JP7413600B1 - Fe-Ni alloy plate and its manufacturing method - Google Patents
Fe-Ni alloy plate and its manufacturing method Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000000956 alloy Substances 0.000 title claims description 76
- 229910045601 alloy Inorganic materials 0.000 title claims description 75
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 title claims description 53
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 45
- 239000002184 metal Substances 0.000 claims description 45
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- 239000010949 copper Substances 0.000 claims description 32
- 238000007670 refining Methods 0.000 claims description 27
- 239000011651 chromium Substances 0.000 claims description 25
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- 239000010936 titanium Substances 0.000 claims description 24
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- 229910005347 FeSi Inorganic materials 0.000 claims description 12
- 238000005097 cold rolling Methods 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
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- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 230000035699 permeability Effects 0.000 abstract description 47
- 230000004907 flux Effects 0.000 abstract description 37
- 230000002829 reductive effect Effects 0.000 abstract description 9
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 238000010586 diagram Methods 0.000 abstract 1
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- 239000002893 slag Substances 0.000 description 45
- 238000011156 evaluation Methods 0.000 description 44
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 34
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 34
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 21
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- 239000000292 calcium oxide Substances 0.000 description 17
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- 239000000395 magnesium oxide Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- 229910004298 SiO 2 Inorganic materials 0.000 description 12
- 229910000889 permalloy Inorganic materials 0.000 description 11
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- 238000000137 annealing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005261 decarburization Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229910000521 B alloy Inorganic materials 0.000 description 5
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- 230000007423 decrease Effects 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229910001339 C alloy Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000009749 continuous casting Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000002542 deteriorative effect Effects 0.000 description 3
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- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910000863 Ferronickel Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
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- 238000001556 precipitation Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
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- 239000006028 limestone Substances 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
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Abstract
【課題】本発明は、優れた初比透磁率と、良好な最大比透磁率及び飽和磁束密度を付与し得ると共に、歩留まりを抑えて製造可能なＦｅ－Ｎｉ系合金及びその製造方法を提供する。【解決手段】質量％で、Ｃ：０．００１～０．０５％、Ｓｉ：０．０５～０．５０％、Ｍｎ：０．２５～１．００％、Ｐ：０．００１～０．０３０％、Ｓ：０．０００１～０．００５０％、Ｎｉ：３５．０～４４．０％、Ｃｒ：０．０１～０．５０％、Ｍｏ：０．００５～０．１０％、Ｃｕ：０．０１～２．００％、Ａｌ：０．０００１～０．１０％、Ｔｉ：０．０５０％以下、Ｃｏ：０．０１～２．００％、Ｗ：０．０１～０．５０％、Ｎ：０．００１～０．０５％、Ｓｎ：０．０００１～０．０５％、Ｍｇ：０．０５０％以下、Ｚｒ：０．０００１～０．０５％、Ｃａ：０．００２０％以下、Ｏ：０．０００２～０．０１％を含み、残部がＦｅ及び不可避的不純物からなるＦｅ－Ｎｉ系合金板。【選択図】図１[Problem] The present invention provides an Fe--Ni alloy that can provide excellent initial relative magnetic permeability, good maximum relative magnetic permeability, and saturation magnetic flux density, and that can be manufactured with reduced yield, and a method for manufacturing the same. . [Solution] In mass %, C: 0.001 to 0.05%, Si: 0.05 to 0.50%, Mn: 0.25 to 1.00%, P: 0.001 to 0.030 %, S: 0.0001 to 0.0050%, Ni: 35.0 to 44.0%, Cr: 0.01 to 0.50%, Mo: 0.005 to 0.10%, Cu: 0. 01 to 2.00%, Al: 0.0001 to 0.10%, Ti: 0.050% or less, Co: 0.01 to 2.00%, W: 0.01 to 0.50%, N: 0.001 to 0.05%, Sn: 0.0001 to 0.05%, Mg: 0.050% or less, Zr: 0.0001 to 0.05%, Ca: 0.0020% or less, O: 0 A Fe--Ni alloy plate containing .0002 to 0.01%, with the remainder consisting of Fe and unavoidable impurities. [Selection diagram] Figure 1
Description
本発明は、Ｆｅ－Ｎｉ系合金板及びその製造方法に関する。 The present invention relates to a Fe--Ni alloy plate and a method for manufacturing the same.
Ｆｅ－Ｎｉ系軟質磁性合金は、ＪＩＳ Ｃ２５３１やＩＥＣ規格に規定されるように、Ｎｉ量によって、パーマロイＣ合金（Ｎｉ：７２～８３質量％）、パーマロイＢ合金（Ｎｉ：４５～５０質量％）、パーマロイＤ合金（Ｎｉ：３５～４０質量％）等に大別される。高グレードなパーマロイＣ合金は高い透磁率、低い保持力を有することから、磁気シールド材や磁気センサ材等の磁気部材に使用されている。しかしながら、パーマロイＣ合金はＮｉを多く含有し高価であることから、磁気部材の材料として、より安価なパーマロイＢ合金へ置き換えられている。また、パーマロイＢ合金は高い飽和磁束密度を有するため、時計のステータや磁気レンズのポールピース等にも活用されている。 Fe-Ni based soft magnetic alloys are permalloy C alloy (Ni: 72 to 83 mass%) and permalloy B alloy (Ni: 45 to 50 mass%) depending on the Ni content as specified in JIS C2531 and IEC standards. , Permalloy D alloy (Ni: 35-40% by mass), etc. High-grade Permalloy C alloy has high magnetic permeability and low coercive force, so it is used for magnetic members such as magnetic shield materials and magnetic sensor materials. However, since Permalloy C alloy contains a large amount of Ni and is expensive, it has been replaced by the cheaper Permalloy B alloy as a material for magnetic members. Furthermore, since Permalloy B alloy has a high saturation magnetic flux density, it is used in things such as stators of watches and pole pieces of magnetic lenses.
近年、自動車センサや磁気シールド材といった軟磁性材料への需要は増加している一方、Ｎｉの価格は上昇傾向にあり、パーマロイＢ合金をよりＮｉ量が少なく安価なＡｌｌｏｙ４２やパーマロイＤ合金へ置き換える動きが進められている。しかしながら、Ｎｉ量の低下に伴い、各磁気特性や耐食性の低下が問題視されており、パーマロイＢ合金の特徴である高い飽和磁束密度の維持が切望されている。特に、自動車センサや磁気シールド材には、３,０００以上の初比透磁率、３０,０００以上の最大比透磁率、及び１．４Ｔ以上の飽和磁束密度を有する軟磁性材料が好適に使用される。 In recent years, demand for soft magnetic materials such as automotive sensors and magnetic shielding materials has increased, while the price of Ni has been on the rise, leading to a movement to replace Permalloy B alloy with Alloy 42 and Permalloy D alloy, which have lower Ni content and are cheaper. is in progress. However, as the amount of Ni decreases, a decrease in magnetic properties and corrosion resistance is considered a problem, and there is a strong desire to maintain the high saturation magnetic flux density that is a characteristic of Permalloy B alloy. In particular, soft magnetic materials having an initial relative magnetic permeability of 3,000 or more, a maximum relative magnetic permeability of 30,000 or more, and a saturation magnetic flux density of 1.4T or more are preferably used for automobile sensors and magnetic shielding materials. Ru.
パーマロイ合金の磁気特性を改善する手法として、特許文献１には連続鋳造スラブに対し均質化熱処理を施し、偏析を軽減することで磁気特性を改善する方法が提案されている。しかしながら、特許文献１には飽和磁束密度について言及されていない。 As a method of improving the magnetic properties of a permalloy alloy, Patent Document 1 proposes a method of subjecting a continuously cast slab to homogenization heat treatment to reduce segregation and thereby improving the magnetic properties. However, Patent Document 1 does not mention saturation magnetic flux density.
また、特許文献２には、Ｆｅ－Ｎｉ系合金の被圧延材に対する磁気焼鈍の温度・時間及びＦｅ－Ｎｉ系合金のＡ系（Ｍｎ－Ｓ系）介在物量を制限し、結晶粒の粒成長を促進させ、磁気特性を改善する方法が提案されている。しかしながら、この方法は、得られる軟磁性部品材料の保磁力、初比透磁率、最大比透磁率の改善を目的としており、飽和磁束密度については検討されていない。 In addition, Patent Document 2 discloses that the temperature and time of magnetic annealing for a rolled Fe-Ni alloy material and the amount of A-based (Mn-S-based) inclusions in the Fe-Ni based alloy are limited, and grain growth of crystal grains is improved. Methods have been proposed to promote this and improve magnetic properties. However, this method aims to improve the coercive force, initial relative permeability, and maximum relative permeability of the obtained soft magnetic component material, and does not consider the saturation magnetic flux density.
上記事情に鑑み、本発明は、優れた初比透磁率と、良好な最大比透磁率及び飽和磁束密度を付与し得ると共に、歩留まりを抑えて製造可能なＦｅ－Ｎｉ系合金及びその製造方法を提供することを目的とする。 In view of the above circumstances, the present invention provides an Fe-Ni alloy that can provide excellent initial relative magnetic permeability, good maximum relative magnetic permeability, and saturation magnetic flux density, and that can be manufactured with a reduced yield, and a method for manufacturing the same. The purpose is to provide.
発明者らは、上記課題を解決するべく鋭意検討を重ねた結果、Ｆｅ－Ｎｉ系合金が有する合金組成を厳密に制御することにより、初比透磁率、最大比透磁率及び飽和磁束密度の磁気特性を改善することができ、さらには歩留まりを抑えて製造可能なＦｅ－Ｎｉ系合金が得られることを見出し、本発明に至った。 As a result of intensive studies to solve the above problems, the inventors have determined that by strictly controlling the alloy composition of the Fe-Ni alloy, the initial relative permeability, maximum relative permeability, and saturation magnetic flux density can be improved. It has been discovered that an Fe--Ni alloy can be obtained that has improved properties and can be manufactured with reduced yield, leading to the present invention.
本発明の要旨は、以下の通りである。
［１］炭素（Ｃ）：０．００１～０．０５質量％、
ケイ素（Ｓｉ）：０．０５～０．５０質量％、
マンガン（Ｍｎ）：０．２５～１．００質量％、
リン（Ｐ）：０．００１～０．０３０質量％、
硫黄（Ｓ）：０．０００１～０．００５０質量％、
ニッケル（Ｎｉ）：３５．０～４４．０質量％、
クロム（Ｃｒ）：０．０１～０．５０質量％、
モリブデン（Ｍｏ）：０．００５～０．１０質量％、
銅（Ｃｕ）：０．０１～２．００質量％、
アルミニウム（Ａｌ）：０．０００１～０．１０質量％、
チタン（Ｔｉ）：０．０５０質量％以下、
コバルト（Ｃｏ）：０．０１～２．００質量％、
タングステン（Ｗ）：０．０１～０．５０質量％、
窒素（Ｎ）：０．００１～０．０５質量％、
スズ（Ｓｎ）：０．０００１～０．０５質量％、
マグネシウム（Ｍｇ）：０．０５０質量％以下、
ジルコニウム（Ｚｒ）：０．０００１～０．０５質量％、
カルシウム（Ｃａ）：０．００２０質量％以下、
酸素（Ｏ）：０．０００２～０．０１質量％を含み、
残部が鉄（Ｆｅ）及び不可避的不純物からなることを特徴とするＦｅ－Ｎｉ系合金板。
［２］下記式（Ａ）の関係式を満たすようにＣｕ、Ｃｏ及びＷを含有する、［１］に記載のＦｅ－Ｎｉ系合金板。
1.5≦20[Cu％]+20[Co％]+80[W％]＜50.0 …（Ａ）
（式（Ａ）中、％は質量％を表す。）
［３］下記式（Ｂ）の関係式を満たすようにＣｕ、Ｃｏ、Ｗ、Ｃｒ、Ｍｏ、Ｐ及びＳを含有する、上記［１］又は［２］に記載のＦｅ－Ｎｉ系合金板。
10≦50([Cu％]+[Co％])+100[W％]+200[Cr％]+800[Mo％]-100[P％]-1000[S％] …（Ｂ）
（式（Ｂ）中、％は質量％を表す。）
［４］Ｆｅ－Ｎｉ系合金の原料を含む溶湯を、ＡＯＤ炉又はＶＯＤ炉のいずれかの二次精錬容器にて酸化精錬を行う工程と、
酸化精錬後の溶湯中にＡｌ及び／又はＦｅＳｉ合金を投入して、溶湯中のＡｌの含有量が０．０００１～０．１０質量％、Ｓｉの含有量が０．０５～０．５０質量％、Ｓの含有量が０．０００１～０．００５０質量％、Ｏの含有量が０．０００２～０．０１質量％の範囲になるように脱酸及び脱硫処理をする工程と、
脱酸及び脱硫処理後の溶湯を連続鋳造してスラブを形成する工程と、
得られたスラブを熱間圧延、次いで冷間圧延を行う工程と、
を含むことを特徴とする、上記［１］～［３］のいずれか１つに記載のＦｅ－Ｎｉ系合金板の製造方法。
The gist of the invention is as follows.
[1] Carbon (C): 0.001 to 0.05% by mass,
Silicon (Si): 0.05 to 0.50% by mass,
Manganese (Mn): 0.25 to 1.00% by mass,
Phosphorus (P): 0.001 to 0.030% by mass,
Sulfur (S): 0.0001 to 0.0050% by mass,
Nickel (Ni): 35.0 to 44.0% by mass,
Chromium (Cr): 0.01 to 0.50% by mass,
Molybdenum (Mo): 0.005 to 0.10% by mass,
Copper (Cu): 0.01 to 2.00% by mass,
Aluminum (Al): 0.0001 to 0.10% by mass,
Titanium (Ti): 0.050% by mass or less,
Cobalt (Co): 0.01 to 2.00% by mass,
Tungsten (W): 0.01 to 0.50% by mass,
Nitrogen (N): 0.001 to 0.05% by mass,
Tin (Sn): 0.0001 to 0.05% by mass,
Magnesium (Mg): 0.050% by mass or less,
Zirconium (Zr): 0.0001 to 0.05% by mass,
Calcium (Ca): 0.0020% by mass or less,
Oxygen (O): Contains 0.0002 to 0.01% by mass,
An Fe--Ni alloy plate characterized in that the remainder consists of iron (Fe) and inevitable impurities.
