JP7446600B2 - Manufacturing method of Cu-Mn-Al magnet - Google Patents
Manufacturing method of Cu-Mn-Al magnet Download PDFInfo
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- JP7446600B2 JP7446600B2 JP2019231653A JP2019231653A JP7446600B2 JP 7446600 B2 JP7446600 B2 JP 7446600B2 JP 2019231653 A JP2019231653 A JP 2019231653A JP 2019231653 A JP2019231653 A JP 2019231653A JP 7446600 B2 JP7446600 B2 JP 7446600B2
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- 229910018657 Mn—Al Inorganic materials 0.000 title claims description 51
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 230000005291 magnetic effect Effects 0.000 claims description 86
- 238000010438 heat treatment Methods 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 18
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- 239000000956 alloy Substances 0.000 claims description 15
- 229910052748 manganese Inorganic materials 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910001291 heusler alloy Inorganic materials 0.000 claims description 4
- 239000012071 phase Substances 0.000 description 44
- 239000000543 intermediate Substances 0.000 description 36
- 239000010949 copper Substances 0.000 description 35
- 239000011572 manganese Substances 0.000 description 29
- 230000000694 effects Effects 0.000 description 17
- 230000005294 ferromagnetic effect Effects 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 13
- 230000005415 magnetization Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 12
- 230000001737 promoting effect Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910016583 MnAl Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Description
特許法第３０条第２項適用 発行者名：国立大学法人東北大学 金属材料研究所、刊行物名：東北大学金属材料研究所 強磁場超伝導材料研究センター 平成３０年度年次報告、発行年月：２０１９年６月 Article 30, Paragraph 2 of the Patent Law applies Publisher's name: National University Corporation Tohoku University, Institute for Materials Research, Publication name: Tohoku University Institute for Materials Research, High-field Superconducting Materials Research Center Annual Report 2018, Publication date : June 2019
特許法第３０条第２項適用 発行者名：日本金属学会・日本鉄鋼協会・軽金属学会 九州支部 合同学術講演大会 実行委員会、刊行物名：令和元年度 合同学術講演大会 講演概要集、発行年月日：２０１９年６月１日 集会名：２０１９年度合同学術講演会、発表名：「Ｃｕ－Ｍｎ－Ａｌ合金の磁場中熱処理効果」、開催日：２０１９年６月１日 Article 30, Paragraph 2 of the Patent Act applies Publisher name: Japan Institute of Metals, Japan Iron and Steel Institute, Kyushu Branch Joint Academic Lecture Conference Executive Committee, Publication name: 2019 Joint Academic Lecture Conference Lecture Summary Collection, Publication Date: June 1, 2019 Meeting name: 2019 Joint Academic Lecture, Presentation name: "Magnetic field heat treatment effect of Cu-Mn-Al alloy", Date: June 1, 2019
特許法第３０条第２項適用 発行者名：公益社団法人 応用物理学会、刊行物名：２０１９年第８０回応用物理学会秋季学術講演会講演予稿集ＤＶＤ、発行年月日：２０１９年９月４日 Article 30, Paragraph 2 of the Patent Act applies Publisher name: Japan Society of Applied Physics, Public Interest Incorporated Association, Publication name: 2019 80th Japan Society of Applied Physics Autumn Academic Lecture Proceedings Collection DVD, Publication date: September 2019 4 days
特許法第３０条第２項適用 集会名：２０１９年第８０回応用物理学会秋季学術講演会、発表名：「Ｒｅｄｕｃｔｉｏｎ ｏｆ ｔｈｅ Ｃｒｙｓｔａｌｌｉｔｅ Ｓｉｚｅ ｉｎ Ｃｕ▲２▼ＭｎＡｌ Ａｌｌｏｙｓ ｂｙ Ｉｎ－ｆｉｅｌｄ Ａｎｎｅａｌｉｎｇ」（「磁場中熱処理によるＣｕ▲２▼ＭｎＡｌ合金の微細化」）、開催日：２０１９年９月１８日 Article 30, Paragraph 2 of the Patent Act applies Meeting name: 2019 80th Japan Society of Applied Physics Autumn Academic Conference, Presentation name: “Reduction of the Crystallite Size in Cu▲2▼MnAl Alloys by In-field Annealing” (“Magnetic field "Refining of Cu▲2▼MnAl alloy by medium heat treatment"), Date: September 18, 2019
