate the thickness of the steel sheet. Further, the length of the crack in the plate width direction is the length in the width direction of the portion penetrating the plate thickness.
表３に、測定結果を示す。スラブ中で所定のＢｉおよびＰｂの一種以上を含むとき、Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇ量の増加に伴い、磁気特性の変動幅を示す指標ΔＢ８は小さくなる。特に、Ｔｅ，Ｉｎ，Ｃｄ，ＺｎおよびＧａからなる群とＡｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇからなる群からそれぞれ１種類以上を組み合わせて、合計０．００１％以上添加した試料符号７〜１３、１５,１６,１９,２０は、ΔＢ８＜０．０４Ｔであり、Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇ添加の効果が大きいことを示している。また、スラブ中でＴｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇ量が０．５００％を超える試料符号１７および、Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇを１種類しか添加しない試料符号２４，２５,２７〜３０,３２〜４１の場合、熱延性が劣位となった。 Table 3 shows the measurement results. When the slab contains one or more of predetermined Bi and Pb, the index ΔB8 indicating the fluctuation range of the magnetic characteristics is as the amount of Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg increases. It becomes smaller. In particular, sample codes 7 to 13 in which one or more of the group consisting of Te, In, Cd, Zn and Ga and the group consisting of Au, Ag, Pd, Pt and Hg are combined and 0.001% or more in total is added. 15,16,19,20 are ΔB8 <0.04T, indicating that the addition of Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg has a large effect. In addition, sample code 17 in which the amount of Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg exceeds 0.500% in the slab, and Te, In, Cd, Zn, Ga, Au, Ag. In the case of sample reference numerals 24, 25, 27 to 30, 32 to 41 to which only one type of Pd, Pt and Hg was added, the heat spreadability was inferior.
表４に各試料の一次被膜の分析結果を示す。スラブにＸ群元素を２種以上含み、合計で０．００１〜０．５００％含有する場合、被膜中のＴｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇ量が範囲内であった。 Table 4 shows the analysis results of the primary coating of each sample. When the slab contains two or more types of X group elements and contains 0.001 to 0.500% in total, the amount of Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg in the coating is in the range. It was inside.
ここで、酸化マグネシウム粉末中の不純物元素としてのＹ群元素の存在量の割合ＲＹ、焼鈍分離剤中の添加剤中の存在量の割合Ｒ’Ｙとその比は次のようにして求める。
酸化マグネシウム粉末中に不純物として含まれるＹ群元素の濃度（％濃度）をＷＹ、Ｙ群元素以外の不純物元素の濃度（％濃度）をＷＸとすると、該酸化マグネシウム粉末単位重量あたりのＭｇの存在量ＸＭｇ（ｍｏｌ／ｇ）および該酸化マグネシウム粉末単位重量当たりのＹの存在量ＸＹ（ｍｏｌ／ｇ）は
ＸＭｇ＝（１００−ＷＹ−ＷＸ）／１００／ＭｇＯ分子量
＝（１００−ＷＹ−ＷＸ）／１００／（Ｍｇの原子量＋Ｏの原子量）
ＸＹ＝ＷＹ／１００／（Ｙ群元素の原子量）
であり、
該酸化マグネシウム粉末中のＭｇの存在量に対するＹ群元素の存在量の割合ＲＹ（％）は、
ＲＹ＝（ＸＹ／ＸＭｇ）・１００
である。
ただし、酸化マグネシウム粉末に２種類以上のＹ群元素が不純物として含まれる場合、上記と同様の手順で、Ｙ群元素すべてにつきＸＹを求め、合計した値ΣＸＹを用いて、
ＲＹ＝（ΣＸＹ／ＸＭｇ）・１００
とする。
また、該酸化マグネシウム粉末を主成分として調製される焼鈍分離剤に添加されるＹ群元素化合物分子におけるＹ群元素の化学量論係数をＺ、該Ｙ群元素化合物の酸化マグネシウム粉末に対する添加割合（％）をＡＹとすると、単位重量の酸化マグネシウム粉末と、単位重量の酸化マグネシウム粉末に対して添加された添加剤とからなる焼鈍分離剤中の添加剤に含まれるＹ群元素の存在量Ｘ‘Ｙは、