[2] The Fe--Ni alloy plate according to [1], which contains Cu, Co, and W so as to satisfy the relational expression (A) below.
1.5≦20[Cu%]+20[Co%]+80[W%]＜50.0…(A)
(In formula (A), % represents mass %.)
[3] The Fe--Ni alloy plate according to [1] or [2] above, which contains Cu, Co, W, Cr, Mo, P, and S so as to satisfy the relational expression (B) below.
10≦50([Cu%]+[Co%])+100[W%]+200[Cr%]+800[Mo%]-100[P%]-1000[S%]...(B)
(In formula (B), % represents mass %.)
[4] A step of oxidizing and refining the molten metal containing the Fe-Ni alloy raw material in a secondary refining vessel of either an AOD furnace or a VOD furnace;
Al and/or FeSi alloy is introduced into the molten metal after oxidation refining, and the Al content in the molten metal is 0.0001 to 0.10% by mass and the Si content is 0.05 to 0.50% by mass. , a step of deoxidizing and desulfurizing so that the content of S is in the range of 0.0001 to 0.0050% by mass and the content of O is in the range of 0.0002 to 0.01% by mass;
a step of continuously casting the molten metal after deoxidation and desulfurization treatment to form a slab;
a step of hot rolling and then cold rolling the obtained slab;
The method for producing a Fe--Ni alloy plate according to any one of [1] to [3] above, comprising:
本発明によれば、Ｆｅ－Ｎｉ系合金が有する合金組成を厳密に制御することにより、優れた初比透磁率と、良好な最大比透磁率及び飽和磁束密度を付与し得ると共に、歩留まりを抑えて製造可能なＦｅ－Ｎｉ系合金板及びその製造方法を提供することができる。 According to the present invention, by strictly controlling the alloy composition of the Fe-Ni alloy, it is possible to provide excellent initial relative magnetic permeability, good maximum relative magnetic permeability, and saturation magnetic flux density, and to suppress yield. It is possible to provide a Fe--Ni alloy plate that can be manufactured using the above methods, and a method for manufacturing the same.
以下に本発明に係るＦｅ－Ｎｉ系合金板及びその製造方法について説明する。本発明に係るＦｅ－Ｎｉ系合金板は、炭素（Ｃ）：０．００１～０．０５質量％、ケイ素（Ｓｉ）：０．０５～０．５０質量％、マンガン（Ｍｎ）：０．２５～１．００質量％、
リン（Ｐ）：０．００１～０．０３０質量％、硫黄（Ｓ）：０．０００１～０．００５０質量％、ニッケル（Ｎｉ）：３５．０～４４．０質量％、クロム（Ｃｒ）：０．０１～０．５０質量％、モリブデン（Ｍｏ）：０．００５～０．１０質量％、銅（Ｃｕ）：０．０１～２．００質量％、アルミニウム（Ａｌ）：０．０００１～０．１０質量％、チタン（Ｔｉ）：０．０５０質量％以下、コバルト（Ｃｏ）：０．０１～２．００質量％、タングステン（Ｗ）：０．０１～０．５０質量％、窒素（Ｎ）：０．００１～０．０５質量％、スズ（Ｓｎ）：０．０００１～０．０５質量％、マグネシウム（Ｍｇ）：０．０５０質量％以下、ジルコニウム（Ｚｒ）：０．０００１～０．０５質量％、カルシウム（Ｃａ）：０．００２０質量％以下、酸素（Ｏ）：０．０００２～０．０１質量％を含み、残部が鉄（Ｆｅ）及び不可避的不純物からなる。このように、Ｆｅ－Ｎｉ系合金が有する合金組成を厳密に制御することにより、優れた初比透磁率と、良好な最大比透磁率及び飽和磁束密度を付与し得ると共に、歩留まりを抑えて製造可能なＦｅ－Ｎｉ系合金板を提供することができる。本発明に係るＦｅ－Ｎｉ系合金板はこのような優れた磁気特性を付与し得るため、自動車センサや磁気シールド材、時計のステータ等の軟磁性材料としての使用に好適である。
The Fe--Ni alloy plate and the method for manufacturing the same according to the present invention will be explained below. The Fe-Ni alloy plate according to the present invention has carbon (C): 0.001 to 0.05% by mass, silicon (Si): 0.05 to 0.50% by mass, and manganese (Mn): 0.25%. ~1.00% by mass,
Phosphorus (P): 0.001 to 0.030% by mass, Sulfur (S): 0.0001 to 0.0050% by mass, Nickel (Ni): 35.0 to 44.0% by mass, Chromium (Cr): 0.01 to 0.50% by mass, molybdenum (Mo): 0.005 to 0.10% by mass, copper (Cu): 0.01 to 2.00% by mass, aluminum (Al): 0.0001 to 0 .10% by mass, titanium (Ti): 0.050% by mass or less, cobalt (Co): 0.01 to 2.00% by mass, tungsten (W): 0.01 to 0.50% by mass, nitrogen (N ): 0.001 to 0.05% by mass, tin (Sn): 0.0001 to 0.05% by mass, magnesium (Mg): 0.050% by mass or less, zirconium (Zr): 0.0001 to 0.05% by mass. 05% by mass, calcium (Ca): 0.0020% by mass or less, oxygen (O): 0.0002 to 0.01% by mass, and the remainder consists of iron (Fe) and inevitable impurities. In this way, by strictly controlling the alloy composition of the Fe-Ni alloy, it is possible to provide excellent initial relative magnetic permeability, good maximum relative magnetic permeability, and saturation magnetic flux density, and at the same time, it is possible to manufacture it with reduced yield. It is possible to provide a possible Fe--Ni alloy plate. Since the Fe-Ni alloy plate according to the present invention can provide such excellent magnetic properties, it is suitable for use as a soft magnetic material for automobile sensors, magnetic shielding materials, stators of watches, and the like.
また、本発明に係るＦｅ－Ｎｉ系合金板は、上記の組成成分を満たすことに加え、下記で表される式（Ａ）を満たすように、Ｆｅ－Ｎｉ系合金板が、Ｃｕ、Ｃｏ及びＷを含有することが好ましい。 In addition to satisfying the above compositional components, the Fe-Ni alloy plate according to the present invention also contains Cu, Co and It is preferable to contain W.
1.5≦20[Cu％]+20[Co％]+80[W％]＜50.0 …（Ａ）
（式（Ａ）中、％は質量％を表す。）
1.5≦20[Cu%]+20[Co%]+80[W%]＜50.0…(A)
(In formula (A), % represents mass %.)
上記式（Ａ）は、Ｎｉと原子半径が近いＣｕ、Ｃｏと、Ｎｉとイオン半径が近いＷについて、Ｆｅ－Ｎｉ系合金の最大比透磁率及び飽和磁束密度に対するＣｕ、Ｃｏ及びＷの添加量の影響を関係式として表したものである。図１は、以下の試験方法（磁気特性試験）によって測定された最大比透磁率及び飽和磁束密度と、上記式（Ａ）の値との関係を表すグラフであり、図２は式（Ａ）の値が５．０以下の領域における飽和磁束密度と式（Ａ）の値との関係を表すグラフである。図１は、式（Ａ）の値が５０．０以上では最大比透磁率が３０，０００より低くなることを示し、図２は、式（Ａ）の値が１．５未満の場合、飽和磁束密度が１．４Ｔより低くなることを示している。そのため、式（Ａ）の値が１．５以上５０．０未満の範囲内になるようにＣｕ、Ｃｏ及びＷがＦｅ－Ｎｉ系合金板に含まれることにより、優れた最大比透磁率と飽和磁束密度を付与し得るＦｅ－Ｎｉ系合金板を得ることができる。 The above formula (A) is based on the amounts of Cu, Co, and W added to the maximum relative magnetic permeability and saturation magnetic flux density of the Fe-Ni alloy for Cu, Co, which has an atomic radius close to that of Ni, and W, which has an ionic radius close to Ni. The influence of is expressed as a relational expression. Figure 1 is a graph showing the relationship between the maximum relative magnetic permeability and saturation magnetic flux density measured by the following test method (magnetic property test) and the value of formula (A) above, and Figure 2 is a graph showing the relationship between the value of formula (A) 2 is a graph showing the relationship between the saturation magnetic flux density and the value of formula (A) in a region where the value of is 5.0 or less. Figure 1 shows that when the value of formula (A) is 50.0 or more, the maximum relative permeability becomes lower than 30,000, and Figure 2 shows that when the value of formula (A) is less than 1.5, the maximum relative permeability becomes saturated. This shows that the magnetic flux density becomes lower than 1.4T. Therefore, by including Cu, Co, and W in the Fe-Ni alloy plate so that the value of formula (A) is within the range of 1.5 or more and less than 50.0, excellent maximum relative magnetic permeability and saturation It is possible to obtain a Fe--Ni alloy plate that can impart magnetic flux density.
＜磁気特性試験＞
１０ｋｇ容量の試験用高周波誘電炉で約３９．３質量％のＮｉを基本成分として含むＦｅ－Ｎｉ系合金を溶解した。この溶解に際し、以下の表１に示すように、各合金においてＣｕ、Ｃｏ及びＷの添加量を種々に変化させた。溶解した合金は、その後鋳型に鋳込み鋼塊とした後、熱間鍛造し、厚さ１０ｍｍの鍛造板とした。その後、焼鈍、研磨による表層のスケール除去を行い、０．８ｍｍの厚さまで冷間圧延を行った。この冷延板をＪＩＳ Ｃ２５３１に基づき、φ４５ｍｍ×３３ｍｍのリング試験片に加工し、真空(≦５．０×１０－３Ｐａ)雰囲気中、１１２５℃の均熱で２．５時間の条件で磁気焼鈍した。その後、ＪＩＳ Ｃ３２０２又はＪＩＳ Ｃ３２１５で規定されるエナメル銅線を１次、２次側共に５０巻きし、最大比透磁率（μｍａｘ）及び飽和磁束密度（Ｂ８００)を測定した。最大比透磁率は１６Ａ／ｍを反転磁場とし測定し、飽和磁束密度は磁場１６００Ａ／ｍの条件下で測定した。その結果を表２に示す。尚、表１中の各成分の数値は「質量％」を表す。
<Magnetic property test>
A Fe--Ni alloy containing about 39.3% by mass of Ni as a basic component was melted in a test high-frequency dielectric furnace with a capacity of 10 kg. During this melting, the amounts of Cu, Co, and W added to each alloy were varied as shown in Table 1 below. The melted alloy was then cast into a mold to form a steel ingot, which was then hot forged to form a forged plate with a thickness of 10 mm. Thereafter, scale was removed from the surface layer by annealing and polishing, and cold rolling was performed to a thickness of 0.8 mm. This cold-rolled plate was processed into a ring test piece of φ45 mm x 33 mm based on JIS C2531, and magnetically heated at 1125°C for 2.5 hours in a vacuum (≦5.0 x 10 -3 Pa) atmosphere. Annealed. Thereafter, an enamelled copper wire specified by JIS C3202 or JIS C3215 was wound 50 times on both the primary and secondary sides, and the maximum relative magnetic permeability (μ max ) and saturation magnetic flux density (B 800 ) were measured. The maximum relative magnetic permeability was measured with a reversal magnetic field of 16 A/m, and the saturation magnetic flux density was measured under a magnetic field of 1600 A/m. The results are shown in Table 2. In addition, the numerical value of each component in Table 1 represents "mass %."
このように、Ｃｕ、Ｃｏ及びＷは、優れた飽和磁束密度を得るために重要な元素であり、Ｃｕ、Ｃｏ及びＷの添加量の関係式としての式（Ａ）の値が１．５以上であることにより、１．４Ｔ以上の飽和磁束密度を得ることができる。一方、式（Ａ）の値が５０．０以上の場合、最大比透磁率が３０，０００未満となってしまう。そのため、式（Ａ）の値は、１．５以上５０．０未満の範囲内であることが好ましく、１．５以上４０．０以下の範囲内であることがより好ましく、１．５以上２５．０以下の範囲内であることがさらに好ましい。 As described above, Cu, Co, and W are important elements for obtaining excellent saturation magnetic flux density, and the value of formula (A) as a relational expression between the amounts of Cu, Co, and W added is 1.5 or more. By doing so, a saturation magnetic flux density of 1.4T or more can be obtained. On the other hand, if the value of formula (A) is 50.0 or more, the maximum relative magnetic permeability will be less than 30,000. Therefore, the value of formula (A) is preferably in the range of 1.5 or more and less than 50.0, more preferably in the range of 1.5 or more and 40.0 or less, and 1.5 or more and less than 25 More preferably, it is within the range of .0 or less.
また、本発明に係るＦｅ－Ｎｉ系合金板は、上記の組成成分を満たすことに加え、下記で表される式（Ｂ）を満たすように、Ｆｅ－Ｎｉ系合金板が、Ｃｕ、Ｃｏ、Ｗ、Ｃｒ、Ｍｏ、Ｐ及びＳを含有することが好ましい。 In addition to satisfying the above compositional components, the Fe-Ni alloy plate according to the present invention also contains Cu, Co, It is preferable to contain W, Cr, Mo, P and S.
10≦50([Cu％]+[Co％])+100[W％]+200[Cr％]+800[Mo％]-100[P％]-1000[S％] …（Ｂ）
（式（Ｂ）中、％は質量％を表す。）
10≦50([Cu%]+[Co%])+100[W%]+200[Cr%]+800[Mo%]-100[P%]-1000[S%]...(B)
(In formula (B), % represents mass %.)