特許法第３０条第２項適用 発行者名：Ｆａｃｕｌｔｙ ｏｆ Ｅｎｇｉｎｅｅｒｉｎｇ Ｐｈｙｓｉｃｓ ａｎｄ Ｎａｎｏｔｅｃｈｎｏｌｏｇｙ，ＶＮＵ Ｕｎｉｖｅｒｓｉｔｙ ｏｆ Ｅｎｇｉｎｅｅｒｉｎｇ ａｎｄ Ｔｅｃｈｎｏｌｏｇｙ，Ｖｉｅｔｎａｍ Ｎａｔｉｏｎａｌ Ｕｎｉｖｅｒｓｉｔｙ，Ｈａｎｏｉ（ベトナム国家大学ハノイ校工科大学、工業物理・ナノテクノロジー学部）、刊行物名：ＦＭＳ－ＮＡＮＯＭＡＴＡ２０１９ ＡＢＳＴＲＡＣＴ ＢＯＯＫ（エフエムエス－ナノマタ２０１９ アブストラクトブック）、発行年月日：２０１９年１１月１０日 集会名：Ｊｏｉｎｔ ５ｔｈ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｓｙｍｐｏｓｉｕｍ ｏｎ Ｆｒｏｎｔｉｅｒｓ ｉｎ Ｍａｔｅｒｉａｌｓ Ｓｃｉｅｎｃｅ ａｎｄ ３ｒｄ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｓｙｍｐｏｓｉｕｍ ｏｎ Ｎａｎｏ－ｍａｔｅｒｉａｌｓ， Ｔｅｃｈｎｏｌｏｇｙ ａｎｄ Ａｐｐｌｉｃａｔｉｏｎｓ（材料科学のフロンティアに関する第５回国際シンポジウムとナノ材料、技術、及び応用に関する第３回国際シンポジウムとの合同シンポジウム）、発表名：「Ｍａｇｎｅｔｉｃ ｐｒｏｐｅｒｔｉｅｓ ｏｆ Ｃｕ－Ｍｎ－Ａｌ ｓｙｓｔｅｍ ａｎｎｅａｌｅｄ ｕｎｄｅｒ ｈｉｇｈ ｍａｇｎｅｔｉｃ ｆｉｅｌｄｓ」（「強磁場中熱処理したＣｕ－Ｍｎ－Ａｌ系の磁気特性」）、開催日：２０１９年１１月１１日Article 30, Paragraph 2 of the Patent Law applies Publisher name: Faculty of Engineering Physics and Nanotechnology, VNU University of Engineering and Technology, Vietnam National Published by nal University, Hanoi (Faculty of Industrial Physics and Nanotechnology, University of Technology, Vietnam National University, Hanoi) Product name: FMS-NANOMATA2019 ABSTRACT BOOK, Publication date: November 10, 2019 Meeting name: Joint 5th International Symposium on Frontiers in Materials Science and 3rd International Symposium on Nano-materials, Technology and Applications (joint symposium between the 5th International Symposium on Frontiers of Materials Science and the 3rd International Symposium on Nanomaterials, Technology, and Applications), Presentation name: "Magnetic properties of Cu-Mn-Al system annealed under" high magnetic fields” (“Magnetic properties of Cu-Mn-Al system heat-treated in a strong magnetic field”), Date: November 11, 2019
本発明は、Ｃｕ－Ｍｎ－Ａｌ系磁石の製造方法に関する。 The present invention relates to a method for manufacturing a Cu--Mn--Al magnet.
特許文献１及び２に開示されているように、Ｍｎ及びＡｌを含むＭｎ－Ａｌ系磁石の中間体、並びにＭｎ及びＢｉを含むＭｎ－Ｂｉ系磁石の中間体に対して、加熱を磁場中で行う磁場中熱処理を施すことが提案されている。 As disclosed in Patent Documents 1 and 2, an Mn-Al magnet intermediate containing Mn and Al and an Mn-Bi magnet intermediate containing Mn and Bi are heated in a magnetic field. It has been proposed to perform heat treatment in a magnetic field.
特許文献１及び２は、強磁性相の合成が促進されるという理由で、磁場中熱処理を推奨している。強磁性相の合成の促進は、得られる磁石の磁化を増強させる要因となる。 Patent Documents 1 and 2 recommend heat treatment in a magnetic field because the synthesis of the ferromagnetic phase is promoted. Accelerating the synthesis of the ferromagnetic phase is a factor that increases the magnetization of the resulting magnet.
しかし、磁石の用途によっては、大きすぎる磁化はむしろ望ましくなく、保磁力が充分に大きい磁石が望まれる場合もある。 However, depending on the purpose of the magnet, excessively large magnetization is rather undesirable, and a magnet with sufficiently large coercive force may be desired.
本発明の目的は、磁化を抑えることができる一方、保磁力を高めることができる、Ｃｕ－Ｍｎ－Ａｌ系磁石の製造方法を提供することである。 An object of the present invention is to provide a method for manufacturing a Cu--Mn--Al magnet that can suppress magnetization while increasing coercive force.
上記目的を達成するために、本発明に係るＣｕ－Ｍｎ－Ａｌ系磁石の製造方法は、
Ｃｕ、Ｍｎ、及びＡｌを含むＣｕ－Ｍｎ－Ａｌ系中間体を準備する準備工程と、
前記Ｃｕ－Ｍｎ－Ａｌ系中間体に対し、前記Ｃｕ－Ｍｎ－Ａｌ系中間体に磁場を与えつつ前記Ｃｕ－Ｍｎ－Ａｌ系中間体を加熱する磁場中熱処理を施す磁場中熱処理工程と、
を有し、
前記磁場中熱処理工程では、前記Ｃｕ－Ｍｎ－Ａｌ系中間体に対し、前記Ｃｕ－Ｍｎ－Ａｌ系中間体に５Ｔ以上の前記磁場を与えつつ前記Ｃｕ－Ｍｎ－Ａｌ系中間体を５００Ｋ以上に加熱する前記磁場中熱処理を、６時間超にわたって施す。
In order to achieve the above object, the method for manufacturing a Cu-Mn-Al magnet according to the present invention includes:
a preparation step of preparing a Cu-Mn-Al intermediate containing Cu, Mn, and Al;
A heat treatment step in a magnetic field of applying a magnetic field to the Cu-Mn-Al-based intermediate while heating the Cu-Mn-Al-based intermediate;
has
In the magnetic field heat treatment step, the Cu-Mn-Al-based intermediate is heated to a temperature of 500 K or more while applying the magnetic field of 5 T or more to the Cu-Mn-Al-based intermediate. The magnetic field heat treatment is carried out for more than 6 hours .