Ｘ‘Ｙ＝（ＡＹ／１００）・Ｚ／（Ｙ群元素化合物の分子量）
であり、
該焼鈍分離剤中の酸化マグネシウム中のＭｇの存在量に対する、添加剤中のＹ群元素の含有量の比Ｒ‘Ｙは、
Ｒ‘Ｙ＝（Ｘ’Ｙ／ＸＭｇ）・１００
である。
ただし、添加剤に含まれるＹ群元素が２種類以上である場合もしくは添加剤種が２種類以上である場合、上記と同様の手順で、すべての添加剤に含まれるＹ群元素すべてにつきＸ‘Ｙを求め、合計した値ΣＸ‘Ｙを用いて、
Ｒ‘Ｙ＝（ΣＸ’Ｙ／ＸＭｇ）・１００
である。
また、該焼鈍分離剤中のＹ群元素の合計存在量に対する、前記酸化マグネシウム粉末中のＹ群元素の合計存在量の比は、
ＸＹ／（Ｘ‘Ｙ＋ＸＹ）
＝｛（ＸＹ／ＸＭｇ）・１００｝/｛（Ｘ’Ｙ／ＸＭｇ）・１００＋（ＸＹ／ＸＭｇ）・１００｝＝ＲＹ／（Ｒ‘Ｙ＋ＲＹ）
で表される。
The concentration of the Y group element contained as an impurity in the magnesium oxide powder (% concentration) W Y, the concentration of impurity elements other than Y group element (percent concentration) and W X, per magnesium oxide powder unit weight Mg The abundance of X Mg (mol / g) and the abundance of Y per unit weight of the magnesium oxide powder XY (mol / g) is X Mg = (100-W Y -W X ) / 100 / MgO molecular weight = ( 100-W Y -W X ) / 100 / (Atomic weight of Mg + Atomic weight of O)
XY = W Y / 100 / (Atomic weight of Y group elements)
And
The ratio of the abundance of Y group elements to the abundance of Mg in the magnesium oxide powder RY (%) is
RY = ( XY / X Mg ) · 100
Is.
However, if two or more Y group element in the magnesium oxide powder is included as an impurity, in the same procedure as above, we obtain the X Y per every Y group element, with a total value .SIGMA.X Y,
RY = (ΣX Y / X Mg ) ・ 100
And.
Further, the chemical quantitative coefficient of the Y group element in the Y group element compound molecule added to the annealing separator prepared with the magnesium oxide powder as the main component is Z, and the addition ratio of the Y group element compound to the magnesium oxide powder ( %) Is A Y, and the abundance of Y group elements contained in the additive in the annealing separator consisting of the unit weight of magnesium oxide powder and the additive added to the unit weight of magnesium oxide powder X. ' Y is
X'Y = (A Y / 100) · Z / (Molecular weight of group Y element compound)
And
該焼for the presence of Mg in the magnesium oxide in the blunt separating agent, the ratio R 'Y content of Y group element in the additive,
R'Y = ( X'Y / X Mg ) · 100
Is.
However, if there are two or more Y group elements contained in the additive, or if there are two or more additive types, the procedure is the same as above, and X'for all Y group elements contained in all the additives. seeking Y, using the total value .SIGMA.X 'Y,
R 'Y = (ΣX' Y / X Mg) · 100
Is.
The ratio of the total abundance of Y group elements in the magnesium oxide powder to the total abundance of Y group elements in the quenching separator is
XY / ( X'Y + XY )
= {(X Y / X Mg ) · 100} / {(X 'Y / X Mg) · 100+ (X Y / X Mg) · 100} = R Y / (R' Y + R Y)
It is represented by.