Ｆｅ－Ｎｉ系軟磁性材料は温度や湿度等の変化により製造工程中に錆が発生する場合があり、錆に起因する磁気特性の劣化が懸念される。Ｃｕ、Ｃｏ、Ｗ、Ｃｒ、Ｍｏ、Ｐ及びＳは、耐発錆性に影響を及ぼす元素であり、本発明では、式（Ｂ）を満たすように、Ｆｅ－Ｎｉ系合金板が、Ｃｕ、Ｃｏ、Ｗ、Ｃｒ、Ｍｏ、Ｐ及びＳを含有することにより、優れた磁気特性の付与に加えて、耐発錆性を併せ持つＦｅ－Ｎｉ系合金板を得ることができる。このように、Ｆｅ－Ｎｉ系合金板が耐発錆性を示すことにより、錆の除去などの余工程や錆の発生を防止する取り扱いを省くことが可能となり、その結果、作業性の低下、工程数増加による生産性の低下を防止することができる。式（Ｂ）の値は、１０以上であることが好ましく、１５以上であることがより好ましく、２０以上であることがさらに好ましい。 Fe--Ni based soft magnetic materials may rust during the manufacturing process due to changes in temperature, humidity, etc., and there is concern that magnetic properties may deteriorate due to rust. Cu, Co, W, Cr, Mo, P, and S are elements that affect rust resistance, and in the present invention, the Fe-Ni alloy plate contains Cu, By containing Co, W, Cr, Mo, P, and S, it is possible to obtain a Fe-Ni alloy plate that not only provides excellent magnetic properties but also has rust resistance. As described above, the Fe-Ni alloy plate exhibits rust resistance, which makes it possible to eliminate extra steps such as removing rust and handling to prevent rust, resulting in decreased workability and It is possible to prevent a decrease in productivity due to an increase in the number of processes. The value of formula (B) is preferably 10 or more, more preferably 15 or more, and even more preferably 20 or more.
Ｃ：０．００１～０．０５質量％
Ｆｅ－Ｎｉ系合金板中に含まれるＣは、合金の強度を維持するために必要な元素である。Ｃの含有量が０．００１質量％未満ではその効果を十分に得られない。一方、Ｃの含有量が０．０５質量％を超えると合金中に含まれるＣｒやＴｉと反応し炭化物を形成し、結晶粒の成長や磁壁の移動を阻み磁気特性が悪化してしまう。そのため、Ｃの含有量は０．００１～０．０５質量％であり、好ましくは０．００１～０．０１質量％であり、より好ましくは０．００１～０．００８質量％である。
C: 0.001 to 0.05% by mass
C contained in the Fe--Ni alloy plate is an element necessary to maintain the strength of the alloy. If the C content is less than 0.001% by mass, the effect cannot be sufficiently obtained. On the other hand, if the C content exceeds 0.05% by mass, it reacts with Cr and Ti contained in the alloy to form carbides, inhibiting the growth of crystal grains and movement of domain walls, resulting in deterioration of magnetic properties. Therefore, the content of C is 0.001 to 0.05% by mass, preferably 0.001 to 0.01% by mass, and more preferably 0.001 to 0.008% by mass.
Ｓｉ：０．０５～０．５０質量％
Ｆｅ－Ｎｉ系合金板中に含まれるＳｉは、Ｆｅ－Ｎｉ系合金板を製造する際に行われる脱酸処理に有効な元素である。Ｓｉの含有量が０．０５質量％未満ではその効果を十分に得られない。一方、Ｓｉの含有量が０．５０質量％を超えると、Ｆｅ－Ｎｉ合金の規則格子が最適な状態ではなくなり、磁気特性を悪化させてしまう。そのため、Ｓｉの含有量は０．０５～０．５０質量％であり、好ましいＳｉの含有量の下限値は０．１０質量％であり、好ましいＳｉの含有量の上限値は０．２５質量％である。すなわち、Ｓｉの含有量は、好ましくは０．０５～０．２５質量％であり、より好ましくは０．１０～０．２５質量％である。
Si: 0.05 to 0.50% by mass
Si contained in the Fe--Ni alloy sheet is an effective element in the deoxidation treatment performed when manufacturing the Fe--Ni alloy sheet. If the Si content is less than 0.05% by mass, the effect cannot be sufficiently obtained. On the other hand, if the Si content exceeds 0.50% by mass, the ordered lattice of the Fe--Ni alloy will no longer be in an optimal state, resulting in deterioration of the magnetic properties. Therefore, the Si content is 0.05 to 0.50% by mass, the lower limit of the preferred Si content is 0.10% by mass, and the upper limit of the preferred Si content is 0.25% by mass. It is. That is, the Si content is preferably 0.05 to 0.25% by mass, more preferably 0.10 to 0.25% by mass.
Ｍｎ：０．２５～１．００質量％
Ｆｅ－Ｎｉ系合金板中に含まれるＭｎは、熱間加工性を低下させるＳと結合してＭｎＳを形成し、Ｓによる熱間加工性の低下を抑え、また、ＭｎＳの形成に伴い、打抜き性を改善させるのに有効な元素である。Ｍｎの含有量が０．２５質量％未満ではその効果を十分に得られない。一方、Ｍｎの含有量が１．００質量％を超えると、ＭｎＳが過剰に形成されて、結晶粒の成長や磁壁の移動を阻み磁気特性が悪化してしまう。そのため、Ｍｎの含有量は０．２５～１．００質量％であり、好ましくは０．２５～０．６０質量％であり、より好ましくは０．２５～０．５７質量％である。
Mn: 0.25 to 1.00% by mass
Mn contained in the Fe-Ni alloy sheet combines with S, which reduces hot workability, to form MnS, suppresses the reduction in hot workability caused by S, and also improves the punching process due to the formation of MnS. It is an effective element for improving sex. If the Mn content is less than 0.25% by mass, the effect cannot be sufficiently obtained. On the other hand, when the Mn content exceeds 1.00% by mass, MnS is formed excessively, inhibiting the growth of crystal grains and movement of domain walls, resulting in deterioration of magnetic properties. Therefore, the Mn content is 0.25 to 1.00% by mass, preferably 0.25 to 0.60% by mass, and more preferably 0.25 to 0.57% by mass.
Ｐ：０．００１～０．０３０質量％
Ｆｅ－Ｎｉ系合金板中に含まれるＰは、結晶粒界に偏析することによってＳの結晶粒界への偏析を抑制し、ＭｎＳの分散析出を促進させ、打抜き性を改善させるのに有効な元素である。Ｐの含有量が０．００１質量％未満ではその効果を十分に得られない。一方、０．０３０質量％を超えると、Ｐが結晶粒界に過剰に偏析し、熱間加工性を悪化させるだけでなく、耐発錆性を低下させる。そのため、Ｐの含有量は０．００１～０．０３０質量％であり、好ましくは０．００１～０．０２０質量％であり、より好ましくは０．００１～０．０１９質量％である。
P: 0.001 to 0.030% by mass
P contained in the Fe-Ni alloy plate is effective in suppressing the segregation of S in the grain boundaries by segregating in the grain boundaries, promoting the dispersed precipitation of MnS, and improving the punching property. It is an element. If the P content is less than 0.001% by mass, the effect cannot be sufficiently obtained. On the other hand, if it exceeds 0.030% by mass, P segregates excessively at grain boundaries, which not only deteriorates hot workability but also reduces rust resistance. Therefore, the content of P is 0.001 to 0.030% by mass, preferably 0.001 to 0.020% by mass, and more preferably 0.001 to 0.019% by mass.
Ｓ：０．０００１～０．００５０質量％
Ｆｅ－Ｎｉ系合金板中に含まれるＳは、ＭｎやＭｇと結合してＭｎＳやＭｇＳを形成し、打抜き性を改善させるのに有効な元素である。Ｓの含有量が０．０００１質量％未満ではその効果を十分に得られない。一方、Ｓの含有量が０．００５０質量％を超えると、Ｓが粒界に偏析して低融点化合物を形成し、熱間加工性が著しく低下してしまうだけでなく、耐発錆性を低下させてしまう。そのため、Ｓの含有量は０．０００１～０．００５０質量％であり、好ましいＳの含有量の下限値は０．０００３質量％、より好ましくは０．０００５質量％であり、好ましいＳの含有量の上限値は０．００４０質量％であり、より好ましくは０．００３０質量％である。すなわち、Ｓの含有量は、好ましくは０．０００３～０．００４０質量％であり、より好ましくは０．０００５～０．００３０質量％である。
S: 0.0001 to 0.0050% by mass
S contained in the Fe--Ni alloy plate is an effective element for combining with Mn and Mg to form MnS and MgS and improving punching properties. If the S content is less than 0.0001% by mass, the effect cannot be sufficiently obtained. On the other hand, if the S content exceeds 0.0050% by mass, S will segregate at grain boundaries and form a low melting point compound, which will not only significantly reduce hot workability but also reduce rust resistance. It will lower it. Therefore, the S content is 0.0001 to 0.0050% by mass, and the lower limit of the preferred S content is 0.0003% by mass, more preferably 0.0005% by mass. The upper limit of is 0.0040% by mass, more preferably 0.0030% by mass. That is, the content of S is preferably 0.0003 to 0.0040% by mass, more preferably 0.0005 to 0.0030% by mass.
Ｎｉ：３５．０～４４．０質量％
Ｆｅ－Ｎｉ系合金板中に含まれるＮｉは、磁気特性を確保するために重要な元素である。Ｎｉの含有量が３５．０質量％未満ではその効果を十分に得られない。一方、Ｎｉの含有量が４４．０質量％を超えると熱間圧延時に圧延板の表面に傷がついたり、耳割れが発生し、歩留まりが低下してしまう。そのため、Ｎｉの含有量は３５．０～４４．０質量％であり、好ましいＮｉの含有量の下限値は３５．７質量％、より好ましくは４０．５質量％であり、好ましいＮｉの含有量の上限値は４２．６質量％であり、より好ましくは４１．５質量％である。すなわち、Ｎｉの含有量は、好ましくは３５．７～４２．６質量％であり、より好ましくは４０．５～４１．５質量％である。
Ni: 35.0 to 44.0% by mass
Ni contained in the Fe--Ni alloy plate is an important element for ensuring magnetic properties. If the Ni content is less than 35.0% by mass, the effect cannot be sufficiently obtained. On the other hand, if the Ni content exceeds 44.0% by mass, the surface of the rolled plate will be scratched or edge cracks will occur during hot rolling, resulting in a decrease in yield. Therefore, the Ni content is 35.0 to 44.0% by mass, and the lower limit of the preferred Ni content is 35.7% by mass, more preferably 40.5% by mass. The upper limit of is 42.6% by mass, more preferably 41.5% by mass. That is, the Ni content is preferably 35.7 to 42.6% by mass, more preferably 40.5 to 41.5% by mass.
Ｃｒ：０．０１～０．５０質量％
Ｆｅ－Ｎｉ系合金板中に含まれるＣｒは、耐発錆性を確保するために有効な元素である。Ｃｒの含有量が０．０１質量％未満ではその効果を十分に得られない。一方、Ｃｒの含有量が０．５０質量％を超えると、Ｆｅ－Ｎｉ系合金中に存在するＣと結合してＣｒ系炭化物を形成し、磁壁の移動を阻み磁気特性を悪化させてしまう。そのため、Ｃｒの含有量は０．０１～０．５０質量％であり、好ましいＣｒの含有量の下限値は０．０２質量％、より好ましくは０．０３質量％であり、好ましいＣｒの含有量の上限値は０．１０質量％であり、より好ましくは０．０８質量％である。すなわち、Ｃｒの含有量は、好ましくは０．０２～０．１０質量％であり、より好ましくは０．０３～０．０８質量％である。
Cr: 0.01 to 0.50% by mass
Cr contained in the Fe--Ni alloy plate is an effective element for ensuring rust resistance. If the Cr content is less than 0.01% by mass, the effect cannot be sufficiently obtained. On the other hand, if the Cr content exceeds 0.50% by mass, it combines with C present in the Fe--Ni alloy to form Cr-based carbides, which impede movement of domain walls and deteriorate magnetic properties. Therefore, the Cr content is 0.01 to 0.50% by mass, and the lower limit of the preferred Cr content is 0.02% by mass, more preferably 0.03% by mass. The upper limit of is 0.10% by mass, more preferably 0.08% by mass. That is, the Cr content is preferably 0.02 to 0.10% by mass, more preferably 0.03 to 0.08% by mass.
Ｍｏ：０．００５～０．１０質量％
Ｆｅ－Ｎｉ系合金板中に含まれるＭｏは、耐発錆性を確保するために有効な元素であると同時に、結晶磁気異方性や磁歪に影響する規則格子の生成条件を制御するために重要な元素である。Ｍｏの含有量が０．００５質量％未満ではその効果を十分に得られない。一方、Ｍｏの含有量が０．１０質量％を超えると飽和磁束密度を低下させてしまう。そのため、Ｍｏの含有量は０．００５～０．１０質量％であり、好ましいＭｏの含有量の下限値は０．０１質量％であり、好ましいＭｏの含有量の上限値は０．０５質量％である。すなわち、Ｍｏの含有量は、好ましくは０．０１～０．０５質量％である。
Mo: 0.005 to 0.10% by mass
Mo contained in the Fe-Ni alloy plate is an effective element for ensuring rust resistance, and at the same time it is an effective element for controlling the formation conditions of the ordered lattice that affects crystal magnetic anisotropy and magnetostriction. It is an important element. If the Mo content is less than 0.005% by mass, the effect cannot be sufficiently obtained. On the other hand, if the Mo content exceeds 0.10% by mass, the saturation magnetic flux density will be reduced. Therefore, the content of Mo is 0.005 to 0.10% by mass, the lower limit of the preferred content of Mo is 0.01% by mass, and the upper limit of the preferred content of Mo is 0.05% by mass. It is. That is, the content of Mo is preferably 0.01 to 0.05% by mass.