前記準備工程では、Ｃｕ、Ｍｎ、及びＡｌを含む原料粉体を焼結させることにより、Ｃｕ、Ｍｎ、及びＡｌの合金を含む前記Ｃｕ－Ｍｎ－Ａｌ系中間体を準備してもよい。 In the preparation step, the Cu--Mn--Al-based intermediate containing an alloy of Cu, Mn, and Al may be prepared by sintering raw material powder containing Cu, Mn, and Al.
前記合金が、Ｌ２１構造を有するホイスラー合金であってもよい。 The alloy may be a Heusler alloy having an L2 1 structure.
これまで強磁性相の合成を促進する目的で行われてきた磁場中熱処理は、Ｃｕ－Ｍｎ－Ａｌ系中間体に対しては、強磁性相の結晶子を微細化し、かつ非磁性相の合成を促進する効果をもたらすことが判明した。強磁性相の結晶子が微細化され、非磁性相の合成が促進される結果、得られるＣｕ－Ｍｎ－Ａｌ系磁石の磁化を抑えることができる一方、保磁力を高めることができる。 Heat treatment in a magnetic field, which has been carried out for the purpose of promoting the synthesis of the ferromagnetic phase, has been used to refine the crystallites of the ferromagnetic phase and synthesize the non-magnetic phase for Cu-Mn-Al intermediates. It was found that it has the effect of promoting As the crystallites of the ferromagnetic phase are refined and the synthesis of the non-magnetic phase is promoted, the magnetization of the resulting Cu--Mn--Al based magnet can be suppressed, while the coercive force can be increased.
図１に示すフローチャートに沿って、実施形態に係るＣｕ－Ｍｎ－Ａｌ系磁石の製造方法について説明する。 A method for manufacturing a Cu--Mn--Al based magnet according to an embodiment will be described along the flowchart shown in FIG.
（ａ）混合工程
まず、Ｃｕを主成分とする銅粉体、Ｍｎを主成分とするマンガン粉体、及びＡｌを主成分とするアルミニウム粉体を混合し、原料粉体を得る（ステップＳ１）。本明細書において“主成分とする”とは、純度が９７質量％以上、好ましくは９９質量％以上であることを意味する。
(a) Mixing process First, a copper powder containing Cu as a main component, a manganese powder containing Mn as a main component, and an aluminum powder containing Al as a main component are mixed to obtain a raw material powder (Step S1) . In this specification, "containing as a main component" means that the purity is 97% by mass or more, preferably 99% by mass or more.
原料粉体の粒度は、後述する焼結工程（ステップＳ３）において合金が生成される反応を促進する観点から、１ｍｍ未満であることが好ましく、７５μｍ未満であることがより好ましい。本明細書において、粒子の粒径がｄ未満とは、粒子がＪＩＳ－Ｚ８８０１に規定する目開きｄの篩を通過する粒度であることを意味する。 The particle size of the raw material powder is preferably less than 1 mm, more preferably less than 75 μm, from the viewpoint of promoting the reaction that produces an alloy in the sintering step (step S3) described below. In this specification, the particle size of particles less than d means that the particles have a particle size that allows the particles to pass through a sieve having a mesh size d defined in JIS-Z8801.
（ｂ）成形工程
次に、上述した原料粉体を成形することにより、成形体となす（ステップＳ２）。原料粉体の成形方法としては、加圧を伴う方法、例えば、原料粉体を型に充填してプレスする型成形法が典型的である。但し、これに限られない。原料粉体を噴射し、積層させながら造形する積層造形法を用いてもよい。なお、成形に際して、得られる成形体の保形性を高める結合剤を使用してもよい。
(b) Molding process Next, the raw material powder described above is molded to form a molded body (step S2). A typical method for molding the raw material powder is a method that involves pressurization, for example, a molding method in which the raw material powder is filled into a mold and pressed. However, it is not limited to this. An additive manufacturing method may be used in which raw material powder is injected and shaped while being layered. In addition, during molding, a binder may be used to improve the shape retention of the resulting molded product.
（ｃ）焼結工程
次に、得られた成形体を焼結させることにより、Ｃｕ、Ｍｎ、及びＡｌの合金であるＣｕ－Ｍｎ－Ａｌ系合金を含むＣｕ－Ｍｎ－Ａｌ系中間体を得る（ステップＳ３）。
(c) Sintering process Next, by sintering the obtained compact, a Cu-Mn-Al intermediate containing a Cu-Mn-Al alloy that is an alloy of Cu, Mn, and Al is obtained. (Step S3).
焼結の温度は、合金が生成される反応を有意に進行させるため、Ａｌの合金の融点以上、具体的には、９３３Ｋ以上であることが好ましい。また、焼結の温度は、１０７３Ｋ以上であることがより好ましく、１１２３Ｋ以上であることがより好ましい。 The sintering temperature is preferably higher than the melting point of the Al alloy, specifically 933K or higher, in order to significantly advance the reaction that produces the alloy. Further, the sintering temperature is more preferably 1073K or higher, and more preferably 1123K or higher.
Ｃｕ－Ｍｎ－Ａｌ系合金は、ｂｃｃ構造を有するβ相を含む多結晶体である。また、Ｃｕ－Ｍｎ－Ａｌ系合金は、Ｃｕを内割で４０ｍｏｌ％以上含み、Ｍｎを内割で２０ｍｏｌ％以上含み、Ａｌを内割で２０ｍｏｌ％以上含む。 The Cu-Mn-Al alloy is a polycrystalline body containing a β phase having a bcc structure. Further, the Cu-Mn-Al alloy contains Cu in an internal ratio of 40 mol% or more, internally contains Mn in an internal ratio of 20 mol% or more, and internally contains Al in an internal ratio of 20 mol% or more.
