JPH02133517A - Method for annealing thin amorphous alloy strip - Google Patents
Method for annealing thin amorphous alloy stripInfo
- Publication number
- JPH02133517A JPH02133517A JP28582988A JP28582988A JPH02133517A JP H02133517 A JPH02133517 A JP H02133517A JP 28582988 A JP28582988 A JP 28582988A JP 28582988 A JP28582988 A JP 28582988A JP H02133517 A JPH02133517 A JP H02133517A
- Authority
- JP
- Japan
- Prior art keywords
- amorphous alloy
- annealing
- boron
- alloy ribbon
- iron
- 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
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 53
- 238000000137 annealing Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052742 iron Inorganic materials 0.000 claims abstract description 32
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 23
- 239000000956 alloy Substances 0.000 claims abstract description 23
- 229910052796 boron Inorganic materials 0.000 claims abstract description 20
- 239000012298 atmosphere Substances 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 238000007743 anodising Methods 0.000 claims description 6
- 229910018540 Si C Inorganic materials 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- 229910000676 Si alloy Inorganic materials 0.000 claims 1
- 230000006866 deterioration Effects 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000010408 film Substances 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- 239000011162 core material Substances 0.000 description 8
- 238000002048 anodisation reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 235000002906 tartaric acid Nutrition 0.000 description 4
- 239000011975 tartaric acid Substances 0.000 description 4
- 229910000976 Electrical steel Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002233 thin-film X-ray diffraction Methods 0.000 description 2
- 229910001339 C alloy Inorganic materials 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000576 Laminated steel Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910004160 TaO2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- NQKXFODBPINZFK-UHFFFAOYSA-N dioxotantalum Chemical compound O=[Ta]=O NQKXFODBPINZFK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000005381 magnetic domain Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、電力用変圧器や回転殿等の電気機器に使用
される鉄心のような磁性材料に用いて好適な、表面被膜
を有する非晶質合金薄帯の焼鈍方法に関し、特にかかる
焼鈍のさいに懸念された鉄…特性の劣化を有利に防止し
、ようどするものである。Detailed Description of the Invention (Field of Industrial Application) The present invention is directed to a non-magnetic material having a surface coating, which is suitable for use in magnetic materials such as iron cores used in electrical equipment such as power transformers and rotating shafts. Regarding the method of annealing a crystalline alloy ribbon, the present invention advantageously prevents and prevents the deterioration of the properties of iron, which was a concern during such annealing.
（従来の技術）
変圧器や回転機等の電気機器に使用される鉄心材料には
、イ）れた励磁特性及び鉄用特性が必要とされる。(Prior Art) Iron core materials used in electrical equipment such as transformers and rotating machines require (a) excellent excitation characteristics and iron characteristics.
このため、従来かような特性を満足する素材として、け
い素鋼板、殊に方向性けい素姫仮が多用されてきた。For this reason, silicon steel sheets, especially oriented silicon Himekari, have been widely used as a material satisfying these characteristics.
一力、含ボロンＦｅ基非晶質合金薄帯は、鉄ｔｎが低く
また励磁特性に優れ−でいるばかりでなく、飽和磁束密
度も比較的高いことから鉄心材料として必要な特性を満
足していることが知られている。First, boron-containing Fe-based amorphous alloy ribbon not only has a low iron tn and excellent excitation characteristics, but also has a relatively high saturation magnetic flux density, so it satisfies the characteristics required as an iron core material. It is known that there are
さらに結晶化温度も５００ ’Ｃ以上であるから、耐熱
性の面からも問題がなく、このことは長ル１間の実トラ
ンスを用いた実証テス１−でも確認されている。Furthermore, since the crystallization temperature is 500'C or higher, there is no problem in terms of heat resistance, and this was also confirmed in demonstration test 1- using an actual transformer between lengths 1.
非晶質合金薄帯の一般的な製造方法である液体急冷法に
おいては、凝固速度を大きくする必要があることから得
られる非晶質合金薄帯の板厚は極めて薄く、通常は５０
μｍ以下である。したがって変圧器などシこ用いる鉄心
を作製する際には、けい素鋼板以上に多数回の巻き加工
や積み加工が必要となる。In the liquid quenching method, which is a common manufacturing method for amorphous alloy ribbons, it is necessary to increase the solidification rate, so the thickness of the amorphous alloy ribbons obtained is extremely thin, usually 50 mm.
It is less than μm. Therefore, when manufacturing an iron core for use in transformers, etc., it is necessary to wind and stack the iron core more times than silicon steel sheets.