Ｃｕ：０．０１～２．００質量％
Ｆｅ－Ｎｉ系合金板中に含まれるＣｕは、飽和磁束密度を確保すると同時に、耐発錆性を確保するために重要な元素である。Ｃｕの含有量が０．０１質量％未満では耐発錆性を十分に得られない。一方、Ｃｕの含有量が２．００質量％を超えると、スリット加工又は打抜き加工時にバリやダレが発生し、製品形状の悪化を招く。そのため、Ｃｕの含有量は０．０１～２．００質量％であり、好ましくは０．０１～０．５０質量％であり、より好ましくは０．０１～０．４０質量％である。
Cu: 0.01 to 2.00% by mass
Cu contained in the Fe--Ni alloy plate is an important element for ensuring saturation magnetic flux density and rust resistance. If the Cu content is less than 0.01% by mass, sufficient rust resistance cannot be obtained. On the other hand, when the Cu content exceeds 2.00% by mass, burrs and sag occur during slitting or punching, leading to deterioration of the product shape. Therefore, the Cu content is 0.01 to 2.00% by mass, preferably 0.01 to 0.50% by mass, and more preferably 0.01 to 0.40% by mass.
Ａｌ：０．０００１～０．１０質量％
Ｆｅ－Ｎｉ系合金板中に含まれるＡｌは、Ｆｅ－Ｎｉ系合金板を製造する際に行われる脱酸処理に有効な元素である。Ａｌの含有量が０．０００１質量％未満ではその効果を十分に得られず、また、Ｆｅ－Ｎｉ系合金中のＯの濃度を高めてしまうため、酸化物系介在物の個数が増加し、磁気特性を低下させてしまう。一方、Ａｌの含有量が０．１０質量％を超えると、スラグ中のＭｇＯを還元する力が強くなり過ぎてしまい、Ｆｅ－Ｎｉ系合金中のＭｇの濃度が高まり、低融点の金属間化合物であるＮｉ２Ｍｇが生成し、熱間加工性を低下させてしまう。また、それと同時に、スラグ中のＣａＯを還元する力も強くなり過ぎてしまい、鋼中のＣａの濃度が高まり、磁気特性が低下する。そのため、Ａｌの含有量は０．０００１～０．１０質量％であり、好ましくは０．０００１～０．０５０質量％であり、より好ましくは０．０００１～０．０４５質量％である。
Al: 0.0001 to 0.10% by mass
Al contained in the Fe--Ni alloy sheet is an effective element in the deoxidation treatment performed when manufacturing the Fe--Ni alloy sheet. If the Al content is less than 0.0001% by mass, the effect cannot be sufficiently obtained, and the concentration of O in the Fe-Ni alloy increases, resulting in an increase in the number of oxide inclusions. This will deteriorate the magnetic properties. On the other hand, when the Al content exceeds 0.10% by mass, the power to reduce MgO in the slag becomes too strong, the concentration of Mg in the Fe-Ni alloy increases, and low melting point intermetallic compounds Ni 2 Mg is generated, which deteriorates hot workability. At the same time, the power to reduce CaO in the slag becomes too strong, increasing the concentration of Ca in the steel and deteriorating its magnetic properties. Therefore, the Al content is 0.0001 to 0.10% by mass, preferably 0.0001 to 0.050% by mass, and more preferably 0.0001 to 0.045% by mass.
Ｔｉ：０．０５０質量％以下
Ｆｅ－Ｎｉ系合金板中に含まれるＴｉは、Ｆｅ－Ｎｉ系合金中に存在するＣやＮと結合してＴｉ系炭化物や窒化物を形成する。Ｔｉの含有量が多すぎると、結晶粒の成長や磁壁の移動を阻み磁気特性を悪化させてしまう。一方、Ｔｉは窒化物の形成により、打抜き性の改善に有効なＭｎＳの核となり、析出を促進させる。そのため磁気特性と打抜き性のバランスを考慮し、Ｔｉの含有量は０．０５０質量％以下であり、好ましいＴｉの含有量の下限値は０．００１質量％であり、好ましいＴｉの含有量の上限値は０．０２０質量％である。すなわち、Ｔｉの含有量は、好ましくは０．００１～０．０２０質量％である。
Ti: 0.050% by mass or less Ti contained in the Fe--Ni alloy plate combines with C and N present in the Fe--Ni alloy to form Ti-based carbides and nitrides. If the Ti content is too high, it will inhibit the growth of crystal grains and the movement of domain walls, resulting in deterioration of magnetic properties. On the other hand, by forming nitrides, Ti becomes a nucleus of MnS, which is effective in improving punching properties, and promotes precipitation. Therefore, considering the balance between magnetic properties and punchability, the Ti content is 0.050% by mass or less, the lower limit of the preferred Ti content is 0.001% by mass, and the upper limit of the preferred Ti content is 0.001% by mass. The value is 0.020% by mass. That is, the Ti content is preferably 0.001 to 0.020% by mass.
Ｃｏ：０．０１～２．００質量％
Ｆｅ－Ｎｉ系合金板中に含まれるＣｏは、飽和磁束密度を確保すると同時に、耐発錆性を確保するために重要な元素である。Ｃｏの含有量が０．０１質量％未満では耐発錆性を十分に得られない。一方、Ｃｏの含有量が２．００質量％を超えると、スリット加工又は打抜き加工時にバリやダレが発生し、製品形の悪化を招く。そのため、Ｃｏの含有量は０．０１～２．００質量％であり、好ましくは０．０１～１．００質量％であり、より好ましくは０．０１～０．５０質量％である。
Co: 0.01 to 2.00% by mass
Co contained in the Fe--Ni alloy plate is an important element for ensuring saturation magnetic flux density and rust resistance. If the Co content is less than 0.01% by mass, sufficient rust resistance cannot be obtained. On the other hand, if the Co content exceeds 2.00% by mass, burrs and sagging occur during slitting or punching, leading to deterioration of the product shape. Therefore, the Co content is 0.01 to 2.00% by mass, preferably 0.01 to 1.00% by mass, and more preferably 0.01 to 0.50% by mass.
Ｗ：０．０１～０．５０質量％
Ｆｅ－Ｎｉ系合金板中に含まれるＷは、飽和磁束密度を確保すると同時に、耐発錆性を確保するために重要な元素である。Ｗの含有量が０．０１質量％未満では耐発錆性を十分に得られない。一方、Ｗの含有量が０．５０質量％を超えると、スリット加工又は打抜き加工時に反りが発生し、製品形の悪化を招く。そのため、Ｗの含有量は０．０１～０．５０質量％であり、好ましくは０．０１～０．１０質量％であり、より好ましくは０．０１～０．０５質量％である。
W: 0.01 to 0.50% by mass
W contained in the Fe--Ni alloy plate is an important element for ensuring saturation magnetic flux density and rust resistance. If the W content is less than 0.01% by mass, sufficient rust resistance cannot be obtained. On the other hand, if the W content exceeds 0.50% by mass, warping occurs during slitting or punching, leading to deterioration of the product shape. Therefore, the content of W is 0.01 to 0.50% by mass, preferably 0.01 to 0.10% by mass, and more preferably 0.01 to 0.05% by mass.
Ｎ：０．００１～０．０５質量％
Ｆｅ－Ｎｉ系合金板中に含まれるＮは、Ｆｅ－Ｎｉ系合金の強度を確保するために必要な元素である。Ｎの含有量が０．００１質量％未満ではその効果を十分に得られない。一方、Ｎの含有量が０．０５質量％を超えると、Ｆｅ－Ｎｉ系合金中にＴｉが存在する場合、Ｔｉと結合することで窒化物が形成され、結晶粒の成長や磁壁の移動を阻み磁気特性を悪化させてしまう。そのため、Ｎの含有量は０．００１～０．０５質量％であり、好ましいＮｉの含有量の上限値は０．０１質量％であり、より好ましくは０．００６質量％である。すなわち、Ｎｉの含有量は、好ましくは０．００１～０．０１質量％であり、より好ましくは０．００１～０．００６質量％である。
N: 0.001 to 0.05% by mass
N contained in the Fe-Ni alloy plate is an element necessary to ensure the strength of the Fe-Ni alloy. If the N content is less than 0.001% by mass, the effect cannot be sufficiently obtained. On the other hand, if the N content exceeds 0.05% by mass, if Ti is present in the Fe-Ni alloy, it will combine with Ti to form nitrides, which will inhibit the growth of crystal grains and the movement of domain walls. This results in deterioration of the magnetic properties. Therefore, the N content is 0.001 to 0.05% by mass, and the preferable upper limit of the Ni content is 0.01% by mass, more preferably 0.006% by mass. That is, the Ni content is preferably 0.001 to 0.01% by mass, more preferably 0.001 to 0.006% by mass.
Ｓｎ：０．０００１～０．０５質量％
Ｆｅ－Ｎｉ系合金板中に含まれるＳｎは、めっき性を確保するために必要な元素である。Ｓｎの含有量が０．０００１質量％未満ではその効果を十分に得られない。一方、Ｓｎの含有量が０．０５質量％を超えると熱間加工性を低下させてしまう。そのため、Ｓｎの含有量は０．０００１～０．０５質量％であり、好ましいＳｎの含有量の上限値は０．０１質量％であり、より好ましくは０．００５質量％である。すなわち、Ｓｎの含有量は、好ましくは０．０００１～０．０１質量％であり、より好ましくは０．０００１～０．００５質量％である。
Sn: 0.0001 to 0.05% by mass
Sn contained in the Fe--Ni alloy plate is an element necessary to ensure plating properties. If the Sn content is less than 0.0001% by mass, the effect cannot be sufficiently obtained. On the other hand, if the Sn content exceeds 0.05% by mass, hot workability will be reduced. Therefore, the Sn content is 0.0001 to 0.05% by mass, and the preferred upper limit of the Sn content is 0.01% by mass, more preferably 0.005% by mass. That is, the content of Sn is preferably 0.0001 to 0.01% by mass, more preferably 0.0001 to 0.005% by mass.
Ｍｇ：０．０５質量％以下
Ｆｅ－Ｎｉ系合金板中に含まれるＭｇは、Ｆｅ－Ｎｉ系合金中に存在するＳと結合してＭｇＳを形成する。Ｍｇの含有量が多すぎると、ＭｇＳが過剰に形成され、結晶粒の成長や磁壁の移動を阻み磁気特性を悪化させてしまう。しかしながら、Ｍｇは製造都合上不可逆的に混入する。そのため、磁気特性の観点から、Ｍｇの含有量は０．０５質量％以下であり、好ましくは０．０１質量％以下であり、より好ましくは０．００５質量％以下である。
Mg: 0.05% by mass or less Mg contained in the Fe--Ni alloy plate combines with S present in the Fe--Ni alloy to form MgS. If the Mg content is too high, MgS will be formed excessively, inhibiting the growth of crystal grains and movement of domain walls, and deteriorating magnetic properties. However, Mg is irreversibly mixed in due to manufacturing convenience. Therefore, from the viewpoint of magnetic properties, the Mg content is 0.05% by mass or less, preferably 0.01% by mass or less, and more preferably 0.005% by mass or less.
Ｚｒ：０．０００１～０．０５質量％
Ｆｅ－Ｎｉ系合金板中に含まれるＺｒは、Ｆｅ－Ｎｉ系合金の強度を確保するために必要な元素である。Ｚｒの含有量が０．０００１質量％未満ではその効果を十分に得られない。一方、Ｚｒの含有量が０．０５質量％を超えると磁気特性を低下させてしまう。そのため、Ｚｒの含有量は０．０００１～０．０５質量％であり、好ましくは０．０００１～０．０１質量％であり、より好ましくは０．０００１～０．００８質量％である。
Zr: 0.0001 to 0.05% by mass
Zr contained in the Fe-Ni alloy plate is an element necessary to ensure the strength of the Fe-Ni alloy. If the Zr content is less than 0.0001% by mass, the effect cannot be sufficiently obtained. On the other hand, if the Zr content exceeds 0.05% by mass, the magnetic properties will be deteriorated. Therefore, the content of Zr is 0.0001 to 0.05% by mass, preferably 0.0001 to 0.01% by mass, and more preferably 0.0001 to 0.008% by mass.
Ｃａ：０．００２０質量％以下
Ｆｅ－Ｎｉ系合金板中に含まれるＣａは、Ｆｅ－Ｎｉ系合金中に存在するＡｌと結合してＣａ－Ａｌ酸化物系介在物を形成する。Ｃａの含有量が多すぎると、Ｃａ－Ａｌ酸化物系介在物が過剰に形成され、結晶粒の成長や磁壁の移動を阻み磁気特性を悪化させてしまう。一方、ＣａはＳｉＯ２活量を抑制し、また、Ｏの含有量を制御して介在物量を低減するために重要な元素である。そのため、磁気特性の観点から、Ｃａの含有量は０．００２０質量％以下であり、好ましいＣａの含有量の下限値は０．０００１質量％であり、好ましいＣａの含有量の上限値は０．００１０質量％である。すなわち、Ｃａの含有量は、好ましくは０．０００１～０．００１０質量％である。
Ca: 0.0020% by mass or less Ca contained in the Fe--Ni alloy plate combines with Al present in the Fe--Ni alloy to form Ca--Al oxide inclusions. If the Ca content is too high, excessive Ca--Al oxide inclusions will be formed, inhibiting the growth of crystal grains and movement of domain walls, and deteriorating magnetic properties. On the other hand, Ca is an important element for suppressing the SiO 2 activity and controlling the O content to reduce the amount of inclusions. Therefore, from the viewpoint of magnetic properties, the Ca content is 0.0020% by mass or less, the preferred lower limit of the Ca content is 0.0001% by mass, and the preferred upper limit of the Ca content is 0.0001% by mass. 0010% by mass. That is, the Ca content is preferably 0.0001 to 0.0010% by mass.