具体的には、Ｃｕ－Ｍｎ－Ａｌ系合金は、いずれも強磁性体であるＣｕ５０Ｍｎ２５Ａｌ２５、又はＣｕ４５Ｍｎ２０Ａｌ３５よりなるものであってもよい。このうちＣｕ５０Ｍｎ２５Ａｌ２５は、Ｌ２１構造を有するホイスラー合金である。 Specifically, the Cu-Mn-Al alloy may be made of Cu 50 Mn 25 Al 25 or Cu 45 Mn 20 Al 35 , both of which are ferromagnetic. Among these, Cu 50 Mn 25 Al 25 is a Heusler alloy having an L2 1 structure.
なお、Ｃｕ－Ｍｎ－Ａｌ系合金に占めるＣｕ、Ｍｎ、及びＡｌのモル比は、ステップＳ１の混合工程における銅粉体、マンガン粉体、及びアルミニウム粉体の配合割合によって調整できる。 Note that the molar ratio of Cu, Mn, and Al in the Cu--Mn--Al alloy can be adjusted by adjusting the mixing ratio of copper powder, manganese powder, and aluminum powder in the mixing process of step S1.
但し、Ｃｕ－Ｍｎ－Ａｌ系中間体は、その全体が完全に合金化されていなくてもよく、合金化されずに独立しているＣｕ、Ｍｎ、及びＡｌを含んでいてもよい。また、Ｃｕ－Ｍｎ－Ａｌ系中間体は、Ｃｕ、Ｍｎ、及びＡｌ以外の不可避的不純物を内割で５質量％以下含んでもよい。 However, the entirety of the Cu-Mn-Al intermediate may not be completely alloyed, and may contain Cu, Mn, and Al that are independent without being alloyed. Further, the Cu-Mn-Al intermediate may contain 5% by mass or less of unavoidable impurities other than Cu, Mn, and Al.
なお、以上説明したステップＳ１からＳ３は、Ｃｕ、Ｍｎ、及びＡｌを含むＣｕ－Ｍｎ－Ａｌ系中間体を準備する準備工程の一例である。 Note that steps S1 to S3 described above are an example of a preparation process for preparing a Cu-Mn-Al intermediate containing Cu, Mn, and Al.
（ｄ）磁場中熱処理工程
次に、Ｃｕ－Ｍｎ－Ａｌ系中間体に対し、Ｃｕ－Ｍｎ－Ａｌ系中間体に磁場を与えつつＣｕ－Ｍｎ－Ａｌ系中間体を加熱する磁場中熱処理を施す（ステップＳ４）。これにより、等方性磁石であるＣｕ－Ｍｎ－Ａｌ系磁石が得られる。
(d) Magnetic field heat treatment step Next, the Cu-Mn-Al intermediate is subjected to magnetic field heat treatment in which the Cu-Mn-Al intermediate is heated while applying a magnetic field to the Cu-Mn-Al intermediate. (Step S4). As a result, a Cu--Mn--Al based magnet, which is an isotropic magnet, is obtained.
特許文献１及び２が教示するように、これまで磁場中熱処理は、強磁性相の合成を促進する目的で行われてきた。しかし、本願発明者らの研究によれば、磁場中熱処理は、Ｃｕ－Ｍｎ－Ａｌ系中間体に対しては、従来の効果とは逆の効果、具体的には、強磁性相の結晶子サイズを微細化し、かつ非磁性相の合成を促進する効果をもたらすことが判明した。 As taught in Patent Documents 1 and 2, heat treatment in a magnetic field has heretofore been performed for the purpose of promoting the synthesis of a ferromagnetic phase. However, according to the research of the present inventors, heat treatment in a magnetic field has an effect opposite to the conventional effect on Cu-Mn-Al intermediates. It has been found that this has the effect of reducing the size and promoting the synthesis of a non-magnetic phase.
磁場中熱処理によって、Ｃｕ－Ｍｎ－Ａｌ系中間体における強磁性相の結晶子が微細化され、非磁性相の合成が促進される結果、得られるＣｕ－Ｍｎ－Ａｌ系磁石の磁化を抑えることができる一方、保磁力を高めることができる。 Heat treatment in a magnetic field refines the crystallites of the ferromagnetic phase in the Cu-Mn-Al intermediate and promotes the synthesis of the non-magnetic phase, thereby suppressing the magnetization of the resulting Cu-Mn-Al magnet. While it is possible to increase the coercive force.
なお、磁場中熱処理でＣｕ－Ｍｎ－Ａｌ系中間体に与える磁場は、磁化を抑制する効果と保磁力を高める効果とを一層充分に得るために、５Ｔ以上であることが好ましく、１０Ｔ以上であることがより好ましい。 In addition, the magnetic field applied to the Cu-Mn-Al intermediate during magnetic field heat treatment is preferably 5T or more, and preferably 10T or more in order to obtain a more sufficient effect of suppressing magnetization and increasing coercive force. It is more preferable that there be.