巻き加工や積み加工の結果、積層鋼板に生じた層間絶縁
抵抗が小ざいと、渦電流が生じて鉄Ｆ員増大の原因とな
る。この渦電流）員を減少させるために、けい素鋼板で
は表面絶縁被膜の存在が不可欠となっている。If the interlayer insulation resistance generated in the laminated steel plate as a result of winding or stacking is small, eddy currents will occur, causing an increase in the iron F member. In order to reduce this eddy current, the presence of a surface insulating coating is essential for silicon steel sheets.
この点、非晶質合金薄帯の場合には、合金自体の電気抵
抗が高く、また適度の表面凹凸のために、ある程度の層
間抵抗が得られることから、鉄心材料として用いる際に
も絶縁被膜は必要ないと考えられたこともあった。In this regard, in the case of amorphous alloy ribbons, the electrical resistance of the alloy itself is high, and due to the moderate surface roughness, a certain degree of interlayer resistance can be obtained. It was sometimes thought that it was not necessary.
し、かじながら非晶質合金薄帯の製造技術が向」ニし・
、表面が著しく平滑になったこともあり、広幅非品質合
金薄帯の場合には表面絶縁被膜の必要性が認識されるよ
うになった。さらに変圧器の鉄心（オｆ）用非晶質合金
としてばＦｅ−Ｂ−Ｓｉ系及びＦｅ−Ｂ５１− Ｃ系合
金がｊΔし２ているが、これら合金の耐食性があまり良
好でなく、室内で放置するだけで発錆するとい・）欠点
があった。この耐食性を１与する意味からも表面被膜は
必要と考えられる。However, the manufacturing technology for amorphous alloy ribbons is progressing.
As the surface became significantly smoother, the need for a surface insulating coating was recognized in the case of wide non-quality alloy ribbons. Furthermore, Fe-B-Si and Fe-B51-C alloys are used as amorphous alloys for transformer cores (off), but these alloys do not have very good corrosion resistance and cannot be used indoors. There was a drawback that it would rust if left alone. The surface coating is considered to be necessary in order to provide this corrosion resistance.
そこで特開昭６１−２２７１９４ 号及び同６３−８６
８８９号各公報においては、非晶質合金薄帯の表面上に
、陽極処理によってＡ１□Ｏｚ 、ＺｒＯ□、ＴａＯ２
等の酸化物表面被膜を施す方法を提案している。殊にア
ルミニ・酸ソーダを含む電解液中での陽極処理により、
非晶質合金薄帯の表面に均一な膜厚でＡｌ２Ｏ，を形成
さ仕ることが磁気特性および耐食性の点から好ましいと
されている。Therefore, JP-A-61-227194 and JP-A-63-86
In each publication No. 889, A1□Oz, ZrO□, TaO2 are deposited on the surface of an amorphous alloy ribbon by anodizing.
proposed a method of applying an oxide surface coating such as In particular, by anodizing in an electrolyte containing aluminum and acid soda,
It is said that it is preferable to form Al2O with a uniform thickness on the surface of the amorphous alloy ribbon from the viewpoint of magnetic properties and corrosion resistance.
しかしなから、単にアルミン酸ソーダを含む電解液中で
非晶質合金薄帯に電解処理を施しても、被膜形成速度は
極めて遅く、工業的通板速度を確保できなかった。However, even if an amorphous alloy ribbon is simply electrolytically treated in an electrolytic solution containing sodium aluminate, the film formation rate is extremely slow, and an industrial threading rate cannot be ensured.
一方特開昭６３−１０９１９４号及び同６３〜１０３０
９８ルー公報にて提案された、アルミン酸ソーダ及び酒
石酸を含む電解液中での多段陽極処理によれば、被膜形
成速度は高くなり、容易に酸化物表面被膜が得られた。On the other hand, JP-A-63-109194 and JP-A No. 63-1030
According to the multi-stage anodization in an electrolytic solution containing sodium aluminate and tartaric acid, which was proposed in the 98-Ru publication, the film formation rate was increased and an oxide surface film was easily obtained.
（発明が解決しようとする課題）
上記のように陽極処理を行って得られた被膜付き非晶質
合金薄帯は、不活性ガス雰囲気中で焼鈍した場合、鉄）
員などの磁気特性が不安定となり、時には無処理材に比
較しても悪くなることが判明した。(Problems to be Solved by the Invention) When the coated amorphous alloy ribbon obtained by anodizing as described above is annealed in an inert gas atmosphere,
It was found that the magnetic properties of the materials became unstable, and were sometimes even worse than untreated materials.