Ｏ：０．０００２～０．０１質量％
Ｆｅ－Ｎｉ系合金板中（溶湯中）に含まれるＯの含有量が０．０００２質量％未満では、スラグ中のＣａＯが還元されて溶湯中のＣａの濃度が高まり、Ｃａ－Ａｌ酸化物系介在物が過剰に形成され、結晶粒の成長や磁壁の移動を阻み磁気特性を悪化させてしまう。一方、Ｏの含有量が０．０１質量％を超えると、他の元素と酸化物系介在物が形成され、磁壁の移動を阻み磁気特性を悪化させてしまう。そのため、Ｏの含有量は０．０００２～０．０１質量％であり、好ましいＯの含有量の下限値は０．０００５質量％であり、好ましいＯの含有量の上限値は０．００８質量％である。すなわち、Ｏの含有量は、好ましくは０．０００５～０．００８質量％である。
O: 0.0002 to 0.01% by mass
If the content of O contained in the Fe-Ni alloy plate (in the molten metal) is less than 0.0002% by mass, CaO in the slag will be reduced and the concentration of Ca in the molten metal will increase, causing Ca-Al oxide-based Inclusions are excessively formed and impede growth of crystal grains and movement of domain walls, resulting in deterioration of magnetic properties. On the other hand, when the content of O exceeds 0.01% by mass, oxide-based inclusions are formed with other elements, which impede movement of domain walls and deteriorate magnetic properties. Therefore, the content of O is 0.0002 to 0.01% by mass, the lower limit of the preferred content of O is 0.0005% by mass, and the upper limit of the preferred content of O is 0.008% by mass. It is. That is, the content of O is preferably 0.0005 to 0.008% by mass.
本発明に係るＦｅ－Ｎｉ系合金板において、上記成分以外の残部はＦｅ及び不可避的不純物であり、主成分としてＦｅが含有されている。 In the Fe-Ni alloy plate according to the present invention, the remainder other than the above components is Fe and unavoidable impurities, and Fe is contained as the main component.
Ｆｅ－Ｎｉ系合金板の厚さは、特に限定されるものではないが、０．０５ｍｍ以上６．００ｍｍ以下であることが好ましく、０．０８ｍｍ以上４．００ｍｍ以下であることがより好ましい。 The thickness of the Fe--Ni alloy plate is not particularly limited, but is preferably 0.05 mm or more and 6.00 mm or less, more preferably 0.08 mm or more and 4.00 mm or less.
次に、本発明に係るＦｅ－Ｎｉ系合金板の製造方法について説明する。本発明に係るＦｅ－Ｎｉ系合金板の製造方法は、（ａ）Ｆｅ－Ｎｉ系合金の原料を含む溶湯を、ＡＯＤ炉又はＶＯＤ炉のいずれかの二次精錬容器にて酸化精錬を行う工程（以下、「工程（ａ）」ともいう）と、（ｂ）酸化精錬後の溶湯中にＡｌ及び／又はＦｅＳｉ合金を投入して、溶湯中のＡｌの含有量が０．０００１～０．１０質量％、Ｓｉの含有量が０．０５～０．５０質量％、Ｓの含有量が０．０００１～０．００５０質量％、Ｏの含有量が０．０００２～０．０１質量％の範囲になるように脱酸及び脱硫処理をする工程（以下、「工程（ｂ）」ともいう）と、（ｃ）脱酸及び脱硫処理後の溶湯を連続鋳造してスラブを形成する工程（以下、「工程（ｃ）」ともいう）と、（ｄ）得られたスラブを熱間圧延、次いで冷間圧延を行う工程（以下、「工程（ｄ）」ともいう）と、を含んでいる。 Next, a method for manufacturing an Fe--Ni alloy plate according to the present invention will be explained. The method for producing a Fe-Ni alloy plate according to the present invention includes (a) a step of oxidizing and refining a molten metal containing a raw material of an Fe-Ni alloy in a secondary refining vessel of either an AOD furnace or a VOD furnace; (hereinafter also referred to as "step (a)"), and (b) adding Al and/or FeSi alloy to the molten metal after oxidation refining, so that the Al content in the molten metal is 0.0001 to 0.10. mass%, Si content in the range of 0.05 to 0.50 mass%, S content in the range of 0.0001 to 0.0050 mass%, and O content in the range of 0.0002 to 0.01 mass%. (hereinafter also referred to as "step (b)"), and (c) a step of continuously casting the molten metal after the deoxidation and desulfurization treatment to form a slab (hereinafter referred to as "step (b)"). (d) hot rolling and then cold rolling the obtained slab (hereinafter also referred to as "step (d)").
工程（ａ）
工程（ａ）では、Ｆｅ－Ｎｉ系合金の原料を含む溶湯を、ＡＯＤ（Ａｒｇｏｎ Ｏｘｙｇｅｎ Ｄｅｃａｒｂｕｒｉｚａｔｉｏｎ）炉又はＶＯＤ（Ｖａｃｕｕｍ Ｏｘｙｇｅｎ Ｄｅｃａｒｂｕｒｉｚａｔｉｏｎ）炉のいずれかの二次精錬容器を用いて酸化精錬が行われる。溶湯は、Ｆｅ－Ｎｉ系合金の原料を電気炉で溶解させることで得られる。原料として、例えば、鉄屑、ニッケル、フェロニッケル等を用いることができ、Ｆｅ－Ｎｉ系合金スラブ片、Ｆｅ－Ｎｉ系の屑等を用いてもよい。得られた溶湯をＡＯＤ炉又はＶＯＤ炉のいずれかの二次精錬容器を用いて脱炭することにより、脱炭後の酸化性スラグ、すなわち、ＦｅＯ含有スラグであるＦｅＯ－ＣａＯ－ＳｉＯ２系スラグを排滓することが可能である。このスラグにはクロム酸化物、タングステン酸化物、チタン酸化物、リン酸化物も含有されており、これらの酸化物も、系外に排出することができる。これにより、得られるＦｅ－Ｎｉ系合金板において、Ｃｒの含有量を上記範囲内に制御することができ、さらには、Ｗの含有量、Ｔｉの含有量も上記範囲内に制御しやすくなり、その上、有害な不純物元素であるＰの含有量を０．０３０質量％以下に低減できる。このように、二次精錬容器としてＡＯＤ炉又はＶＯＤ炉のいずれかを用いて酸化精錬を行うことにより、上述の酸化性スラグを系外に排出することが可能となる。尚、ＶＯＤ炉は一旦除滓場に取鍋を移し、除滓機で排滓を行うため、溶湯温度が下がりやすいことから、ＡＯＤ炉の利用がより有効である。
Process (a)
In step (a), oxidation refining is performed on the molten metal containing the Fe-Ni alloy raw material using a secondary refining vessel such as an AOD (Argon Oxygen Decarburization) furnace or a VOD (Vacuum Oxygen Decarburization) furnace. The molten metal is obtained by melting Fe--Ni alloy raw materials in an electric furnace. As the raw material, for example, iron scraps, nickel, ferronickel, etc. can be used, and Fe--Ni alloy slab pieces, Fe--Ni-based scraps, etc. may also be used. By decarburizing the obtained molten metal using a secondary refining vessel such as an AOD furnace or a VOD furnace, oxidizing slag after decarburization, that is, FeO-CaO-SiO 2- based slag, which is FeO-containing slag. It is possible to remove the slag. This slag also contains chromium oxide, tungsten oxide, titanium oxide, and phosphorus oxide, and these oxides can also be discharged from the system. As a result, in the obtained Fe-Ni alloy plate, the Cr content can be controlled within the above range, and furthermore, the W content and Ti content can also be easily controlled within the above range, Moreover, the content of P, which is a harmful impurity element, can be reduced to 0.030% by mass or less. In this way, by performing oxidation refining using either the AOD furnace or the VOD furnace as the secondary refining vessel, it becomes possible to discharge the above-mentioned oxidizing slag to the outside of the system. In addition, in the case of a VOD furnace, the ladle is first moved to a slag removal site and the sludge is removed by a slag removal machine, so the temperature of the molten metal tends to drop, so it is more effective to use an AOD furnace.
また、工程（ａ）によって、得られるＦｅ－Ｎｉ系合金板が、上記式（Ａ）を満たすように、Ｃｕ、Ｃｏ及びＷの含有量を適切に制御することができる。すなわち、上記式（Ａ）の値を１．５以上５０．０未満の範囲内に制御しやすくなり、好ましくは１．５以上４０．０以下の範囲内に、より好ましくは１．５以上２５．０以下の範囲内に抑えることが可能となる。 In addition, the contents of Cu, Co, and W can be appropriately controlled by step (a) so that the obtained Fe--Ni alloy plate satisfies the above formula (A). That is, the value of the above formula (A) can be easily controlled within the range of 1.5 or more and less than 50.0, preferably within the range of 1.5 or more and 40.0 or less, more preferably 1.5 or more and less than 25 It is possible to suppress the value within a range of .0 or less.
工程（ｂ）
工程（ｂ）では、酸化精錬後の溶湯中にＡｌ及び／又はＦｅＳｉ合金を投入して脱酸及び脱硫処理が施される。酸化精錬により、上述の酸化性スラグを排滓したとしても溶湯上には１トン程度の酸化性スラグが依然として残っている。そのため、残存する酸化性スラグ中のＦｅＯ濃度、溶湯中の酸素濃度を考慮して、それに見合う量のＡｌ及び／又はＦｅＳｉ合金を溶湯中に投入し、溶湯を脱酸及び脱硫させる。特に、溶湯中に含まれるＡｌの含有量が０．０００１～０．１質量％の範囲内、Ｓｉの含有量が０．０５～０．５質量％の範囲内に調製されるようにＡｌ及びＦｅＳｉ合金を投入することにより、最も好ましい形態で脱酸及び脱硫が進行し、得られるＦｅ－Ｎｉ系合金板において、Ｏの含有量を０．０００２～０．０１質量％の範囲内、Ｓの含有量を０．０００１～０．００５０質量％の範囲内にそれぞれ制御できる他、その他の熱力学的に不安定な元素も上述の範囲内に制御できる。以下に、その理論を説明する。
Process (b)
In step (b), Al and/or FeSi alloy is introduced into the molten metal after oxidation refining to perform deoxidation and desulfurization treatment. Even if the above-mentioned oxidizing slag is removed by oxidation refining, about 1 ton of oxidizing slag still remains on the molten metal. Therefore, in consideration of the FeO concentration in the remaining oxidizing slag and the oxygen concentration in the molten metal, an amount of Al and/or FeSi alloy corresponding to the concentration is poured into the molten metal to deoxidize and desulfurize the molten metal. In particular, Al and Si are adjusted so that the content of Al contained in the molten metal is within the range of 0.0001 to 0.1% by mass, and the content of Si is within the range of 0.05 to 0.5% by mass. By adding the FeSi alloy, deoxidation and desulfurization proceed in the most preferable manner, and in the resulting Fe-Ni alloy plate, the content of O is within the range of 0.0002 to 0.01% by mass, and the content of S is In addition to controlling the content within the range of 0.0001 to 0.0050% by mass, other thermodynamically unstable elements can also be controlled within the above range. The theory will be explained below.
上述の工程（ａ）及び工程（ｂ）を含む精錬過程では、得られるスラグが非常に重要な役割を果たす。形成させるスラグは特に限定されるものではないが、ＣａＯ－ＳｉＯ２－Ａｌ２Ｏ３－ＭｇＯ－Ｆ系スラグが形成されることが好ましい。このようなスラグに含まれるＣａＯは、石灰石を焼成してＣＯ２を解離しＣａＯとして得た生石灰を溶湯中に投入することにより形成でき、ＳｉＯ２はＦｅＳｉ合金投入後の酸化により形成できる。スラグ中でＣａＯは特に重要な役割を果たし、スラグ中のＣａＯ濃度は、４０～７０質量％に制御することが好ましい。ＭｇＯは、ＡＯＤ炉又はＶＯＤ炉のいずれかの二次精錬容器の耐火物に、ドロマイト系煉瓦、マグネシア煉瓦、ＭｇＯ－Ｃ系煉瓦等のマグネシア含有煉瓦を用い、スラグ中にＭｇＯを溶損させることにより形成できる。また、このような煉瓦は高価であるために、煉瓦はできる限り寿命を延ばしてコストを抑えることが好ましく、ＭｇＯ含有の廃煉瓦を使用してもよい。Ｆは溶湯中に蛍石を投入することで制御できる。Ｆは重要な成分であり、スラグの流動性を確保して、スラグ／溶湯間における下記の反応が進行し、Ｏの含有量を０．０００２～０．０１質量％の範囲内、Ｓの含有量を０．０００１～０．００５０質量％の範囲内、Ｃａの含有量を０．００２０質量％以下にそれぞれ制御できる。そのため、スラグ中のＦ濃度は１～１０質量％に制御することが好ましい。尚、下記の各反応において、下線は溶湯に含まれる成分、括弧内はスラグに含まれる成分である。 In the refining process including the above steps (a) and (b), the obtained slag plays a very important role. Although the slag to be formed is not particularly limited, it is preferable to form a CaO--SiO 2 -Al 2 O 3 -MgO--F based slag. CaO contained in such slag can be formed by calcining limestone to dissociate CO 2 and pouring quicklime obtained as CaO into the molten metal, and SiO 2 can be formed by oxidation after feeding the FeSi alloy. CaO plays a particularly important role in the slag, and the CaO concentration in the slag is preferably controlled to 40 to 70% by mass. For MgO, use magnesia-containing bricks such as dolomite bricks, magnesia bricks, and MgO-C bricks as refractories in the secondary refining container of either the AOD furnace or the VOD furnace, and dissolve MgO in the slag. It can be formed by Further, since such bricks are expensive, it is preferable to extend the life of the bricks to reduce costs as much as possible, and waste bricks containing MgO may be used. F can be controlled by adding fluorite into the molten metal. F is an important component, ensuring the fluidity of the slag, allowing the following reaction between slag and molten metal to proceed, and keeping the O content within the range of 0.0002 to 0.01% by mass and the S content. The amount of Ca can be controlled within the range of 0.0001 to 0.0050% by mass, and the content of Ca can be controlled within the range of 0.0020% by mass or less. Therefore, it is preferable to control the F concentration in the slag to 1 to 10% by mass. In each reaction below, the underlined components are components contained in the molten metal, and the components in parentheses are components contained in the slag.