また、磁場中熱処理でＣｕ－Ｍｎ－Ａｌ系中間体を加熱する温度は、ステップＳ３の焼結工程で成形体を加熱する温度よりも低い。但し、磁化を抑制する効果と保磁力を高める効果とを一層充分に得るために、磁場中熱処理でＣｕ－Ｍｎ－Ａｌ系中間体を加熱する温度は、５００Ｋ以上であることが好ましく、５５０Ｋ以上であることがより好ましい。 Further, the temperature at which the Cu--Mn--Al intermediate is heated in the magnetic field heat treatment is lower than the temperature at which the compact is heated in the sintering step of step S3. However, in order to more fully obtain the effect of suppressing magnetization and the effect of increasing coercive force, the temperature at which the Cu-Mn-Al intermediate is heated by heat treatment in a magnetic field is preferably 500K or higher, and preferably 550K or higher. It is more preferable that
また、磁場中熱処理の初期の段階においては、強磁性相の結晶子が粗大化しうる。そこで、強磁性相の結晶子を微細化し、非磁性相の合成を促進する効果を一層確実に得るために、磁場中熱処理を継続させる時間は、６時間超であることが好ましく、１０時間以上であることがより好ましく、２０時間以上であることがより好ましい。 Furthermore, in the initial stage of heat treatment in a magnetic field, the crystallites of the ferromagnetic phase may become coarse. Therefore, in order to more reliably obtain the effect of refining the crystallites of the ferromagnetic phase and promoting the synthesis of the non-magnetic phase, it is preferable that the heat treatment in the magnetic field be continued for more than 6 hours, and more than 10 hours. It is more preferable that it is, and it is more preferable that it is 20 hours or more.
以上、実施形態に係るＣｕ－Ｍｎ－Ａｌ系磁石の製造方法について例示的に述べたが、以下の変形も可能である。 The method for manufacturing a Cu--Mn--Al magnet according to the embodiment has been exemplified above, but the following modifications are also possible.
磁場中熱処理に供するＣｕ－Ｍｎ－Ａｌ系中間体は、必ずしも焼結によって形成されたものでなくてもよい。Ｃｕの原料、Ｍｎの原料、及びＡｌの原料の混合物を液相状態へと完全に溶融させたものを冷却して得た合金であってもよい。 The Cu--Mn--Al intermediate to be subjected to heat treatment in a magnetic field does not necessarily have to be formed by sintering. An alloy obtained by completely melting a mixture of a Cu raw material, a Mn raw material, and an Al raw material to a liquid phase state and cooling the mixture may also be used.
また、ステップＳ３の焼結工程と、ステップＳ４の磁場中熱処理工程とを、同一の加熱炉としての電気炉を用いて、連続して行ってもよい。また、Ｃｕ－Ｍｎ－Ａｌ系合金の形成と、強磁性相の結晶子の微細化及び非磁性相の合成とが、１つの工程で行われてもよい。 Further, the sintering step in step S3 and the magnetic field heat treatment step in step S4 may be performed continuously using the same electric furnace as the heating furnace. Further, the formation of the Cu--Mn--Al alloy, the refinement of the crystallites of the ferromagnetic phase, and the synthesis of the non-magnetic phase may be performed in one step.
以下、本実施形態に係るＣｕ－Ｍｎ－Ａｌ系磁石の用途について例示的に述べる。本実施形態に係るＣｕ－Ｍｎ－Ａｌ系磁石は、例えば、磁気ディスク、磁気テープといった磁気メモリにおける磁気記録層に用いることができる。本実施形態に係るＣｕ－Ｍｎ－Ａｌ系磁石は、磁場中熱処理によって磁化が抑えられているため、近傍の他の機器に磁気的な悪影響を与えにくい。また、本実施形態に係るＣｕ－Ｍｎ－Ａｌ系磁石は、磁場中熱処理によって保磁力が高められているので、磁気的な反転が生じ難く、ビット情報を安定して保持できる。 Hereinafter, applications of the Cu--Mn--Al based magnet according to the present embodiment will be exemplified. The Cu--Mn--Al based magnet according to this embodiment can be used, for example, in a magnetic recording layer in a magnetic memory such as a magnetic disk or a magnetic tape. Since the Cu--Mn--Al based magnet according to the present embodiment has its magnetization suppressed by heat treatment in a magnetic field, it is unlikely to have an adverse magnetic effect on other devices in the vicinity. Further, since the Cu--Mn--Al based magnet according to the present embodiment has increased coercive force by heat treatment in a magnetic field, magnetic reversal is less likely to occur and bit information can be stably held.
［実施例１］
まず、いずれも純度が９９．９質量％で粒径が７５μｍ未満の銅粉体、マンガン粉体、及びアルミニウム粉体よりなる原料粉体を成形したものを、１１７３Ｋの温度で４８時間にわたって焼結させたのち、氷水でクエンチした。このようにして、反応焼結法により、Ｌ２１構造を有するＣｕ５０Ｍｎ２５Ａｌ２５相の多結晶体であるホイスラー合金よりなるＣｕ－Ｍｎ－Ａｌ系中間体を準備した。
[Example 1]
First, raw material powders consisting of copper powder, manganese powder, and aluminum powder, all of which have a purity of 99.9% by mass and a particle size of less than 75 μm, are molded and sintered at a temperature of 1173K for 48 hours. After that, it was quenched with ice water. In this manner, a Cu--Mn--Al intermediate made of a Heusler alloy, which is a polycrystalline Cu 50 Mn 25 Al 25 phase having an L2 1 structure, was prepared by the reaction sintering method.
次に、そのＣｕ－Ｍｎ－Ａｌ系中間体に対して、５７３Ｋの温度で磁場中熱処理を施すことにより、Ｃｕ－Ｍｎ－Ａｌ系磁石を得た。 Next, the Cu--Mn--Al-based intermediate was heat-treated in a magnetic field at a temperature of 573 K to obtain a Cu--Mn--Al based magnet.