（実施例２）
真空溶解炉にて、質量％で、Ｃ：０．０９％、Ｓｉ：３．１％、Ａｌ：０．０３％、Ｎ：０．０１％、Ｓ＋０．４Ｓｅ：０．０３％、Ｍｎ：０．０８％、Ｓｎ：０．１または０．３％、Ｂｉ，Ｐｂ添加量および、Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇの添加量を種々変えて含有するスラブを作製した。この化学組成は表５に示す。このスラブに、加熱条件を１３５０℃、１時間とした熱間圧延を施し、板厚２．０ｍｍの熱延板に仕上げた。
(Example 2)
In a vacuum melting furnace, in mass%, C: 0.09%, Si: 3.1%, Al: 0.03%, N: 0.01%, S + 0.4Se: 0.03%, Mn: 0 .08%, Sn: 0.1 or 0.3%, Bi, Pb addition amount and Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg addition amounts are contained in various variations. A slab was made. This chemical composition is shown in Table 5. This slab was hot-rolled under heating conditions of 1350 ° C. for 1 hour to finish a hot-rolled plate having a plate thickness of 2.0 mm.
上記熱延板に、１０８０℃、１２０秒の焼鈍を施し、次いで、酸洗の後、冷間圧延で板厚０．２３ｍｍの冷延板に仕上げた。この冷延板に、水素を含む湿潤雰囲気中にて、昇温速度３００℃／ｓで８４０℃、１１０秒の脱炭焼鈍を施し、その後、表６に示す酸化マグネシウム粉末を主成分とする焼鈍分離剤を水スラリーにて塗布し、次いで、１２００℃、２０時間の仕上焼鈍を施した。 The hot-rolled plate was annealed at 1080 ° C. for 120 seconds, then pickled and then cold-rolled to finish a cold-rolled plate having a plate thickness of 0.23 mm. This cold-rolled sheet is subjected to decarburization annealing at a heating rate of 300 ° C./s for 110 seconds in a moist atmosphere containing hydrogen, and then annealing containing magnesium oxide powder as a main component shown in Table 6. The separating agent was applied with a water slurry and then subjected to finish annealing at 1200 ° C. for 20 hours.
仕上焼鈍後の鋼板を水洗した後、磁気測定用の単板サイズに剪断し、リン酸アルミニウムとコロイダルシリカを主成分とする被膜液を塗布して焼き付け、絶縁被膜付き方向性電磁鋼板を作製した。 After the finish annealed steel sheet was washed with water, it was sheared to a single plate size for magnetic measurement, and a coating liquid containing aluminum phosphate and colloidal silica as main components was applied and baked to prepare a grain-oriented electrical steel sheet with an insulating film. ..
作製した方向性電磁鋼板の磁束密度Ｂ８を測定した。Ｂ８は、磁化力８００Ａ／ｍにおける磁束密度であり、Ｗ６０ｍｍ×Ｌ３００ｍｍの単板で評価した。溶解成分毎に、測定用の単板を５枚用意し、Ｂ８を測定した。５枚のＢ８測定値のうち、最高値をＢ８ｍａｘとし、最低値をＢ８ｍｉｎとし、その差をΔＢ８として、磁気特性の変動幅を示す指標とした。 The magnetic flux density B8 of the prepared grain-oriented electrical steel sheet was measured. B8 is the magnetic flux density at a magnetization force of 800 A / m, and was evaluated with a single plate of W60 mm × L300 mm. Five veneers for measurement were prepared for each dissolved component, and B8 was measured. Of the five B8 measured values, the highest value was B8max, the lowest value was B8min, and the difference was ΔB8, which was used as an index showing the fluctuation range of the magnetic characteristics.
また熱延性は、熱延板のエッジ部を目視で観察し、クラックの発生頻度により以下の３段階で評価した。
良好・・・・熱延板のエッジ（板幅端部）を圧延方向に１０００ｍｍにわたり目視観察し、板幅方向の長さが２０ｍｍ以上のクラックの個数が１個以下であること
可・・・・・熱延板のエッジ（板幅端部）を圧延方向に１０００ｍｍにわたり目視観察し、板幅方向の長さが２０ｍｍ以上のクラックの個数が２個以上であること
割れ・・・・熱間圧延中に破断すること
なお、ここでのクラックは鋼板エッジに発生するもののうち、板厚を貫通したものである。また、クラックの板幅方向の長さは板厚を貫通した部位の幅方向の長さである。
The heat ductility was evaluated by visually observing the edge portion of the hot-rolled plate and evaluating it in the following three stages according to the frequency of crack occurrence.