すなわち非晶質合金薄帯を変圧器用鉄心として使用する
場合、通常巻鉄心又は積鉄心に組み立てた後、磁場焼鈍
を施すことによって内部応力の緩和と磁区の制′４１■
とを図ることが必要なわけであるが、かような焼鈍処理
によって磁気特性の著しい劣化が生じたのである。In other words, when an amorphous alloy ribbon is used as a transformer core, it is assembled into a normal wound core or a laminated core and then subjected to magnetic field annealing to relieve internal stress and control magnetic domains.
However, such annealing treatment caused a significant deterioration of the magnetic properties.
なおこのような磁場焼鈍条件としては、通常Ｎ２又はＡ
ｒのような不活性雰囲気で、非晶質合金ｙＥｊ、ｊ＋ｐ
が結晶化しない範囲の焼鈍温度及び焼鈍時間が採用され
る。Note that such magnetic field annealing conditions are usually N2 or A
In an inert atmosphere such as r, the amorphous alloy yEj,j+p
The annealing temperature and annealing time are adopted within a range in which the crystallization does not occur.
この発明の目的は、陽極処理によって絶縁被膜を施した
非晶質合金薄帯に焼鈍、特にひずみ取り焼鈍を施しても
、磁気特性の劣化を招くことがない有利な焼鈍方法を提
案することにある。The purpose of this invention is to propose an advantageous annealing method that does not cause deterioration of magnetic properties even when an amorphous alloy ribbon that has been anodized with an insulating film is subjected to annealing, especially strain relief annealing. be.
（課題を解決するための手段）
この発明においては、非晶質合金薄帯表面に均一な膜厚
の被膜を形成させる表面被膜処理方法として陽極処理法
を採用し、例えばアルミン酸ソーダ及び酒石酸を含む電
解液中での陽極処理によってＡｌｚＯｓ被膜を形成させ
た。(Means for Solving the Problems) In the present invention, an anodic treatment method is adopted as a surface coating treatment method for forming a coating with a uniform thickness on the surface of an amorphous alloy ribbon, for example, using sodium aluminate and tartaric acid. An AlzOs film was formed by anodization in an electrolyte containing the following.
ところがこのようなＡｉｚ（ｈ被膜を有するＦｅ−ＢＳ
ｉ系非晶質合金薄帯をドライネ活性（Ｎ２）ガス雰囲気
中において４００ ’Ｃで焼鈍したところ、鉄損特性が
劣化し、同時に薄帯表面にはα−Ｆｅの結晶化が生じて
いることが見出された。さらにこのαＦｅの結晶は非晶
質合金薄４）Ｆの最表面に形成されていること、そして
この表面結晶層の除去によって鉄損特性は回復すること
が判明した。However, such Aiz(Fe-BS with h coating)
When an i-based amorphous alloy ribbon was annealed at 400'C in a dryene activated (N2) gas atmosphere, the core loss characteristics deteriorated, and at the same time, α-Fe crystallization occurred on the ribbon surface. was discovered. Furthermore, it was found that this αFe crystal was formed on the outermost surface of the amorphous alloy thin 4)F, and that the iron loss characteristics were recovered by removing this surface crystal layer.
発明者らは、かかる陽極処理被膜を有する非晶質合金薄
帯の焼鈍による鉄損劣化の原因について鋭意検討を加え
た結果、次のような新たな知見を得た。The inventors conducted extensive studies on the cause of core loss deterioration due to annealing of an amorphous alloy ribbon having such an anodized film, and as a result, the following new findings were obtained.
まず陽極処理によって非晶質合金薄帯表面に形成された
ＡｌｚＯｚ被膜は、水和酸化物であって、含水量は極め
て多いことがわかった。このため表面被膜中に多量の水
分が含まれていると、焼鈍過程で脱水することに伴い焼
鈍雰囲気中の水蒸気猾が増大すると考えられる。First, it was found that the AlzOz film formed on the surface of the amorphous alloy ribbon by anodization is a hydrated oxide and has an extremely high water content. For this reason, if a large amount of water is contained in the surface coating, it is thought that water vapor in the annealing atmosphere will increase due to dehydration during the annealing process.
含ボロン鉄基非晶質合金薄帯は、このように雰囲気中に
水分があると、焼鈍過程において合金中のボロンが選択
的に酸化されて合金表面近傍のボロン量が減少する。そ
の結果、薄帯表面近傍の結晶化温度は顕著に低下するか
ら焼鈍によって表面結晶化が進行し、鉄損は劣化するこ
とになると考えられる。In the boron-containing iron-based amorphous alloy ribbon, when there is moisture in the atmosphere, boron in the alloy is selectively oxidized during the annealing process, and the amount of boron near the alloy surface is reduced. As a result, the crystallization temperature near the surface of the ribbon decreases markedly, so it is thought that surface crystallization progresses due to annealing, and the iron loss deteriorates.