Ｓｉ＋２Ｏ → （ＳｉＯ２） （１）
２（ＣａＯ）＋Ｓｉ → （ＳｉＯ２）＋２Ｃａ （２）
Ｃａ＋Ｓ → （ＣａＳ） （３）
Si +2 O → (SiO 2 ) (1)
2 (CaO) + Si → (SiO 2 ) + 2 Ca (2)
Ca + S → (CaS) (3)
上記式（１）で表される反応を有効に右辺に向けて進行させて、Ｏの含有量を０．０００２～０．０１質量％の範囲内に制御するには、スラグ中のＳｉＯ２活量を１０－２～１０－３に低く制御する必要がある。そのためには、上述した通りＣａＯが有効であり、生石灰を溶湯中に投入することでＳｉＯ２活量を制御できる。さらに、上記式（２）で表される反応が右辺に向けて進行し、次いで、生成したＣａが溶湯中のＳと反応して上記式（３）で表される脱硫反応が起こると、Ｓの含有量を０．０００１～０．００５質量％の範囲内に制御できると共に、一旦溶湯中に移行したＣａがＳと反応することでＣａが消費され、Ｃａの含有量を０．００２０質量％以下に制御することが可能である。 In order to effectively advance the reaction expressed by the above formula (1) toward the right side and control the O content within the range of 0.0002 to 0.01% by mass, it is necessary to increase the SiO 2 activity in the slag. It is necessary to control the amount as low as 10 −2 to 10 −3 . For this purpose, CaO is effective as described above, and the SiO 2 activity can be controlled by adding quicklime to the molten metal. Furthermore, the reaction expressed by the above formula (2) progresses toward the right side, and then the generated Ca reacts with S in the molten metal to cause the desulfurization reaction expressed by the above formula (3). The content of Ca can be controlled within the range of 0.0001 to 0.005% by mass, and Ca is consumed by reacting with S once transferred into the molten metal, reducing the Ca content to 0.0020% by mass. It is possible to control as follows.
また、下記式（４）で表されるように、脱酸にはＡｌを用いることも可能である。一般的に工業用ＦｅＳｉ合金中には１質量％程度のＡｌが不純物として含まれる。そのため、ＦｅＳｉ合金を溶湯中に投入することによりＡｌの含有量を０．０００１～０．１０質量％の範囲内に制御することが可能である。また、スラグ中のＡｌ２Ｏ３は溶湯中のＳｉとも反応し得るため、注意を要する。つまり、下記式（５）で表される反応が活発化すると本Ａｌの含有量が０．１０質量％を超えてしまう。下記式（５）で表される反応を制御するには、スラグ中のＡｌ２Ｏ３活量を１０－２～１０－３に低く制御すると、Ａｌ含有量を０．０００１～０．１０質量％の範囲内に制御しやすくなる。そのためには、上述したように、スラグ中のＣａＯ濃度を制御して上記式（２）で表される反応を右辺に向けて進行させ、下記式（５）で表される反応を平衡状態にさせ、反応を安定化させることが好ましい。 Moreover, as represented by the following formula (4), it is also possible to use Al for deoxidation. Generally, industrial FeSi alloys contain about 1% by mass of Al as an impurity. Therefore, by introducing the FeSi alloy into the molten metal, it is possible to control the Al content within the range of 0.0001 to 0.10% by mass. Furthermore, since Al 2 O 3 in the slag can also react with Si in the molten metal, care must be taken. In other words, when the reaction represented by the following formula (5) becomes active, the content of the present Al exceeds 0.10% by mass. In order to control the reaction represented by the following formula (5), by controlling the Al 2 O 3 activity in the slag to a low value of 10 -2 to 10 -3 , the Al content can be reduced to 0.0001 to 0.10 mass. It becomes easier to control within the range of %. In order to do this, as mentioned above, the CaO concentration in the slag is controlled to allow the reaction expressed by the above equation (2) to proceed toward the right side, and the reaction expressed by the following equation (5) is brought to an equilibrium state. It is preferable to stabilize the reaction by
２Ａｌ＋３О → （Ａｌ２Ｏ３） （４）
２（Ａｌ２Ｏ３）＋３Ｓｉ → ３（ＳｉＯ２）＋４Ａｌ （５）
2 Al +3 О → (Al 2 O 3 ) (4)
2(Al 2 O 3 )+3 Si → 3(SiO 2 )+4 Al (5)
Ｍｇの含有量を０．０５０質量％以下に制御するためには、下記式（６）で表される反応を極力抑制する必要がある。この場合、スラグ中のＭｇＯをできる限り低く抑えることが有効であるが、煉瓦の溶損、廃煉瓦の投入が必要なことに鑑み、スラグ中のＭｇＯ濃度は５～２０質量％の範囲内に制御することが好ましい。また、Ｍｇの濃度を抑制するには溶湯中のＳｉ濃度を上記範囲内に制御し、且つスラグ中のＣａＯ濃度を上記の範囲に制御することが好ましい。これにより、Ｍｇの含有量を０．０５０質量％以下に制御することが可能となる。 In order to control the Mg content to 0.050% by mass or less, it is necessary to suppress the reaction represented by the following formula (6) as much as possible. In this case, it is effective to keep the MgO in the slag as low as possible, but in view of the melting of the bricks and the need to input waste bricks, the MgO concentration in the slag should be within the range of 5 to 20% by mass. Preferably controlled. Furthermore, in order to suppress the Mg concentration, it is preferable to control the Si concentration in the molten metal within the above range, and to control the CaO concentration in the slag within the above range. This makes it possible to control the Mg content to 0.050% by mass or less.
２（ＭｇＯ）＋Ｓｉ → （ＳｉＯ２）＋２Ｍｇ （６） 2 (MgO) + Si → (SiO 2 ) + 2 Mg (6)
Ｗは脱炭時にＷＯ３の酸化物が形成されて、その一部が揮発するのと同時に、下記式（７）の反応で表されるようにスラグ中にも移行する。取鍋精錬にてＷの添加量を調製することでＷの含有量を０．０１～０．５０質量％の範囲内に制御することができるが、スラグ中のＣａＯ濃度、ＭｇＯ濃度及びＦ濃度を上記範囲内にそれぞれ制御して、下記式（７）で表される反応を平衡状態にさせ、反応を安定化させることが好ましい。 During decarburization, WO 3 oxide is formed, and at the same time as a part of it volatilizes, it also migrates into the slag as represented by the reaction of formula (7) below. By adjusting the amount of W added in ladle refining, the W content can be controlled within the range of 0.01 to 0.50% by mass, but the CaO concentration, MgO concentration, and F concentration in the slag It is preferable to control each within the above range to bring the reaction represented by the following formula (7) into an equilibrium state and stabilize the reaction.
Ｗ＋３Ｏ → （ＷＯ３） （７） W +3 O → (WO 3 ) (7)
Ｚｒの含有量を０．０００１～０．０５質量％の範囲内に制御するために、Ｗと同様に取鍋精錬にてＺｒの添加量を調製することもできるが、下記式（８）で表されるようにＺｒは酸化しやすい元素である。そのため、スラグ中のＣａＯ濃度、ＭｇＯ濃度及びＦ濃度を上記範囲内にそれぞれ制御し、且つ、Ｏの含有量を０．０００２～０．０１質量％の範囲内に制御することにより、下記式（７）で表される反応の平衡関係を維持し、反応を安定化させることが好ましい。 In order to control the Zr content within the range of 0.0001 to 0.05% by mass, the amount of Zr added can be adjusted by ladle refining in the same way as W, but the amount of Zr added can be adjusted using the following formula (8). As shown, Zr is an element that is easily oxidized. Therefore, by controlling the CaO concentration, MgO concentration, and F concentration in the slag within the above ranges, and controlling the O content within the range of 0.0002 to 0.01% by mass, the following formula ( It is preferable to maintain the equilibrium relationship of the reaction represented by 7) and stabilize the reaction.
Ｚｒ＋２Ｏ → （ＺｒＯ２） （８） Zr +2 O → (ZrO 2 ) (8)
Ｔｉの含有量を０．０５０質量％以下に制御するために、下記式（９）で表される反応を右辺に向けて有効に進行させる。ここでも、スラグ中のＣａＯ濃度、ＭｇＯ濃度及びＦ濃度を上記範囲内にそれぞれ制御し、スラグ中のＴｉＯ２活量を低下させ、かつ、且つ、Ｏの含有量を０．０００２～０．０１質量％の範囲内に制御することにより、下記式（９）で表される反応を右辺に向けて有効に進行させることができ、最終的にＴｉの含有量を０．０５０質量％以下に制御することが可能となる。 In order to control the Ti content to 0.050% by mass or less, the reaction expressed by the following formula (9) is allowed to proceed effectively toward the right side. Here, too, the CaO concentration, MgO concentration, and F concentration in the slag are controlled within the above ranges to reduce the TiO 2 activity in the slag, and to reduce the O content to 0.0002 to 0.01. By controlling the Ti content within the range of mass %, the reaction expressed by the following formula (9) can be effectively progressed toward the right side, and the Ti content is finally controlled to 0.050 mass % or less. It becomes possible to do so.
Ｔｉ＋２Ｏ → （ＴｉＯ２） （９） Ti +2 O → (TiO 2 ) (9)
Ｎの含有量を０．００１～０．０５質量％の範囲内に制御するために、下記式（１０）で表される反応を右辺に向けて有効に進行させる。窒素は電気炉にて原料を溶解する際に大気から容易に混入してしまうが、ＡＯＤ炉又はＶＯＤ炉を用いることで、脱炭時に下記式（１０）の反応が右辺に向けて進行し、Ｎの含有量を上述の範囲内に制御することができる。つまり、酸素吹精の際に、下記式（１１）及び式（１２）で表される反応によりＣＯガスが生成される。こようにして生成したＣＯガスの気泡は溶湯中の溶存窒素を取り込み、ＣＯガス中に窒素ガスの形で移行させることができ、最終的に、ＣＯ気泡が炉外に排出されることによって窒素ガスを除去することができる。ただし、ＣＯガスを系外に除去したとしても、窒素の熱力学的平衡値は０．００１質量％を下回らないため、Ｎの含有量を０．００１～０．０５質量％の範囲内に制御することが可能となる。 In order to control the N content within the range of 0.001 to 0.05% by mass, the reaction expressed by the following formula (10) is allowed to proceed effectively toward the right side. Nitrogen is easily mixed in from the atmosphere when melting raw materials in an electric furnace, but by using an AOD furnace or a VOD furnace, the reaction of the following formula (10) progresses toward the right side during decarburization. The N content can be controlled within the above range. That is, during oxygen blowing, CO gas is generated by the reactions expressed by the following formulas (11) and (12). The CO gas bubbles generated in this way can take in dissolved nitrogen in the molten metal and transfer it into the CO gas in the form of nitrogen gas.Finally, the CO bubbles are discharged outside the furnace and nitrogen is released. Gas can be removed. However, even if CO gas is removed from the system, the thermodynamic equilibrium value of nitrogen does not fall below 0.001% by mass, so the N content is controlled within the range of 0.001 to 0.05% by mass. It becomes possible to do so.
２Ｎ → Ｎ２［ガス］ （１０）
Ｏ２［ガス］＋２Ｆｅ → ２ＦｅＯ［酸素ガス気泡表面］ （１１）
ＦｅＯ［酸素ガス気泡表面］＋Ｃ → ＣＯ［ガス］＋Ｆｅ［液体］ （１２）
2 N → N 2 [Gas] (10)
O2 [gas] + 2 Fe → 2FeO [oxygen gas bubble surface] (11)
FeO [oxygen gas bubble surface] + C → CO [gas] + Fe [liquid] (12)
工程（ｃ）
工程（ｃ）では、脱酸及び脱硫処理後の溶湯を連続鋳造してスラブを形成する。連続鋳造の条件は、特に限定されるものではないが、連続鋳造は縦型連続鋳造機で行うことができる。
Process (c)
In step (c), the deoxidized and desulfurized molten metal is continuously cast to form a slab. Although the conditions for continuous casting are not particularly limited, continuous casting can be performed using a vertical continuous casting machine.
工程（ｄ）
工程（ｄ）では、得られたスラブを熱間圧延、次いで冷間圧延する。スラブの熱間圧延工程を経て、熱帯を製造し、次いで、得られた熱帯に冷間圧延を施し、被冷間圧延板を作製する。熱間圧延及び冷間圧延の条件は、特に限定されるものではないが、熱間圧延はステッケル圧延機で、冷間圧延はゼンジミア型冷間圧延機で行うことができる。また、冷間圧延工程の前に、必要に応じて焼鈍、酸洗を行い、表面のスケールを除去してもよい。このようにして、本発明に係るＦｅ－Ｎｉ系合金板を製造することができる。
Process (d)
In step (d), the obtained slab is hot rolled and then cold rolled. A slab is manufactured through a hot rolling process of the slab, and then the resulting slab is subjected to cold rolling to produce a cold-rolled plate. The conditions for hot rolling and cold rolling are not particularly limited, but hot rolling can be performed using a Steckel rolling mill, and cold rolling can be performed using a Sendzimir type cold rolling mill. Moreover, before the cold rolling process, annealing and pickling may be performed as necessary to remove scale on the surface. In this way, the Fe--Ni alloy plate according to the present invention can be manufactured.