Good ... The edge (plate width end) of the hot-rolled plate is visually observed over 1000 mm in the rolling direction, and the number of cracks with a length of 20 mm or more in the plate width direction can be 1 or less.・ ・ Visually observe the edge (plate width end) of the hot-rolled plate over 1000 mm in the rolling direction, and the number of cracks with a length of 20 mm or more in the plate width direction is 2 or more. Breaking during rolling The cracks here occur at the edges of the steel sheet and penetrate the thickness of the steel sheet. Further, the length of the crack in the plate width direction is the length in the width direction of the portion penetrating the plate thickness.
表７に、測定結果を示す。Ｔｅ，Ｉｎ，Ｃｄ，ＺｎおよびＧａからなる群とＡｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇからなる群からそれぞれ１種類以上を組み合わせて、合計０．００１％以上添加した試料符号９〜１４は、ΔＢ８＜０．０４Ｔであり、Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇ添加の効果が大きいことを示している。Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇを１種類しか添加しない試料符号２５〜３４の場合、熱延性が劣位となった。スラリー成分中の添加剤中のＹ群元素の存在量に対する、酸化マグネシウム粉末中不純物におけるＹ群元素の存在量の比が範囲外であったスラリー１５、１６を用いた試料符号７、８、１９および２０の場合、耐錆性が劣位となった。また、酸化マグネシウム粉末中不純物におけるＹ群元素の存在量が範囲外であったスラリー１１、１２を用いた試料符号１５および１６の場合、耐錆性が劣位となった。また、焼鈍分離剤の添加剤におけるＹ群元素の存在量が範囲外であったスラリー１３、１４を用いた試料符号１７および１８の場合、耐錆性が劣位となった。 Table 7 shows the measurement results. Sample codes 9 to 14 in which one or more of each of the group consisting of Te, In, Cd, Zn and Ga and the group consisting of Au, Ag, Pd, Pt and Hg are combined and 0.001% or more in total are added are ΔB8. <0.04T, indicating that the addition of Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg has a large effect. In the case of sample codes 25 to 34 in which only one type of Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg was added, the heat ductility was inferior. Sample codes 7, 8 and 19 using the slurry 15 and 16 in which the ratio of the abundance of the Y group element in the impurities in the magnesium oxide powder to the abundance of the Y group element in the additive in the slurry component was out of the range. In the case of and 20, the rust resistance was inferior. Further, in the case of sample codes 15 and 16 using the slurries 11 and 12 in which the abundance of Y group elements in the impurities in the magnesium oxide powder was out of the range, the rust resistance was inferior. Further, in the case of sample codes 17 and 18 using the slurries 13 and 14 in which the abundance of the Y group elements in the additive of the annealing separator was out of the range, the rust resistance was inferior.
表８に各試料の一次被膜の分析結果を示す。スラブにＸ群元素を２種以上含み、合計で０．００１〜０．５００％含有する場合、被膜中のＴｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇ量が範囲内であった。
Table 8 shows the analysis results of the primary coating of each sample. When the slab contains two or more types of X group elements and contains 0.001 to 0.500% in total, the amount of Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg in the coating is in the range. It was inside.
（実施例３）
真空溶解炉にて、質量％で、Ｃ：０．０９％、Ｓｉ：３．５％、Ａｌ：０．０３％、Ｎ：０．０１％、Ｓ＋０．４Ｓｅ：０．００９％、Ｍｎ：０．０８％、Ｂｉ：０．００３０％を含有し、さらに、Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇから選ばれる２種類以上の元素を０．００１〜０．０５％の範囲で種々変えて含有するスラブを作製した。この化学組成は表９に示す。このスラブに、加熱条件を１１５０℃、１時間とした熱間圧延を施し、板厚２．０ｍｍの熱延板に仕上げた。
(Example 3)
In a vacuum melting furnace, in mass%, C: 0.09%, Si: 3.5%, Al: 0.03%, N: 0.01%, S + 0.4Se: 0.009%, Mn: 0 .08%, Bi: 0.0030%, and two or more elements selected from Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg 0.001 to 0. A slab containing various changes in the range of 05% was prepared. This chemical composition is shown in Table 9. This slab was hot-rolled under heating conditions of 1150 ° C. for 1 hour to finish a hot-rolled plate having a plate thickness of 2.0 mm.