第１図に、陽極処理によって非晶質合金薄帯の表面上に
形成されたΔ１２０３被膜の赤外反射スペクトルを示す
。同図から明らかなように、表面被膜には、多量の結合
水を含んでいる。このような表面被膜を有する非晶質合
金薄帯に加熱処理を加えながら、赤りＩ反射スペクトル
の変化を調べたところ、２５０〜４００°Ｃの温度領域
で水分の放出が行われることが判明した。FIG. 1 shows the infrared reflection spectrum of the Δ1203 coating formed on the surface of the amorphous alloy ribbon by anodizing. As is clear from the figure, the surface film contains a large amount of bound water. When heat-treating an amorphous alloy ribbon with such a surface coating, we investigated changes in the red I reflection spectrum and found that water was released in the temperature range of 250 to 400°C. did.
この温度領域は、Ｆｅ−Ｂ−３ｉ系非晶質合金の鉄損を
低下させるために行う磁場焼鈍の温度域とほとんど重複
している。したがってアルミナ陽極処理ン１伎股を有す
る非晶質合金薄帯にドライネ活性雰囲気でｉＡ＞’ａを
協ずと、薄帯表面は水分を多量に含んだ雰囲気にさらさ
れることになる。このことが陽極処理被膜を施さｎたＦ
ｅ−Ｂ−Ｓｉ系非晶質合金薄帯にドライＮ２雰囲気中で
の焼鈍を施した際に生じるα−Ｆｅ表面結晶化の原因で
あると考えられる。This temperature range almost overlaps with the temperature range of magnetic field annealing performed to reduce iron loss of the Fe-B-3i amorphous alloy. Therefore, if an amorphous alloy ribbon having a single alumina anodization treatment is subjected to a dry active atmosphere such that iA>'a, the surface of the ribbon will be exposed to an atmosphere containing a large amount of moisture. This means that the anodized coating
This is thought to be the cause of α-Fe surface crystallization that occurs when an e-B-Si amorphous alloy ribbon is annealed in a dry N2 atmosphere.
そこでこの発明では、このような加熱処理過程で地縁被
膜から放出される水分によって合金表面層でボロンが選
択酸化され、表面結晶化が生起するのを抑制するために
、ボロンの選択酸化に先立って強固な酸化膜を生成させ
てボロンの優先的酸化を阻むように、酸素含有雰囲気中
で焼鈍することにしたのである。すなわち焼鈍環境を酸
素含有雰囲気とし、酸素ポテンシャルを高めた場合には
、むしろＳｉが酸化されて薄帯表面に強固な酸化膜が形
成され、若干の水分が雰囲気中に含まれていてもボロン
の選択酸化は生じなくなる。したがって低ボロン領域は
形成されないから、α−Ｒｅ表面結晶化は起こらず、鉄
損の劣化も無いのである。Therefore, in this invention, in order to prevent boron from being selectively oxidized in the alloy surface layer due to moisture released from the edge coating during the heat treatment process and surface crystallization occurring, prior to the selective oxidation of boron, They decided to perform annealing in an oxygen-containing atmosphere to form a strong oxide film and prevent preferential oxidation of boron. In other words, if the annealing environment is an oxygen-containing atmosphere and the oxygen potential is increased, Si will be oxidized and a strong oxide film will be formed on the ribbon surface, and even if some moisture is contained in the atmosphere, boron will not be absorbed. Selective oxidation no longer occurs. Therefore, since a low boron region is not formed, α-Re surface crystallization does not occur and there is no deterioration in iron loss.
この発明は、上記の知見に立脚するものである。This invention is based on the above knowledge.
すなわちこの発明は、表面に陽極処理によって形成され
た酸化物系絶縁被膜を有する含ボロン鉄基非晶質合金薄
帯の焼鈍に際し、
焼鈍環境として酸素含有雰囲気を用いることを特徴とす
る非晶質合金薄帯の焼鈍方法である。That is, the present invention provides an amorphous material characterized by using an oxygen-containing atmosphere as an annealing environment when annealing a boron-containing iron-based amorphous alloy ribbon having an oxide-based insulating film formed on the surface by anodizing. This is a method of annealing alloy ribbon.
この発明を適用して好適な含ボロン鉄基非晶質合金とし
ては、Ｆｅ−Ｂ−Ｓｉ系の他、Ｆｅ−Ｂ−３ｉ−Ｃ系、
Ｆｅ−（Ｍｎ、 Ｎｉ） −Ｂ−Ｓｉ系、Ｆｅ−（Ｍｎ
、Ｎ１）−Ｂ−Ｓｉ −Ｃ系などがある。Boron-containing iron-based amorphous alloys to which this invention is applied include Fe-B-Si, Fe-B-3i-C,
Fe-(Mn, Ni)-B-Si system, Fe-(Mn
, N1)-B-Si-C system, etc.