磁場中熱処理がもたらす効果の、磁場の強さに対する依存性を確認するために、磁場中熱処理の継続時間を４８時間に固定したうえで、Ｃｕ－Ｍｎ－Ａｌ系中間体に与える磁場が、０Ｔである場合、５Ｔである場合、及び１０Ｔである場合のそれぞれについてＣｕ－Ｍｎ－Ａｌ系磁石を得た。そして、得られた３種のＣｕ－Ｍｎ－Ａｌ系磁石に含まれる晶相を、Ｘ線回折装置を用いて同定した。 In order to confirm the dependence of the effect of heat treatment in a magnetic field on the strength of the magnetic field, the duration of heat treatment in a magnetic field was fixed at 48 hours, and the magnetic field applied to the Cu-Mn-Al intermediate was set to 0T. Cu--Mn--Al based magnets were obtained for the following cases: 5 T, and 10 T. Then, the crystal phases contained in the three types of Cu--Mn--Al magnets obtained were identified using an X-ray diffraction device.
図２に、それら３種のＣｕ－Ｍｎ－Ａｌ系磁石のＸ線回折パターンを示す。横軸は、角度２θを単位“度”で示す。縦軸は、回折ビームの強度を相対目盛で示す。なお、図２には、回折ピークによって同定される晶相を付記している。“Ｌ２１”と付記された回折ピークは、強磁性のＣｕ５０Ｍｎ２５Ａｌ２５相の存在を示している。“Ｃｕ９Ａｌ４”と付記された回折ピークは、非磁性のＣｕ９Ａｌ４相の存在を示している。 FIG. 2 shows the X-ray diffraction patterns of these three types of Cu--Mn--Al based magnets. The horizontal axis indicates the angle 2θ in degrees. The vertical axis indicates the intensity of the diffracted beam on a relative scale. Note that in FIG. 2, crystal phases identified by diffraction peaks are added. The diffraction peak labeled “L2 1 ” indicates the presence of a ferromagnetic Cu 50 Mn 25 Al 25 phase. The diffraction peak labeled “Cu 9 Al 4 ” indicates the presence of a nonmagnetic Cu 9 Al 4 phase.
図２に示すように、０Ｔの熱処理を行った場合は、Ｌ２１構造に由来する回折ピークだけが観測された。一方、５Ｔの磁場中熱処理を行った場合、Ｃｕ９Ａｌ４相に由来する回折ピークも観測された。さらに、１０Ｔの磁場中熱処理を行った場合は、Ｃｕ９Ａｌ４相に由来する回折ピークの高さが、５Ｔの磁場中熱処理を行った場合よりも高まった。 As shown in FIG. 2, when 0T heat treatment was performed, only the diffraction peak derived from the L2 1 structure was observed. On the other hand, when heat treatment was performed in a 5T magnetic field, a diffraction peak derived from the Cu 9 Al 4 phase was also observed. Furthermore, when heat treatment was performed in a 10T magnetic field, the height of the diffraction peak derived from the Cu 9 Al 4 phase was higher than when heat treatment was performed in a 5T magnetic field.
この結果より、磁場中熱処理が、Ｃｕ－Ｍｎ－Ａｌ系中間体に対しては、非磁性相であるＣｕ９Ａｌ４相の合成を促進する効果をもたらし、かつその効果は、Ｃｕ－Ｍｎ－Ａｌ系中間体に与える磁場が大きいほど高まることが分かった。 These results show that heat treatment in a magnetic field has the effect of promoting the synthesis of the non-magnetic phase Cu 9 Al 4 phase for Cu-Mn-Al intermediates, and that this effect is greater than that of Cu-Mn- It was found that the larger the magnetic field applied to the Al-based intermediate, the higher the effect.
また、５Ｔの磁場中熱処理を行った場合、Ｌ２１構造に由来する回折ピークの高さが、０Ｔの熱処理を行った場合よりも低下した。１０Ｔの磁場中熱処理を行った場合は、Ｌ２１構造に由来する回折ピークの高さがさらに低下した。 Furthermore, when heat treatment was performed in a magnetic field at 5T, the height of the diffraction peak derived from the L2 1 structure was lower than when heat treatment was performed at 0T. When heat treatment was performed in a magnetic field of 10 T, the height of the diffraction peak derived from the L2 1 structure was further reduced.
この結果より、磁場中熱処理が、Ｃｕ－Ｍｎ－Ａｌ系中間体に対しては、強磁性相であるＣｕ５０Ｍｎ２５Ａｌ２５相の、非磁性相であるＣｕ９Ａｌ４相への分解を伴う微細化を促進する効果をもたらし、かつその効果は、Ｃｕ－Ｍｎ－Ａｌ系中間体に与える磁場が大きいほど高まることが分かった。 From this result, heat treatment in a magnetic field can suppress the decomposition of the ferromagnetic phase, Cu 50 Mn 25 Al 25 phase, into the non-magnetic phase, Cu 9 Al 4 phase, for Cu-Mn-Al intermediates. It has been found that the larger the magnetic field applied to the Cu--Mn--Al-based intermediate, the greater the effect of promoting the accompanying refinement.
また、回折ピークの半値幅は、その回折ピークによって同定される結晶子のサイズ（以下、結晶子サイズと記す。）に依存する。具体的には、結晶子が小さいほど半値幅が広い。なお、“結晶子”とは、多結晶体において単結晶とみなせる最大の集まりを意味する。 Further, the half-value width of a diffraction peak depends on the size of a crystallite identified by the diffraction peak (hereinafter referred to as crystallite size). Specifically, the smaller the crystallite, the wider the half width. Note that "crystallite" means the largest collection of polycrystals that can be considered a single crystal.