上記熱延板に、１０５０℃、１２０秒の焼鈍を施し、次いで、酸洗の後、冷間圧延で板厚０．２３ｍｍの冷延板に仕上げた。この冷延板に、水素を含む湿潤雰囲気中にて、昇温速度１００℃／ｓで８５０℃、１２０秒の脱炭焼鈍を施し、その後、アンモニアを含有する雰囲気にて、７５０℃、６０秒の焼鈍を施し、鋼中の窒素量を増加させた。 The hot-rolled plate was annealed at 1050 ° C. for 120 seconds, then pickled and then cold-rolled to finish a cold-rolled plate having a plate thickness of 0.23 mm. This cold-rolled sheet is decarburized and annealed at a heating rate of 100 ° C./s for 120 seconds in a moist atmosphere containing hydrogen, and then decarburized and annealed at a heating rate of 100 ° C./s for 120 seconds, and then at 750 ° C. for 60 seconds in an atmosphere containing ammonia. Was annealed to increase the amount of nitrogen in the steel.
焼鈍後の冷延板に、不純物元素としてＣａを０．２％含有する酸化マグネシウム粉末を主成分とし、前記酸化マグネシウム粉末の重量に対して２．０％の硫酸カルシウム半水和物を添加剤として加え、さらに、前記酸化マグネシウム粉末の重量に対して５．０％のＴｉＯ２を添加剤として加えた混合粉末と純水とを混合、撹拌して調製した水スラリーを鋼板表裏面に塗布・乾燥させた。このとき、酸化マグネシウム粉末の不純物元素としてＣａが、該酸化マグネシウム粉末中のＭｇの存在量に対して０．２０％の存在比で含有されており、
また、前記焼鈍分離剤は酸化マグネシウム粉末以外の添加剤に含まれるＣａ元素の存在量が、焼鈍分離剤の中の酸化マグネシウム粉末に含まれるＭｇの存在量に対して０．５６％の存在比となるように含有されており，
またさらに、前記焼鈍分離剤中のＣａの総量に対する、前記焼鈍分離剤中の酸化マグネシウム粉末中の不純物元素としてのＣａの割合が、０．２６である。
その後、１２００℃、２０時間の仕上焼鈍を施した。仕上焼鈍後の鋼板を水洗した後、磁気測定用の単板サイズに剪断し、リン酸アルミニウムとコロイダルシリカを主成分とする被膜液を塗布して焼き付け、絶縁被膜付き方向性電磁鋼板を作製した。
Magnesium oxide powder containing 0.2% Ca as an impurity element is the main component of the cold-rolled plate after annealing, and 2.0% calcium sulfate hemihydrate is added to the weight of the magnesium oxide powder. Further, a water slurry prepared by mixing and stirring a mixed powder in which 5.0% of TiO 2 was added as an additive to the weight of the magnesium oxide powder and pure water was applied to the front and back surfaces of the steel plate. It was dried. At this time, Ca is contained as an impurity element of the magnesium oxide powder in a abundance ratio of 0.20% with respect to the abundance of Mg in the magnesium oxide powder.
Further, the abundance ratio of the Ca element contained in the additive other than the magnesium oxide powder of the annealing separator is 0.56% with respect to the abundance of Mg contained in the magnesium oxide powder in the annealing separator. It is contained so that
Furthermore, the ratio of Ca as an impurity element in the magnesium oxide powder in the annealing separator to the total amount of Ca in the annealing separator is 0.26.