（作用）
以下この発明のＩＭＶＡとなった実験について説明する
。(Function) The experiment that led to the IMVA of this invention will be described below.
Ｆｅｅｏ Ｂ ＋ ｚｓｉａ組成（原子％）の溶融合金
をスリット状の注湯、ノズルから、高速回転する調合金
製の冷却用ロール直−ヒに射出して鋤、速凝固させ、５
０ｍ１Ｉ＋幅の非晶質合金薄帯を作製した。A molten alloy having a composition of Feeo B + zsia (atomic %) is poured into a slit, and is injected from a nozzle directly into a cooling roll made of prepared alloy that rotates at high speed, and is rapidly solidified.
An amorphous alloy ribbon with a width of 0 m1I+ was produced.
次いで３ｗｔ％のアルミン酸ナト・リウムと１ｗｔ％の
酒石酸を含む水溶液を電解液として、液温４０’Ｃ１電
流密度１０ Ａ／ｄｍ”で非晶質合金薄帯側を陽極にし
て電解処理を施し、たところ、２秒間の電解後には平均
膜７杓０．０８μｍのアルミナ被膜が形成された。Next, electrolytic treatment was performed using an aqueous solution containing 3 wt% sodium/lium aluminate and 1 wt% tartaric acid as an electrolyte at a liquid temperature of 40'C1 and a current density of 10 A/dm'' with the amorphous alloy ribbon side as the anode. However, after 2 seconds of electrolysis, an alumina film with an average thickness of 0.08 μm was formed.
このようにして表面被膜を施した非晶質合金薄帯に対し
て、空気気流中で３８０ ”Ｃ１１時間の磁場焼鈍を行
い、磁気特性を測定したところ、５０１（ｚ、１．３
Ｔ テノ鉄損は０．０９Ｗ／ｋｇ”ｉｎ’あり、また１
００Ａ／ｍテの磁束密度は１．４２ Ｔであった。この
焼鈍後の薄帯表面について薄膜Ｘ線回折で調べたが、ハ
ローパターンのみが観察され、表面結晶化は生じていな
かった。The amorphous alloy ribbon with the surface coating thus applied was subjected to magnetic field annealing for 380"C11 hours in an air stream, and its magnetic properties were measured.
T Teno iron loss is 0.09W/kg"in', and 1
The magnetic flux density at 00 A/m was 1.42 T. The surface of this annealed ribbon was examined by thin film X-ray diffraction, but only a halo pattern was observed, and no surface crystallization occurred.
このように、３００〜４５０°Ｃでの焼鈍を酸素介在雰
囲気中でおこなうことによって、アルミナ陽極酸化膜を
処理したＦｅ−Ｂ−Ｓｉ系非晶質合金薄帯の鉄損を劣化
させることなく、１．ＩＩＦの焼鈍を行うことができる
。In this way, by performing annealing at 300 to 450°C in an oxygen-mediated atmosphere, the iron loss of the Fe-B-Si amorphous alloy ribbon treated with the alumina anodic oxide film is not deteriorated. 1. IIF annealing can be performed.
ここに焼鈍雰囲気中の酸累含有星は、２νｏｆ％以」二
とするのが好ましい。２νｏ１％に満たないとボロンの
酸化に先立つＳｉ０２膜の形成が充分とはいいがたいか
らである。一方酸素含有遣の上限は、特にないが、経済
性の観点から空気を使える意味で２０νｏ１％程度とす
るのが好ましい。Here, it is preferable that the number of acid-containing stars in the annealing atmosphere is 2νof% or more. This is because if the 2νo is less than 1%, the formation of the Si02 film prior to the oxidation of boron cannot be said to be sufficient. On the other hand, there is no particular upper limit to the oxygen content, but it is preferably about 20νo1% from the economic point of view, meaning that air can be used.