そこで、Ｃｕ－Ｍｎ－Ａｌ系磁石におけるＣｕ５０Ｍｎ２５Ａｌ２５相の結晶子サイズの、磁場中熱処理の継続時間に対する依存性を確認するために、Ｃｕ－Ｍｎ－Ａｌ系中間体に与える磁場が、０Ｔである場合、及び５Ｔである場合のそれぞれについて、磁場中熱処理の継続時間を種々変更した。 Therefore, in order to confirm the dependence of the crystallite size of the Cu 50 Mn 25 Al 25 phase in the Cu-Mn-Al based magnet on the duration of the heat treatment in the magnetic field, we investigated whether the magnetic field applied to the Cu-Mn-Al based intermediate was , 0T, and 5T, the duration of the heat treatment in the magnetic field was varied.
図３に、Ｃｕ５０Ｍｎ２５Ａｌ２５相の結晶子サイズの時間変化を示す。横軸は、磁場中熱処理の継続時間を示す。縦軸は、Ｃｕ－Ｍｎ－Ａｌ系磁石に含まれるＣｕ５０Ｍｎ２５Ａｌ２５相の平均的な結晶子サイズを示す。結晶子サイズは、Ｘ線回折パターンの回折ピークの半値幅を用い、Ｈａｌｄｅｒ－Ｗａｇｎｅｒの関係式によって推定した。 FIG. 3 shows the change in crystallite size of the Cu 50 Mn 25 Al 25 phase over time. The horizontal axis indicates the duration of heat treatment in a magnetic field. The vertical axis indicates the average crystallite size of the Cu 50 Mn 25 Al 25 phase contained in the Cu--Mn--Al based magnet. The crystallite size was estimated by the Halder-Wagner relation using the half-width of the diffraction peak in the X-ray diffraction pattern.
図３に示すように、Ｃｕ－Ｍｎ－Ａｌ系中間体に与える磁場が０Ｔである場合、及び５Ｔである場合のいずれにおいても、６時間までは、Ｃｕ５０Ｍｎ２５Ａｌ２５相の結晶子が粗大化した。一方、その後は、いずれの場合においても、Ｃｕ５０Ｍｎ２５Ａｌ２５相の結晶子が微細化する傾向がみられる。 As shown in Figure 3, in both cases where the magnetic field applied to the Cu-Mn-Al intermediate is 0T and 5T, the crystallites of the Cu 50 Mn 25 Al 25 phase are It has become coarser. On the other hand, thereafter, in any case, the crystallites of the Cu 50 Mn 25 Al 25 phase tend to become finer.
但し、５Ｔの磁場中熱処理を行った場合の方が、０Ｔの熱処理を行った場合よりも、Ｃｕ５０Ｍｎ２５Ａｌ２５相の結晶子が速やかに微細化されている。 However, the crystallites of the Cu 50 Mn 25 Al 25 phase are more quickly refined when heat treatment is performed in a magnetic field at 5 T than when heat treatment is performed at 0 T.
この結果より、Ｃｕ－Ｍｎ－Ａｌ系中間体に対しては、磁場中熱処理が、強磁性相であるＣｕ５０Ｍｎ２５Ａｌ２５相の結晶子の微細化を促進する効果をもたらすことが判明した。 These results revealed that for Cu-Mn-Al intermediates, heat treatment in a magnetic field has the effect of promoting refinement of the crystallites of the ferromagnetic phase, Cu 50 Mn 25 Al 25 phase. .
次に、磁場中熱処理で得られたＣｕ－Ｍｎ－Ａｌ系磁石の磁気履歴曲線を、振動試料型磁力計によって測定した。また、比較のために、０Ｔの熱処理で得られたＣｕ－Ｍｎ－Ａｌ系磁石の磁気履歴曲線も測定した。 Next, the magnetic hysteresis curve of the Cu--Mn--Al magnet obtained by heat treatment in a magnetic field was measured using a vibrating sample magnetometer. For comparison, the magnetic hysteresis curve of a Cu--Mn--Al magnet obtained by heat treatment at 0 T was also measured.
図４に、それぞれのＣｕ－Ｍｎ－Ａｌ系磁石の磁気履歴曲線を示す。横軸は、Ｃｕ－Ｍｎ－Ａｌ系磁石に与えた外部磁場の強さを表す。縦軸は、Ｃｕ－Ｍｎ－Ａｌ系磁石の単位質量あたりの磁化を表す。 FIG. 4 shows the magnetic history curves of each Cu--Mn--Al based magnet. The horizontal axis represents the strength of the external magnetic field applied to the Cu--Mn--Al based magnet. The vertical axis represents magnetization per unit mass of the Cu--Mn--Al based magnet.
図４に示すように、０Ｔの熱処理を行った場合の飽和磁化は７７ｅｍｕ／ｇであるのに対し、１０Ｔの磁場中熱処理を行った場合の飽和磁化は、それよりも著しく小さい１２ｅｍｕ／ｇであった。また、０Ｔの熱処理を行った場合の保磁力は略ゼロであったのに対し、１０Ｔの磁場中熱処理を行った場合の保磁力は、２．３ｋＯｅ以上であった。 As shown in Figure 4, the saturation magnetization when heat-treated at 0T is 77 emu/g, whereas the saturation magnetization when heat-treated in a 10T magnetic field is significantly smaller, 12 emu/g. there were. Further, the coercive force when heat treatment was performed at 0 T was approximately zero, whereas the coercive force when heat treatment was performed in a magnetic field at 10 T was 2.3 kOe or more.