Then, finish annealing was performed at 1200 ° C. for 20 hours. After the finish annealed steel sheet was washed with water, it was sheared to a single plate size for magnetic measurement, and a coating liquid containing aluminum phosphate and colloidal silica as main components was applied and baked to prepare a grain-oriented electrical steel sheet with an insulating film. ..
表１０に、測定結果を示す。Ｂ８ｍａｘ、Ｂ８ｍｉｎ、及び、ΔＢ８および熱延性の定義または評価は、実施例１と同様である。Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇ量の増加に伴い、概して磁気特性の変動幅を示す指標ΔＢ８は小さくなる。特に、Ｔｅ，Ｉｎ，Ｃｄ，ＺｎおよびＧａからなる群とＡｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇからなる群からそれぞれ１種類以上を組み合わせて、合計０．００１％以上添加した試料符号７〜１１は、ΔＢ８≦０．０１７Ｔかつ、熱延性が良好であり、Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇ添加の効果が大きいことを示している。 Table 10 shows the measurement results. The definitions or evaluations of B8max, B8min, and ΔB8 and heat ductility are the same as in Example 1. As the amounts of Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg increase, the index ΔB8 indicating the fluctuation range of the magnetic characteristics generally becomes smaller. In particular, sample codes 7 to 11 in which one or more of the group consisting of Te, In, Cd, Zn and Ga and the group consisting of Au, Ag, Pd, Pt and Hg are combined and 0.001% or more in total are added are , ΔB8 ≦ 0.017T, and the heat ductility is good, indicating that the effect of adding Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg is large.
表１１に各試料の一次被膜の分析結果を示す。スラブにＴｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇを０．００１〜０．０５％の範囲で添加した試料符号１〜１１は、Ｔｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇ添加の効果が顕著に発現していることを示し、被膜中のＴｅ，Ｉｎ，Ｃｄ，Ｚｎ，Ｇａ，Ａｕ，Ａｇ，Ｐｄ，ＰｔおよびＨｇ量が範囲内であった。
Table 11 shows the analysis results of the primary coating of each sample. Sample codes 1 to 11 in which Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg were added to the slab in the range of 0.001 to 0.05% are Te, In, Cd, Zn, It was shown that the effect of adding Ga, Au, Ag, Pd, Pt and Hg was remarkably exhibited, and the amount of Te, In, Cd, Zn, Ga, Au, Ag, Pd, Pt and Hg in the coating was in the range. It was inside.
本発明によれば、良好な磁気特性と良好な被膜密着性を備える方向性電磁鋼板を、工業的な規模で、安定的に製造することができる。したがって、本発明は、電磁鋼板製造産業において利用可能性が大きいものである。 According to the present invention, a grain-oriented electrical steel sheet having good magnetic properties and good film adhesion can be stably manufactured on an industrial scale. Therefore, the present invention has great utility in the electrical steel sheet manufacturing industry.
Claims (5)
酸化マグネシウム粉末を主成分とする焼鈍分離剤であって、
該焼鈍分離剤の酸化マグネシウム粉末は、不純物元素としてＣａ，Ｓｒ，Ｂａ，Ｃｅ，Ｐｒ，Ｅｕ，及びＧｄからなる群から選択される少なくとも一種以上の元素の合計存在量が，該酸化マグネシウム粉末中のＭｇの存在量に対して０．０２〜０．８％の存在比で含有し，
さらに前記焼鈍分離剤は酸化マグネシウム粉末以外にＣａ，Ｓｒ，Ｂａ，Ｃｅ，Ｐｒ，Ｅｕ，及びＧｄからなる群から選択される少なくとも一種以上の元素を含む添加剤を、それぞれの元素の合計存在量が、焼鈍分離剤の中に含まれるＭｇの存在量に対して０．２〜５．０％の存在比となるように含有し，
さらに、前記焼鈍分離剤中のＣａ，Ｓｒ，Ｂａ，Ｃｅ，Ｐｒ，Ｅｕ，及びＧｄの総量に対する、前記焼鈍分離剤中の酸化マグネシウム粉末中の不純物元素としてのＣａ，Ｓｒ，Ｂａ，Ｃｅ，Ｐｒ，Ｅｕ，及びＧｄの総量の割合が、０．０２〜０．６６である焼鈍分離剤を鋼板表裏面に塗布・乾燥したのち、
最終仕上焼鈍を施すことを特徴とする方向性電磁鋼板の製造方法。 By mass%, Si: 2.5 to 4.5%, C: 0.02 to 0.10%, acid-soluble Al: 0.01 to 0.05%, N: 0.003 to 0.02%, S + 0.4 · Se: 0.003 to 0.04%, Mn: 0.04 to 0.20%, total of one or more types of Bi and Pb: 0.0005 to 0.05%, and Te, In, A slab containing at least two or more selected from the group consisting of Cd, Zn, Ga, Au, Ag, Pd, Pt, and Hg: 0.001 to 0.500%, with the balance being Fe and impurities. Is heated to 1000 to 1450 ° C., hot-rolled to obtain a hot-rolled plate, the hot-rolled plate is annealed, and then pickled and then cold-rolled once or twice with annealing. A plate is prepared, and the cold-rolled plate is decarburized and annealed, and if necessary, nitriding is performed during or after the annealing, and then,
An annealing separator containing magnesium oxide powder as the main component.