またＦｅ−Ｂ−Ｓｉ系、Ｆｅ−Ｂ −Ｓｉ−Ｃ系、Ｆｅ
−（門ｎ、Ｎ１）Ｂ−Ｓｉ系、及びＦｅ−（Ｍｎ、 Ｎ
ｉ） −Ｂ −Ｓｉ−Ｃ系の含ボロン鉄基非晶質合金は
、結晶化温度を高め、鉄損を減少させるために！３．Ｓ
ｔをそれぞれ７〜１６原子％、４へ１４原子％含有させ
ることが好ましく、また磁束密度の低下を抑え、鉄１員
を減少させるためにＭｎ＋Ｎｉを１種又は２種の合計で
０．５〜１０原子％含有させることが好ましい。Ｍｎ、
Ｎｉを含有させる場合にはＦｅを６５〜８５原子％の１
ｎ囲とすることが望ましい。Also, Fe-B-Si system, Fe-B-Si-C system, Fe
-(phylum n, N1) B-Si system, and Fe-(Mn, N
i) -B -Si-C type boron-containing iron-based amorphous alloy to increase crystallization temperature and reduce iron loss! 3. S
It is preferable to contain 7 to 16 at% of t and 14 at% of t to 4, respectively, and 0.5 to 0.5 to 10% of one or two types of Mn+Ni in total in order to suppress a decrease in magnetic flux density and reduce iron 1 member. It is preferable to contain 10 atom %. Mn,
When Ni is contained, 65 to 85 at% of Fe is 1
It is desirable to set the range to n.
Ｃは通常、工業的に利用できる鉄中には、−船釣に含有
されている元素であるが、本発明の対象とする磁性材料
として使用されるＦ６基非晶質合金中に含有される場合
は２原子％以下であることが望ましい６２原子％を超え
ると、鉄１員が劣化し、また、非晶質形成能も低下する
からである。C is an element that is normally contained in iron that can be used industrially, but it is also contained in the F6-based amorphous alloy used as the magnetic material that is the object of the present invention. In this case, the content is preferably 2 at % or less, but if it exceeds 62 at %, the iron 1-member will deteriorate and the ability to form an amorphous state will also decrease.
（実施例）
丈茄Ｍ−１−
Ｆｅ７ｅ Ｂ ＋ ｏｓｉ ＋ ｚｍ成（原子％）にな
る幅５ｃｍ、板厚２８μｍの非晶實合金薄１１Ｐ壱陽極
とし、３１言％のアルミン酸ナトリウムと１ｗｔ％の酒
石酸とを含む水溶液中において電解処理を施した。この
際、電解液の液温を４０°Ｃ１電流密度を１０ Ａ７ｄ
ｌｌ＋”とじたところ、２秒間の電解後には平均膜７杓
０．０８＃ｍのアルミナ被膜が形成された。(Example) The anode was made of a thin 11P amorphous alloy with a width of 5 cm and a plate thickness of 28 μm, consisting of Fe7e B + osi + Zm (atomic %), and 31% sodium aluminate and 1 wt%. Electrolytic treatment was performed in an aqueous solution containing tartaric acid. At this time, the temperature of the electrolyte was set to 40°C, the current density was set to 10 A7d
After 2 seconds of electrolysis, an alumina film with an average thickness of 7 ml and 0.08 #m was formed.
次二二（５ｖｏＨ０２＋９５ ｖｏｌχＮ２）の混合ガ
ス雰囲気中で３７０°Ｃ，１時間の磁場焼鈍を行い、そ
のまま冷り口した。このようにし７て得られた屯ｉ（被
膜付き非晶質合金薄帯の鉄ｔｆｌＷ＋ １ｙｓｏ ハ０
．１２１４／ｋｇ ′Ｔニアった。なお表面層を薄ｉｆ
Ａ Ｘ線回折で調べたが、結晶質物質は検出されなかっ
た。Magnetic field annealing was performed at 370°C for 1 hour in a mixed gas atmosphere of 22 (5voH02+95volχN2), and then cooled. Thus obtained tun i (coated amorphous alloy ribbon iron tflW+ 1yso ha0
．． 1214/kg 'T near. Note that if the surface layer is thin
A No crystalline material was detected by X-ray diffraction.
実−３！： ３！Ｉ！ＪＬ
合金組成をＦｃｔ７Ｍｎｌ Ｂ １ｘｓｉ＋ｏとする他
は、実施例１と同様に処理した。得られた絶縁被膜付き
非晶質合金薄帯の磁場中焼鈍後の鉄損Ｗｌ：ｌ／Ｓ。は
０．１０Ｗ／ｋｇであった。なお薄膜Ｘ線回折でも表面
層に結晶質物質は検出されなかった。Fruit-3! : 3! I! JL The process was carried out in the same manner as in Example 1, except that the alloy composition was changed to Fct7MnlB1xsi+o. Iron loss Wl of the obtained amorphous alloy ribbon with an insulating film after annealing in a magnetic field: l/S. was 0.10W/kg. Furthermore, no crystalline substance was detected in the surface layer by thin film X-ray diffraction.