冷間圧延して得られた被冷間圧延板に磁気焼鈍を行うことにより、Ｆｅ－Ｎｉ系合金に磁気特性が付与される。磁気焼鈍の条件は、特に限定されるものではなく、従来公知の方法により、適宜行うことができる。このような工程を経て、好ましくは初比透磁率（μi）が３，０００以上、より好ましくは３，５００以上、好ましくは最大比透磁率（μｍａｘ）が３０，０００以上、より好ましくは３５，０００以上、好ましくは飽和磁束密度（Ｂ８００)が１．４Ｔ以上、より好ましくは１．４５Ｔ以上の磁気特性を示すＦｅ－Ｎｉ系合金板を実現できる。 Magnetic properties are imparted to the Fe--Ni alloy by magnetically annealing the cold-rolled sheet obtained by cold rolling. The conditions for magnetic annealing are not particularly limited, and can be performed as appropriate by conventionally known methods. Through such a process, the initial relative magnetic permeability (μ i ) is preferably 3,000 or more, more preferably 3,500 or more, and preferably the maximum relative magnetic permeability (μ max ) is 30,000 or more, more preferably It is possible to realize a Fe--Ni alloy plate exhibiting magnetic properties of 35,000 or more, preferably a saturation magnetic flux density (B 800 ) of 1.4T or more, more preferably 1.45T or more.
次に、本発明の実施例を説明するが、本発明はその趣旨を超えない限り、これらの実施例に限定されるものではない。 Next, examples of the present invention will be described, but the present invention is not limited to these examples unless it exceeds the spirit thereof.
＜実施例１～４０、比較例１～１０＞
鉄屑、ニッケル、フェロニッケル等を含む原料６０ｔを電気炉で溶解した。その後、ＡＯＤ炉又はＶＯＤ炉で、脱炭、脱クロム、脱燐等の処理のために、酸化精錬を行った。ここで、ＡＯＤ炉又はＶＯＤ炉の二次精錬容器の耐火物にドロマイト煉瓦、マグクロ煉瓦、マグネシア煉瓦、ＭｇＯ－Ｃ系煉瓦をチャージ毎に、操業上の運転サイクルにしたがってライニングした。次いで、形成された酸化性スラグ、すなわち、ＦｅＯ含有スラグであるＦｅＯ－ＣａＯ－ＳｉＯ２系スラグを排滓した。このスラグにはＣｒ酸化物、Ｗ酸化物、Ｔｉ酸化物、燐酸化物も含有されており極力系外に排出した。その後、溶湯をＡｌ及び／又はＦｅＳｉ合金を用いて得られる溶湯中に含まれるＡｌ、Ｓｉ、Ｓ及びＯの含有量を調製しながら脱酸及び脱硫した。この際に、ＣａＯ－ＳｉＯ２－Ａｌ２Ｏ３－ＭｇＯ－Ｆ系スラグを造滓した。すなわち、生石灰を溶湯中に投入してＣａＯを形成し、ＳｉＯ２はＦｅＳｉ合金投入後の酸化により形成した。ＭｇＯ源は、煉瓦溶損防止の目的も担うＭｇＯ含有の廃煉瓦を使用した。Ｆ源は蛍石を溶湯中に投入することで調製し、スラグの流動性を確保した。その後、溶鋼を取鍋に受けて、取鍋精錬にて温度を整えると同時に、合金組成を下記の表３、４に示される化学組成に調製すべく各種成分等を緻密に計算して添加した。尚、表５中のスラグ組成は、ＡＯＤ又はＶＯＤ精錬終了時のスラグ組成を示す。
<Examples 1 to 40, Comparative Examples 1 to 10>
60 tons of raw materials including scrap iron, nickel, ferronickel, etc. were melted in an electric furnace. After that, oxidation refining was performed in an AOD furnace or a VOD furnace for treatments such as decarburization, dechromization, and dephosphorization. Here, the refractory of the secondary refining vessel of the AOD furnace or VOD furnace was lined with dolomite bricks, maguro bricks, magnesia bricks, and MgO-C bricks for each charge according to the operational cycle. Next, the formed oxidizing slag, that is, the FeO--CaO--SiO 2 -based slag, which is FeO-containing slag, was removed. This slag also contained Cr oxide, W oxide, Ti oxide, and phosphorus oxide, and was discharged from the system as much as possible. Thereafter, the molten metal was deoxidized and desulfurized while adjusting the contents of Al, Si, S, and O contained in the molten metal obtained using Al and/or FeSi alloy. At this time, CaO--SiO 2 -Al 2 O 3 -MgO--F based slag was produced. That is, CaO was formed by charging quicklime into the molten metal, and SiO 2 was formed by oxidation after charging the FeSi alloy. As the MgO source, waste bricks containing MgO, which also serve the purpose of preventing brick erosion and damage, were used. The F source was prepared by adding fluorite into the molten metal to ensure fluidity of the slag. After that, the molten steel was placed in a ladle, and the temperature was adjusted by ladle refining, and at the same time, various ingredients were carefully calculated and added in order to adjust the alloy composition to the chemical composition shown in Tables 3 and 4 below. . The slag composition in Table 5 indicates the slag composition at the end of AOD or VOD refining.
次いで、脱酸及び脱硫処理した溶湯を連続鋳造してスラブを形成し、さらに、得られたスラブについて熱間圧延、焼鈍・酸洗を行った。その後、冷間圧延を行い厚さ０．８ｍｍのＦｅ－Ｎｉ系合金板を製造した。 Next, the deoxidized and desulfurized molten metal was continuously cast to form a slab, and the obtained slab was further hot rolled, annealed, and pickled. Thereafter, cold rolling was performed to produce a Fe--Ni alloy plate with a thickness of 0.8 mm.
＜磁気特性＞
得られたＦｅ－Ｎｉ系合金板をＪＩＳ Ｃ２５３１に基づき、φ４５ｍｍ×３３ｍｍのリング試験片に加工し、真空(５．０×１０－３Ｐａ以下)雰囲気中、１１２５℃の均熱で２．５時間の条件で磁気焼鈍したのち、ＪＩＳ Ｃ３２０２又はＪＩＳ Ｃ３２１５で規定されるエナメル銅線を１次、２次側共に５０巻きし、初比透磁率（μi）、最大比透磁率（μｍａｘ）及び飽和磁束密度（Ｂ８００)をそれぞれ測定した。初比透磁率及び最大比透磁率は１６Ａ／ｍを反転磁場とし測定を行い、初比透磁率は０．８Ａ／ｍの値とした。また、飽和磁束密度は磁場１６００Ａ／ｍの条件下で測定を行った。測定結果をもとに磁気特性の総合評価を行い、以下に示す初比透磁率、最大比透磁率及び飽和磁束密度の基準のうち、３項目全てを満足する場合、磁気特性が優れている(○)と評価した。また、以下に示す初比透磁率、最大比透磁率及び飽和磁束密度の基準のうち、２項目のみ満足する場合、磁気特性が良好である(△)と評価し、１項目のみ満足する又は全て満足しない場合、磁気特性が劣っている(×)として評価した。その結果を表５に示す。
・初比透磁率：３，０００以上
・最大比透磁率：３０，０００以上
・飽和磁束密度：１．４（Ｔ）以上
<Magnetic properties>
The obtained Fe-Ni alloy plate was processed into a ring test piece of φ45 mm x 33 mm based on JIS C2531, and soaked at 1125°C in a vacuum (5.0 x 10 -3 Pa or less) atmosphere to a temperature of 2.5 mm. After magnetic annealing under certain conditions, enamelled copper wire specified by JIS C3202 or JIS C3215 was wound 50 times on both the primary and secondary sides to obtain initial relative permeability (μ i ) and maximum relative permeability (μ max ). and saturation magnetic flux density (B 800 ) were measured. The initial relative magnetic permeability and the maximum relative magnetic permeability were measured using a reversal magnetic field of 16 A/m, and the initial relative magnetic permeability was set to a value of 0.8 A/m. Moreover, the saturation magnetic flux density was measured under the condition of a magnetic field of 1600 A/m. Comprehensive evaluation of magnetic properties is performed based on the measurement results, and if all three of the following criteria of initial relative magnetic permeability, maximum relative magnetic permeability, and saturation magnetic flux density are satisfied, the magnetic properties are excellent ( It was evaluated as ○). In addition, if only two of the following criteria for initial relative magnetic permeability, maximum relative magnetic permeability, and saturation magnetic flux density are satisfied, the magnetic properties are evaluated as good (△), and if only one item is satisfied or all of the items are satisfied. If not satisfied, the magnetic properties were evaluated as poor (×). The results are shown in Table 5.
・Initial relative magnetic permeability: 3,000 or more ・Maximum relative magnetic permeability: 30,000 or more ・Saturation magnetic flux density: 1.4 (T) or more
＜耐発錆性＞
耐発錆性を評価するため、上記で得た冷延板を４０×５０ｍｍの試験片に切断後、その表面を４００番の耐水研磨紙で湿式研磨を行い、発錆加速試験を行った。発錆加速試験は温度７０℃、相対湿度１００％の条件で行い、蒸留水２００ｍｌを入れた１０００ｍｌビーカー内で水に濡れないよう試験片を７２時間水平に保持した。その後、発錆度合いをＪＩＳ Ｇ０５９５に基づきレーティングナンバー（ＲＮ）を用いて、以下の３段階で評価した。その結果を表５に示す。
・〇：ＲＮが２．５より大きい
・△：ＲＮが２．０以上２．５以下
・×：ＲＮが２．０未満
<Rust resistance>
In order to evaluate rust resistance, the cold-rolled plate obtained above was cut into test pieces of 40 x 50 mm, and the surface thereof was wet-polished with No. 400 water-resistant abrasive paper to perform a rust acceleration test. The accelerated rusting test was conducted at a temperature of 70° C. and a relative humidity of 100%, and the test piece was held horizontally for 72 hours in a 1000 ml beaker containing 200 ml of distilled water so as not to get wet. Thereafter, the degree of rusting was evaluated in the following three stages using rating numbers (RN) based on JIS G0595. The results are shown in Table 5.
・○: RN is greater than 2.5 ・△: RN is 2.0 or more and 2.5 or less ・×: RN is less than 2.0
＜総合評価＞
上記試験の総合評価として、以下の４段階で評価した。その結果を表５に示す。
・◎：磁気特性及び耐発錆性の両方の評価が「○」
・〇：磁気特性の評価「〇」且つ耐発錆性の評価「△」
・△：磁気特性の評価「△」、又は磁気特性の評価「〇」且つ耐発錆性の評価「×」
・×：磁気特性の評価「×」、又は製品として歩留まりに劣る
<Comprehensive evaluation>
As a comprehensive evaluation of the above test, evaluation was made in the following four stages. The results are shown in Table 5.
・◎: Evaluation of both magnetic properties and rust resistance is "○"
・〇: Evaluation of magnetic properties “〇” and evaluation of rust resistance “△”
・△: Magnetic property evaluation “△” or magnetic property evaluation “〇” and rust resistance evaluation “×”
・×：Evaluation of magnetic properties is “×” or product yield is poor.
表３～６に示されるように、本発明に規定される化学組成の範囲を満たすＦｅ－Ｎｉ系合金板を用いた実施例１～３０では、磁気特性及び耐発錆性のいずれの評価も「○」であり、総合評価も「◎」であった。 As shown in Tables 3 to 6, in Examples 1 to 30 using Fe-Ni alloy plates satisfying the chemical composition range specified in the present invention, both magnetic properties and rust resistance were evaluated. The rating was "○", and the overall evaluation was also "◎".
実施例３１～３４では、得られたＦｅ－Ｎｉ系合金板は本発明に規定される化学組成の範囲を満たし、また、磁気特性の評価も「○」であったものの、耐発錆性の評価が「△」となってしまい、総合評価は「〇」であった。 In Examples 31 to 34, the obtained Fe-Ni alloy plates satisfied the chemical composition range specified in the present invention, and the magnetic properties were evaluated as "○", but the rust resistance was poor. The evaluation was "△", and the overall evaluation was "○".
実施例３５では、得られたＦｅ－Ｎｉ系合金板は本発明に規定される化学組成の範囲を満たしているものの、式（Ａ）の値が５０．４であり、また、最大比透磁率が３０，０００未満であったため、磁気特性の評価は「△」であった。一方、耐発錆性の評価は「〇」であったため、総合評価は「△」であった。 In Example 35, although the obtained Fe-Ni alloy plate satisfies the chemical composition range specified in the present invention, the value of formula (A) is 50.4, and the maximum relative permeability is was less than 30,000, so the evaluation of the magnetic properties was "Δ". On the other hand, since the rust resistance evaluation was "○", the overall evaluation was "△".
実施例３６では、得られたＦｅ－Ｎｉ系合金板は本発明に規定される化学組成の範囲を満たしているものの、式（Ａ）の値が１．４であり、また、飽和磁束密度が１．４Ｔ未満であったため、磁気特性の評価は「△」であった。一方、耐発錆性の評価は「〇」であったため、総合評価は「△」であった。 In Example 36, although the obtained Fe-Ni alloy plate satisfies the chemical composition range specified in the present invention, the value of formula (A) is 1.4, and the saturation magnetic flux density is Since it was less than 1.4T, the evaluation of the magnetic properties was "△". On the other hand, since the rust resistance evaluation was "○", the overall evaluation was "△".
実施例３７では、得られたＦｅ－Ｎｉ系合金板は本発明に規定される化学組成の範囲を満たしているものの、式（Ａ）の値が１．３であり、また、飽和磁束密度が１．４Ｔ未満であったため、磁気特性の評価は「△」であった。一方、耐発錆性の評価は「〇」であったため、総合評価は「△」であった。 In Example 37, although the obtained Fe-Ni alloy plate satisfies the chemical composition range specified in the present invention, the value of formula (A) is 1.3, and the saturation magnetic flux density is Since it was less than 1.4T, the evaluation of the magnetic properties was "△". On the other hand, since the rust resistance evaluation was "○", the overall evaluation was "△".