この結果より、磁場中熱処理は、Ｃｕ－Ｍｎ－Ａｌ系中間体に対しては、磁化を抑える一方、保磁力を高める効果をもたらすことが分かった。 From this result, it was found that heat treatment in a magnetic field has the effect of suppressing magnetization and increasing coercive force for the Cu--Mn--Al intermediate.
磁化が抑えられる理由は、図２を参照して述べたように、磁場中熱処理によって、強磁性相の合成が抑えられ、かつ非磁性相の合成が促進されたためである。 The reason why the magnetization is suppressed is that, as described with reference to FIG. 2, the heat treatment in the magnetic field suppresses the synthesis of the ferromagnetic phase and promotes the synthesis of the nonmagnetic phase.
また、保磁力が高められる理由は、強磁性相の結晶子が微細化され、かつ非磁性相が合成されたことにより、微細な強磁性相の結晶子が非磁性相によって分断されて組織中に散在した状態になるためと推定される。 In addition, the reason why the coercive force is increased is that the crystallites of the ferromagnetic phase are made finer and the non-magnetic phase is synthesized. It is presumed that this is because they are scattered throughout the area.
［実施例２］
Ｃｕ－Ｍｎ－Ａｌ系中間体におけるＣｕ、Ｍｎ、Ａｌのモル比が実施例１の場合と異なる場合にも、磁場中熱処理によって保磁力が高められるか否かを確認するために、反応焼結法によって、Ｃｕ４５Ｍｎ２０Ａｌ３５相の多結晶体であるＣｕ－Ｍｎ－Ａｌ系中間体を得た。反応焼結の条件は実施例１と同じである。
[Example 2]
In order to confirm whether the coercive force can be increased by heat treatment in a magnetic field even when the molar ratio of Cu, Mn, and Al in the Cu-Mn-Al intermediate is different from that in Example 1, reaction sintering was conducted. By this method, a polycrystalline Cu--Mn--Al intermediate having a Cu 45 Mn 20 Al 35 phase was obtained. The reaction sintering conditions are the same as in Example 1.
そして、そのＣｕ－Ｍｎ－Ａｌ系中間体に磁場中熱処理を施すことで得たＣｕ－Ｍｎ－Ａｌ系磁石の保磁力を調べた。また、比較のために、０Ｔの熱処理で得たＣｕ－Ｍｎ－Ａｌ系磁石の保磁力も調べた。 Then, the coercive force of a Cu-Mn-Al-based magnet obtained by subjecting the Cu-Mn-Al-based intermediate to heat treatment in a magnetic field was investigated. For comparison, the coercive force of a Cu--Mn--Al magnet obtained by heat treatment at 0 T was also investigated.
図５に、それぞれのＣｕ－Ｍｎ－Ａｌ系磁石の保磁力の時間変化を示す。横軸は、磁場中熱処理又は熱処理の継続時間を示す。縦軸は、保磁力を示す。図５に示すように、磁場中熱処理は、Ｃｕ４５Ｍｎ２０Ａｌ３５相の多結晶体に対しても保磁力の上昇を促進する効果を示すことが確認された。 FIG. 5 shows the change in coercive force of each Cu--Mn--Al based magnet over time. The horizontal axis indicates the duration of heat treatment in a magnetic field or heat treatment. The vertical axis indicates coercive force. As shown in FIG. 5, it was confirmed that the heat treatment in a magnetic field has the effect of promoting an increase in coercive force also for the polycrystalline body of the Cu 45 Mn 20 Al 35 phase.
Claims (3)
前記Ｃｕ－Ｍｎ－Ａｌ系中間体に対し、前記Ｃｕ－Ｍｎ－Ａｌ系中間体に磁場を与えつつ前記Ｃｕ－Ｍｎ－Ａｌ系中間体を加熱する磁場中熱処理を施す磁場中熱処理工程と、
を有し、
前記磁場中熱処理工程では、前記Ｃｕ－Ｍｎ－Ａｌ系中間体に対し、前記Ｃｕ－Ｍｎ－Ａｌ系中間体に５Ｔ以上の前記磁場を与えつつ前記Ｃｕ－Ｍｎ－Ａｌ系中間体を５００Ｋ以上に加熱する前記磁場中熱処理を、６時間超にわたって施す、
Ｃｕ－Ｍｎ－Ａｌ系磁石の製造方法。 a preparation step of preparing a Cu-Mn-Al intermediate containing Cu, Mn, and Al;
A heat treatment step in a magnetic field of applying a magnetic field to the Cu-Mn-Al-based intermediate while heating the Cu-Mn-Al-based intermediate;
has
In the magnetic field heat treatment step, the Cu-Mn-Al-based intermediate is heated to a temperature of 500 K or more while applying the magnetic field of 5 T or more to the Cu-Mn-Al-based intermediate. The heat treatment in a magnetic field is performed for more than 6 hours.
A method for manufacturing a Cu-Mn-Al magnet.
請求項１に記載のＣｕ－Ｍｎ－Ａｌ系磁石の製造方法。 In the preparation step, the Cu-Mn-Al intermediate containing an alloy of Cu, Mn, and Al is prepared by sintering raw material powder containing Cu, Mn, and Al.
A method for manufacturing a Cu-Mn-Al magnet according to claim 1.
請求項２に記載のＣｕ－Ｍｎ－Ａｌ系磁石の製造方法。 the alloy is a Heusler alloy having an L2 1 structure;
The method for manufacturing a Cu-Mn-Al magnet according to claim 2.
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