実瀞例ニー
合金組成をＦｅ７−、ＭｎｚＮ＋ ｚ Ｂ ＋ ｚｓｉ
ｑとする池は、実施例１と同様に処理した。得られた鞄
縁被膜付き非晶質合金薄帯の磁場中焼鈍後の鉄狽鵬、７
、。は０．１３Ｗ 、／ ｋ ｇであった。なお薄膜Ｘ
線回折でも表面層に結晶質物Ｉ′ｊは検出されなかった
。Actual example knee alloy composition is Fe7-, MnzN+ z B + zsi
The pond designated as q was treated in the same manner as in Example 1. The obtained amorphous alloy ribbon with bag edge coating was annealed in a magnetic field, 7
,. was 0.13W,/kg. In addition, thin film
No crystalline substance I'j was detected in the surface layer by line diffraction.
対答１うＬ・１−
合金組成をＦｅｔｔＭｎｌＢ＋ｚＳｉｑＣ＋ とする他
は実施例１と同様に処理して、童縁被膜付き非晶質合金
薄帯を作った。Answer 1 L.1- An amorphous alloy ribbon with a fringe coating was produced in the same manner as in Example 1 except that the alloy composition was changed to FettMnlB+zSiqC+.
次に空気気流中で３８０°Ｃ１１時間の磁場焼鈍を施し
たところ鉄損−７／・、。は０．０９Ｗ／ｋｇであった
。なお５ｅｌｌ莫Ｘ綿回折でも表面層に結晶物質器よ検
出されなかった。Next, magnetic field annealing was performed at 380°C for 11 hours in an air stream, resulting in an iron loss of -7/. was 0.09W/kg. In addition, no crystalline material was detected in the surface layer even by 5ell MoX cotton diffraction.
、比−較一例」一
実施例２と同じ合金組成になる非晶質合金；■帯を実施
例１と同）峠こ電′Ａ￥処理Ｌ、得られた絶♀（破膜付
き非晶質合金薄帯にドライＡｒガス気流中で磁場中焼鈍
（３７０’Ｃ３１時間、２００ＯＡ／ｍ）を施したとこ
ろ、鉄１ｉｉＷＢｚｓ。は０．２９讐／ｋｇまで劣化し
た。また薄膜Ｘ線回折５二より薄）１）表面を３Ｊすべ
たところ、α−Ｆｅの表面結晶化が確認された。An amorphous alloy having the same alloy composition as Example 2; When a high quality alloy ribbon was annealed in a magnetic field (370'C, 31 hours, 200OA/m) in a dry Ar gas stream, the iron 1iiWBzs. deteriorated to 0.29/kg. Thinner) 1) When the surface was rubbed for 3J, surface crystallization of α-Fe was confirmed.
（発明の効果）
この発明によれば、陽極処理によって絶縁被膜を施しま
た非晶質合金薄帯を、鉄ｔｉ特性の劣化を招くことなく
焼鈍することができる。(Effects of the Invention) According to the present invention, an amorphous alloy ribbon coated with an insulating film by anodization can be annealed without causing deterioration of the iron-ti properties.
第１図は、陽（か処理によって非晶質合金薄帯の表面上
に形成されたＡ１□０３被膜の赤外反射スペク１〜ルを
示すグラフである。
第１２図FIG. 1 is a graph showing the infrared reflection spectra of the A1□03 film formed on the surface of the amorphous alloy ribbon by positive treatment.