実施例３８では、得られたＦｅ－Ｎｉ系合金板は本発明に規定される化学組成の範囲を満たしているものの、式（Ａ）の値が５０．１であり、また、最大比透磁率が３０，０００未満であったため、磁気特性の評価は「△」であった。一方、耐発錆性の評価は「〇」であったため、総合評価は「△」であった。 In Example 38, although the obtained Fe-Ni alloy plate satisfies the chemical composition range specified in the present invention, the value of formula (A) is 50.1, and the maximum relative permeability is was less than 30,000, so the evaluation of the magnetic properties was "Δ". On the other hand, since the rust resistance evaluation was "○", the overall evaluation was "△".
実施例３９では、得られたＦｅ－Ｎｉ系合金板は本発明に規定される化学組成の範囲を満たしているものの、式（Ｂ）の値が９であり、ＲＮが２．０未満であったため、耐発錆性の評価は「×」であった。一方、磁気特性の評価も「○」であったため、総合評価は「△」であった。 In Example 39, although the obtained Fe-Ni alloy plate satisfied the chemical composition range specified in the present invention, the value of formula (B) was 9 and the RN was less than 2.0. Therefore, the evaluation of rust resistance was "x". On the other hand, since the evaluation of magnetic properties was also "○", the overall evaluation was "△".
実施例４０では、得られたＦｅ－Ｎｉ系合金板は本発明に規定される化学組成の範囲を満たしているものの、式（Ａ）の値が１．４であり、また、飽和磁束密度が１．４Ｔ未満であった。さらに、式（Ｂ）の値が０であり、ＲＮが２．０未満であった。そのため、磁気特性の評価が「△」、耐発錆性の評価が「×」であったため、総合評価は「△」であった。 In Example 40, although the obtained Fe-Ni alloy plate satisfies the chemical composition range specified in the present invention, the value of formula (A) is 1.4, and the saturation magnetic flux density is It was less than 1.4T. Furthermore, the value of formula (B) was 0, and RN was less than 2.0. Therefore, the evaluation of magnetic properties was "△" and the evaluation of rust resistance was "x", so the overall evaluation was "△".
比較例１～３では、得られたＦｅ－Ｎｉ系合金板は本発明に規定される化学組成の範囲を満たしておらず、また、初比透磁率が３，０００未満、最大比透磁率が３０，０００未満であったため、磁気特性の評価は「×」であった。さらに、製品としての歩留まりも悪く、このチャージのうち、１コイルは耳割れが酷かったために屑化処理となってしまった。そのため、総合評価は「×」であった。 In Comparative Examples 1 to 3, the obtained Fe-Ni alloy plates did not satisfy the chemical composition range specified in the present invention, and the initial relative magnetic permeability was less than 3,000 and the maximum relative magnetic permeability was less than 3,000. Since it was less than 30,000, the evaluation of the magnetic properties was "x". Furthermore, the yield rate as a product was poor, and one coil of this charge had severe cracking at the edges and had to be scrapped. Therefore, the overall evaluation was "x".
比較例４～５では、得られたＦｅ－Ｎｉ系合金板は本発明に規定される化学組成の範囲を満たしておらず、また、初比透磁率が３，０００未満、飽和磁束密度が１．４Ｔ未満であったため、磁気特性の評価は「×」であった。さらに、式（Ｂ）の値も低く、ＲＮが２．０未満であったため、耐発錆性の評価も「×」であり、総合評価は「×」であった。 In Comparative Examples 4 and 5, the obtained Fe-Ni alloy plates did not satisfy the chemical composition range specified in the present invention, and also had an initial relative permeability of less than 3,000 and a saturation magnetic flux density of 1. Since it was less than .4T, the evaluation of the magnetic properties was "x". Furthermore, since the value of formula (B) was low and RN was less than 2.0, the rust resistance evaluation was also "x", and the overall evaluation was "x".
比較例６では、得られたＦｅ－Ｎｉ系合金板は本発明に規定される化学組成の範囲を満たしておらず、また、飽和磁束密度が１．４Ｔ未満であったため、磁気特性の評価は「△」であった。さらに、式（Ｂ）の値７であり、ＲＮが２．０未満であったため、耐発錆性の評価は「×」であった。一方、製品としての歩留まりが悪く、このチャージのうち、１コイルは耳割れが酷かったために屑化処理となってしまった。そのため、総合評価は「×」であった。 In Comparative Example 6, the obtained Fe-Ni alloy plate did not satisfy the chemical composition range specified in the present invention, and the saturation magnetic flux density was less than 1.4T, so the evaluation of magnetic properties was It was “△”. Furthermore, since the value of formula (B) was 7 and the RN was less than 2.0, the rust resistance was evaluated as "x". On the other hand, the yield rate as a product was poor, and one coil of this charge had severe cracking at the edges, so it was disposed of as scrap. Therefore, the overall evaluation was "x".
比較例７～９では、得られたＦｅ－Ｎｉ系合金板は本発明に規定される化学組成の範囲を満たしておらず、また、初比透磁率が３，０００未満、飽和磁束密度が１．４Ｔ未満であったため、磁気特性の評価は「×」であった。さらに、式（Ｂ）の値も低く、ＲＮが２．０未満であったため、耐発錆性の評価も「×」であり、総合評価は「×」であった。 In Comparative Examples 7 to 9, the obtained Fe-Ni alloy plates did not satisfy the chemical composition range specified in the present invention, and also had an initial relative permeability of less than 3,000 and a saturation magnetic flux density of 1. Since it was less than .4T, the evaluation of the magnetic properties was "x". Furthermore, since the value of formula (B) was low and RN was less than 2.0, the rust resistance evaluation was also "x", and the overall evaluation was "x".
比較例１０では、得られたＦｅ－Ｎｉ系合金板は本発明に規定される化学組成の範囲を満たしておらず、また、初比透磁率が３，０００未満、最大比透磁率が３０，０００未満であったため、磁気特性の評価は「×」であった。さらに、製品としての歩留まりも悪く、このチャージのうち、２コイルは耳割れが酷かったために屑化処理となってしまった。そのため、総合評価は「×」であった。 In Comparative Example 10, the obtained Fe-Ni alloy plate did not satisfy the chemical composition range defined in the present invention, and had an initial relative permeability of less than 3,000, a maximum relative permeability of 30, Since it was less than 000, the evaluation of the magnetic properties was "x". Furthermore, the yield rate as a product was poor, and two of the coils of this charge had severe cracking at the edges, so they were disposed of as scrap. Therefore, the overall evaluation was "x".
本発明に係るＦｅ－Ｎｉ系合金板は、優れた初比透磁率と、良好な最大比透磁率及び飽和磁束密度を付与し得ると共に、歩留まりを抑えて製造可能であるため、例えば、自動車センサや磁気シールド材、時計のステータ等の軟磁性材料として好適に適用できる。
The Fe-Ni alloy plate according to the present invention can provide excellent initial relative magnetic permeability, good maximum relative magnetic permeability and saturation magnetic flux density, and can be manufactured with a low yield, so it can be used, for example, for automobile sensors. It can be suitably applied as a soft magnetic material for magnetic shielding materials, watch stators, etc.
Claims (5)
ケイ素（Ｓｉ）：０．０５～０．５０質量％、
マンガン（Ｍｎ）：０．２５～１．００質量％、
リン（Ｐ）：０．００１～０．０３０質量％、
硫黄（Ｓ）：０．０００１～０．００５０質量％、
ニッケル（Ｎｉ）：３５．０～４４．０質量％、
クロム（Ｃｒ）：０．０１～０．５０質量％、
モリブデン（Ｍｏ）：０．００５～０．１０質量％、
銅（Ｃｕ）：０．０１～２．００質量％、
アルミニウム（Ａｌ）：０．０００１～０．１０質量％、
チタン（Ｔｉ）：０．０５０質量％以下、
コバルト（Ｃｏ）：０．０１～２．００質量％、
タングステン（Ｗ）：０．０１～０．５０質量％、
窒素（Ｎ）：０．００１～０．０５質量％、
スズ（Ｓｎ）：０．０００１～０．０５質量％、
マグネシウム（Ｍｇ）：０．０５０質量％以下、
ジルコニウム（Ｚｒ）：０．０００１～０．０５質量％、
カルシウム（Ｃａ）：０．００２０質量％以下、
酸素（Ｏ）：０．０００２～０．０１質量％を含み、
残部が鉄（Ｆｅ）及び不可避的不純物からなることを特徴とするＦｅ－Ｎｉ系合金板。 Carbon (C): 0.001 to 0.05% by mass,
Silicon (Si): 0.05 to 0.50% by mass,
Manganese (Mn): 0.25 to 1.00% by mass,
Phosphorus (P): 0.001 to 0.030% by mass,
Sulfur (S): 0.0001 to 0.0050% by mass,
Nickel (Ni): 35.0 to 44.0% by mass,
Chromium (Cr): 0.01 to 0.50% by mass,
Molybdenum (Mo): 0.005 to 0.10% by mass,
Copper (Cu): 0.01 to 2.00% by mass,
Aluminum (Al): 0.0001 to 0.10% by mass,
Titanium (Ti): 0.050% by mass or less,
Cobalt (Co): 0.01 to 2.00% by mass,
Tungsten (W): 0.01 to 0.50% by mass,
Nitrogen (N): 0.001 to 0.05% by mass,
Tin (Sn): 0.0001 to 0.05% by mass,
Magnesium (Mg): 0.050% by mass or less,
Zirconium (Zr): 0.0001 to 0.05% by mass,
Calcium (Ca): 0.0020% by mass or less,
Oxygen (O): Contains 0.0002 to 0.01% by mass,
An Fe--Ni alloy plate characterized in that the remainder consists of iron (Fe) and inevitable impurities.
1.5≦20[Cu％]+20[Co％]+80[W％]＜50.0 …（Ａ）
（式（Ａ）中、％は質量％を表す。） The Fe--Ni alloy plate according to claim 1, which contains Cu, Co, and W so as to satisfy the following relational expression (A).
1.5≦20[Cu%]+20[Co%]+80[W%]＜50.0…(A)
(In formula (A), % represents mass %.)
10≦50([Cu％]+[Co％])+100[W％]+200[Cr％]+800[Mo％]-100[P％]-1000[S％] …（Ｂ）
（式（Ｂ）中、％は質量％を表す。） The Fe-Ni alloy plate according to claim 1 or 2, which contains Cu, Co, W, Cr, Mo, P, and S so as to satisfy the following relational expression (B).
10≦50([Cu%]+[Co%])+100[W%]+200[Cr%]+800[Mo%]-100[P%]-1000[S%]...(B)
(In formula (B), % represents mass %.)
酸化精錬後の溶湯中にＡｌ及び／又はＦｅＳｉ合金を投入して、溶湯中のＡｌの含有量が０．０００１～０．１０質量％、Ｓｉの含有量が０．０５～０．５０質量％、Ｓの含有量が０．０００１～０．００５０質量％、Ｏの含有量が０．０００２～０．０１質量％の範囲になるように脱酸及び脱硫処理をする工程と、
脱酸及び脱硫処理後の溶湯を連続鋳造してスラブを形成する工程と、
得られたスラブを熱間圧延、次いで冷間圧延する工程と、
を含むことを特徴とする、請求項１又は２に記載のＦｅ－Ｎｉ系合金板の製造方法。 A step of oxidizing and refining the molten metal containing the Fe-Ni alloy raw material in a secondary refining vessel of either an AOD furnace or a VOD furnace;
Al and/or FeSi alloy is introduced into the molten metal after oxidation refining, and the Al content in the molten metal is 0.0001 to 0.10% by mass and the Si content is 0.05 to 0.50% by mass. , a step of deoxidizing and desulfurizing so that the content of S is in the range of 0.0001 to 0.0050% by mass and the content of O is in the range of 0.0002 to 0.01% by mass;
a step of continuously casting the molten metal after deoxidation and desulfurization treatment to form a slab;
Hot rolling and then cold rolling the obtained slab;
The method for producing a Fe--Ni alloy plate according to claim 1 or 2, comprising:
酸化精錬後の溶湯中にＡｌ及び／又はＦｅＳｉ合金を投入して、溶湯中のＡｌの含有量が０．０００１～０．１０質量％、Ｓｉの含有量が０．０５～０．５０質量％、Ｓの含有量が０．０００１～０．００５０質量％、Ｏの含有量が０．０００２～０．０１質量％の範囲になるように脱酸及び脱硫処理をする工程と、
脱酸及び脱硫処理後の溶湯を連続鋳造してスラブを形成する工程と、
得られたスラブを熱間圧延、次いで冷間圧延する工程と、
を含むことを特徴とする、請求項３に記載のＦｅ－Ｎｉ系合金板の製造方法。
A step of oxidizing and refining the molten metal containing the Fe-Ni alloy raw material in a secondary refining vessel of either an AOD furnace or a VOD furnace;
Al and/or FeSi alloy is introduced into the molten metal after oxidation refining, and the Al content in the molten metal is 0.0001 to 0.10% by mass and the Si content is 0.05 to 0.50% by mass. , a step of deoxidizing and desulfurizing so that the content of S is in the range of 0.0001 to 0.0050% by mass and the content of O is in the range of 0.0002 to 0.01% by mass;
a step of continuously casting the molten metal after deoxidation and desulfurization treatment to form a slab;
Hot rolling and then cold rolling the obtained slab;
The method for manufacturing an Fe--Ni alloy plate according to claim 3, comprising:
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| JP2010534277A (en) | 2007-03-30 | 2010-11-04 | アルセロールミタル−ステンレス・アンド・ニツケル・アロイ | Austenitic iron / nickel / chromium / copper alloy |
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| JP2010534277A (en) | 2007-03-30 | 2010-11-04 | アルセロールミタル−ステンレス・アンド・ニツケル・アロイ | Austenitic iron / nickel / chromium / copper alloy |
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