The magnesium oxide powder of the quenching separator has a total abundance of at least one or more elements selected from the group consisting of Ca, Sr, Ba, Ce, Pr, Eu, and Gd as impurity elements in the magnesium oxide powder. It is contained in an abundance ratio of 0.02 to 0.8% with respect to the abundance of Mg in
Further, the quenching separator contains an additive containing at least one element selected from the group consisting of Ca, Sr, Ba, Ce, Pr, Eu, and Gd in addition to magnesium oxide powder, and the total abundance of each element. Is contained so as to have an abundance ratio of 0.2 to 5.0% with respect to the abundance of Mg contained in the quenching separator.
Further, Ca, Sr, Ba, Ce, Pr as an impurity element in the magnesium oxide powder in the annealing separator with respect to the total amount of Ca, Sr, Ba, Ce, Pr, Eu, and Gd in the annealing separator. , Eu, and Gd are 0.02 to 0.66. After applying and drying the annealing separator on the front and back surfaces of the steel plate,
A method for manufacturing grain-oriented electrical steel sheets, which is characterized by subjecting final finish annealing.
Ｔｅ、Ｉｎ、Ｃｄ、Ｚｎ、及びＧａからなる群から選択される少なくとも一種以上の合計：０．０１％以上、かつＡｕ、Ａｇ、Ｐｄ、Ｐｔ、及びＨｇからなる群から選択される少なくとも一種以上の合計：０．０１％以上、を含有するフォルステライトを主体とする被膜が存在し、請求項３に記載の方向性電磁鋼板。 On the surface of the base steel plate,
Total of at least one selected from the group consisting of Te, In, Cd, Zn, and Ga: 0.01% or more, and at least one selected from the group consisting of Au, Ag, Pd, Pt, and Hg. The directional electromagnetic steel plate according to claim 3, wherein a coating film mainly containing forsterite containing 0.01% or more of the above is present.