Claims (1)
膜を有する含ボロン鉄基非晶質合金薄帯の焼鈍に際し、 焼鈍環境として酸素含有雰囲気を用いることを特徴とす
る非晶質合金薄帯の焼鈍方法。 ２、含ボロン鉄基非晶質合金が、 Ｂ：７〜１６原子％、 Ｓｉ：４〜１４原子％ を含有し、残部は実質的にＦｅの組成になるＦｅ−Ｂ−
Ｓｉ系合金である請求項１記載の非晶質合金薄帯の焼鈍
方法。 ３、含ボロン鉄基非晶質合金が、 Ｂ：７〜１６原子％、 Ｓｉ：４〜１４原子％及び Ｃ：２原子％以下 を含有し、残部は実質的にＦｅの組成になるＦｅ−Ｂ−
Ｓｉ−Ｃ系合金である請求項１記載の非晶質合金薄帯の
焼鈍方法。 ４、含ボロン鉄基非晶質合金が、 Ｂ：７〜１６原子％、 Ｓｉ：４〜１４原子％、 Ｍｎ、Ｎｉの１種又は２種の合計：０．５〜１０原子％
及び Ｆｅ：６５〜８５原子％ からなるＦｅ−（Ｍｎ，Ｎｉ）−Ｂ−Ｓｉ系合金である
請求項１記載の非晶質合金薄帯の焼鈍方法。 ５、含ボロン鉄基非晶質合金が、 Ｂ：７〜１６原子％、 Ｓｉ：４〜１４原子％ Ｃ：２原子％以下、 Ｍｎ、Ｎｉの１種又は２種の合計：０．５〜１０原子％
及び Ｆｅ：６５〜８５原子％ からなるＦｅ−（Ｍｎ，Ｎｉ）−Ｂ−Ｓｉ−Ｃ系合金で
ある請求項１記載の非晶質合金薄帯の焼鈍方法。[Claims] 1. An oxygen-containing atmosphere is used as the annealing environment when annealing a boron-containing iron-based amorphous alloy ribbon having an oxide insulating film formed on the surface by anodizing. Annealing method for amorphous alloy ribbon. 2. The boron-containing iron-based amorphous alloy contains B: 7 to 16 atom%, Si: 4 to 14 atom%, and the balance is substantially Fe-B-
A method for annealing an amorphous alloy ribbon according to claim 1, which is a Si-based alloy. 3. The boron-containing iron-based amorphous alloy contains: B: 7 to 16 atomic %, Si: 4 to 14 atomic %, and C: 2 atomic % or less, and the remainder is Fe- B-
A method of annealing an amorphous alloy ribbon according to claim 1, which is a Si-C alloy. 4. The boron-containing iron-based amorphous alloy contains: B: 7 to 16 at%, Si: 4 to 14 at%, total of one or two of Mn and Ni: 0.5 to 10 at%
The method of annealing an amorphous alloy ribbon according to claim 1, wherein the amorphous alloy ribbon is an Fe-(Mn, Ni)-B-Si alloy consisting of Fe: 65 to 85 atomic %. 5. The boron-containing iron-based amorphous alloy contains: B: 7 to 16 at%, Si: 4 to 14 at%, C: 2 at% or less, total of one or two of Mn and Ni: 0.5 to 10 atomic%
The method of annealing an amorphous alloy ribbon according to claim 1, wherein the amorphous alloy ribbon is an Fe-(Mn, Ni)-B-Si-C alloy consisting of Fe: 65 to 85 atomic %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28582988A JPH02133517A (en) | 1988-11-14 | 1988-11-14 | Method for annealing thin amorphous alloy strip |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28582988A JPH02133517A (en) | 1988-11-14 | 1988-11-14 | Method for annealing thin amorphous alloy strip |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02133517A true JPH02133517A (en) | 1990-05-22 |
Family
ID=17696619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28582988A Pending JPH02133517A (en) | 1988-11-14 | 1988-11-14 | Method for annealing thin amorphous alloy strip |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02133517A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5478411A (en) * | 1990-12-21 | 1995-12-26 | Provost, Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth Near Dublin | Magnetic materials and processes for their production |
| JP2010183838A (en) * | 1998-11-06 | 2010-08-19 | Metglas Inc | Bulk amorphous metal magnetic component for electric motor |
| JP6294534B1 (en) * | 2017-04-03 | 2018-03-14 | 住友電気工業株式会社 | Manufacturing method of iron carbide material and iron carbide thin film material |
| JP6294533B1 (en) * | 2017-04-03 | 2018-03-14 | 住友電気工業株式会社 | Manufacturing method of iron boride material and iron boride thin film material |
| US11955261B2 (en) | 2021-08-25 | 2024-04-09 | Tdk Corporation | Magnetic alloy ribbon, laminate, and magnetic core |
-
1988
- 1988-11-14 JP JP28582988A patent/JPH02133517A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5478411A (en) * | 1990-12-21 | 1995-12-26 | Provost, Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth Near Dublin | Magnetic materials and processes for their production |
| JP2010183838A (en) * | 1998-11-06 | 2010-08-19 | Metglas Inc | Bulk amorphous metal magnetic component for electric motor |
| JP6294534B1 (en) * | 2017-04-03 | 2018-03-14 | 住友電気工業株式会社 | Manufacturing method of iron carbide material and iron carbide thin film material |
| JP6294533B1 (en) * | 2017-04-03 | 2018-03-14 | 住友電気工業株式会社 | Manufacturing method of iron boride material and iron boride thin film material |
| JP2018177543A (en) * | 2017-04-03 | 2018-11-15 | 住友電気工業株式会社 | Production method of iron carbide material, and thin film material of iron carbide |
| US11955261B2 (en) | 2021-08-25 | 2024-04-09 | Tdk Corporation | Magnetic alloy ribbon, laminate, and magnetic core |
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