Ｃａ、Ｓｒ、Ｂａ、Ｃｅ、Ｐｒ、Ｅｕ、及びＧｄからなる群のうち、最大の含有量の元素の板厚方向深さと、ＳおよびＳｅからなる群から選択される元素のうち、最大の含有量の元素の板厚方向深さの差が±１．５μｍ以内の範囲である，フォルステライトを主体とする被膜が存在し、請求項３または４に記載の方向性電磁鋼板。 On the surface of the base steel plate,
The depth in the plate thickness direction of the element having the maximum content in the group consisting of Ca, Sr, Ba, Ce, Pr, Eu, and Gd, and the maximum content of the element selected from the group consisting of S and Se. The directional electromagnetic steel plate according to claim 3 or 4, wherein a film mainly composed of forsterite is present, in which the difference in depth in the plate thickness direction of the amount of elements is within ± 1.5 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020073031A JP2021169648A (en) | 2020-04-15 | 2020-04-15 | Oriented electromagnetic steel sheet and method for producing oriented electromagnetic steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020073031A JP2021169648A (en) | 2020-04-15 | 2020-04-15 | Oriented electromagnetic steel sheet and method for producing oriented electromagnetic steel sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2021169648A true JP2021169648A (en) | 2021-10-28 |
Family
ID=78150167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020073031A Pending JP2021169648A (en) | 2020-04-15 | 2020-04-15 | Oriented electromagnetic steel sheet and method for producing oriented electromagnetic steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2021169648A (en) |
-
2020
- 2020-04-15 JP JP2020073031A patent/JP2021169648A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100979785B1 (en) | Grain oriented electromagnetic steel sheet having excellent film adhesion and process for producing the same | |
| JP6874907B2 (en) | Manufacturing method of grain-oriented electrical steel sheet and grain-oriented electrical steel sheet | |
| JP3386751B2 (en) | Method for producing grain-oriented silicon steel sheet with excellent coating and magnetic properties | |
| JP6146098B2 (en) | Oriented electrical steel sheet and manufacturing method thereof | |
| CN112522613A (en) | High-magnetic-induction oriented silicon steel with excellent bottom layer quality and production method thereof | |
| JP2650817B2 (en) | Method for producing unidirectional silicon steel sheet with excellent coating and magnetic properties | |
| JP2021123768A (en) | Method for producing directional electromagnetic steel sheet and directional electromagnetic steel sheet, and annealing separation agent | |
| JP2021169648A (en) | Oriented electromagnetic steel sheet and method for producing oriented electromagnetic steel sheet | |
| JP2021169646A (en) | Oriented electromagnetic steel sheet, slab for oriented electromagnetic steel sheet, and method for producing oriented electromagnetic steel sheet | |
| JP4291733B2 (en) | Annealing separator and method for producing grain-oriented electrical steel sheet using the same | |
| JP3716608B2 (en) | Method for producing grain-oriented electrical steel sheet | |
| JPH08143975A (en) | Annealing releasing agent and slurry for grain-oriented electrical steel sheet to obtain excellent glass coating and magnetic characteristics | |
| CN112771183B (en) | Grain-oriented electrical steel sheet, method for producing grain-oriented electrical steel sheet, and annealing separator used in production of grain-oriented electrical steel sheet | |
| JP4626155B2 (en) | Oriented electrical steel sheet with low magnetic field magnetic properties and excellent stability over time and method for producing the same | |
| CN113260718B (en) | Grain-oriented electrical steel sheet, method for producing grain-oriented electrical steel sheet, and annealing separator used for production of grain-oriented electrical steel sheet | |
| CN113260720B (en) | Grain oriented electromagnetic steel sheet, method for producing same, and annealing separator | |
| EP3910076A1 (en) | Grain-oriented magnetic steel sheet, annealing separating agent, and method for manufacturing grain-oriented magnetic steel sheet | |
| EP3913084B1 (en) | Method for producing grain oriented electrical steel sheet | |
| CN113195752B (en) | Grain-oriented electrical steel sheet, method for producing grain-oriented electrical steel sheet, and annealing separator used for production of grain-oriented electrical steel sheet | |
| CN113272457B (en) | Method for producing unidirectional electromagnetic steel sheet | |
| EP3910080A1 (en) | Grain-oriented magnetic steel sheet, steel sheet for finish annealing, annealing separating agent, method for manufacturing grain-oriented magnetic steel sheet, and method for manufacturing steel sheet for finish annealing | |
| JP2706039B2 (en) | Method for manufacturing mirror-oriented silicon steel sheet | |
| JP2021123767A (en) | Method for producing directional electromagnetic steel sheet and directional electromagnetic steel sheet, and annealing separation agent | |
| JP2003268452A (en) | Method for manufacturing grain-oriented electromagnetic steel sheet with adequate magnetic property and mirror plane | |
| EP4137599A1 (en) | Non-oriented electromagnetic steel sheet and method for manufacturing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20221205 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20231023 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20231031 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20231220 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240402 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240502 |