JP4076017B2 - Method for producing rare earth magnet powder with excellent magnetic anisotropy - Google Patents
Method for producing rare earth magnet powder with excellent magnetic anisotropy Download PDFInfo
- Publication number
- JP4076017B2 JP4076017B2 JP2003013312A JP2003013312A JP4076017B2 JP 4076017 B2 JP4076017 B2 JP 4076017B2 JP 2003013312 A JP2003013312 A JP 2003013312A JP 2003013312 A JP2003013312 A JP 2003013312A JP 4076017 B2 JP4076017 B2 JP 4076017B2
- Authority
- JP
- Japan
- Prior art keywords
- rare earth
- earth magnet
- hydrogen
- raw material
- alloy raw
- 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.)
- Expired - Fee Related
Links
- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 77
- 150000002910 rare earth metals Chemical class 0.000 title claims description 73
- 239000000843 powder Substances 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 118
- 229910052739 hydrogen Inorganic materials 0.000 claims description 109
- 239000001257 hydrogen Substances 0.000 claims description 109
- 238000010521 absorption reaction Methods 0.000 claims description 52
- 238000010438 heat treatment Methods 0.000 claims description 43
- 239000000956 alloy Substances 0.000 claims description 39
- 229910045601 alloy Inorganic materials 0.000 claims description 39
- 239000002994 raw material Substances 0.000 claims description 39
- 238000000354 decomposition reaction Methods 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 15
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 9
- 230000009466 transformation Effects 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims 1
- 239000011261 inert gas Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 238000007796 conventional method Methods 0.000 description 10
- 230000004907 flux Effects 0.000 description 9
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 230000005415 magnetization Effects 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Hard Magnetic Materials (AREA)
Description
【０００１】
【発明の属する技術分野】
この発明は、磁気異方性に優れた希土類磁石粉末、特に残留磁束密度の一層優れた希土類磁石粉末の製造方法に関するものである。
【０００２】
【従来の技術】
Ｒ（但し、ＲはＹを含む希土類元素を示す。以下同じ）、Ｍ（但し、ＭはＧａ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆ、Ｔａ、Ｗ、Ｎｉ、Ａｌ、Ｔｉ、Ｖ、Ｃｕ、Ｃｒ、Ｇｅ、ＣおよびＳｉの内の１種または２種以上を示す。以下同じ）とすると、原子％で（以下、％は原子％を示す）、Ｒ：１０〜２０％、Ｃｏ：０〜５０％、Ｂ：３〜２０％、Ｍ：０〜５％を含有し、残部がＦｅおよび不可避不純物からなる成分組成を有する希土類磁石合金原料をＡｒガス雰囲気中、温度：６００〜１２００℃に保持して均質化処理し、または均質化処理せずに、水素雰囲気中で室温から温度：５００℃未満までの所定の温度に昇温、または昇温し保持して水素吸収処理したのち、
水素圧力：１０〜１０００ｋＰａの水素雰囲気中で５００〜１０００℃の範囲内の所定の温度に昇温し保持することにより前記希土類磁石合金原料に水素を吸収させて相変態による分解を促す水素吸収・分解処理を施し、
引き続いて、水素吸収・分解処理を施した希土類磁石合金原料を不活性ガス圧：１０〜１０００ｋＰａ、温度：５００〜１０００℃の範囲内の所定の温度で不活性ガス雰囲気中に保持することにより中間熱処理を行い、
さらに引き続いて、必要に応じて、中間熱処理を施した希土類磁石合金原料を５００〜１０００℃の範囲内の所定の温度で、絶対圧：０．６５〜１０ｋＰａ未満の水素雰囲気中または水素分圧：：０．６５〜１０ｋＰａ未満の水素と不活性ガスとの混合ガス雰囲気中に保持することにより希土類磁石合金原料に水素を一部残したまま減圧水素中熱処理を行い、
その後、５００〜１０００℃の範囲内の所定の温度で到達圧：０．１３ｋＰａ以下の真空雰囲気に保持することにより強制的に水素を放出させて相変態を促す脱水素処理を施し、ついで冷却し、粉砕する工程からなる磁気異方性に優れた希土類磁石粉末の製造方法は知られている（特開２０００−２１６１４号公報参照）。
【０００３】
【発明が解決しようとする課題】
近年、電気・電子業界では磁気異方性が一層優れるとともに一層安価な希土類磁石粉末が求められており、一層磁気異方性が優れるとともに一層安価な希土類磁石粉末を効率良く低コストで製造できる方法の研究開発がなされている。
【０００４】
【課題を解決するための手段】
そこで、本発明者らも、一層磁気異方性に優れた希土類磁石粉末を効率良く低コストで製造できる方法を開発すべく研究を行った。その結果、
（ａ）前記従来の磁気異方性に優れた希土類磁石粉末の製造方法における水素吸収・分解処理後に不活性ガスを供給して不活性ガス圧：１０〜１０００ｋＰａ、温度：５００〜１０００℃の範囲内の所定の温度で不活性ガス雰囲気中に保持する中間熱処理に代えて、５００〜１０００℃の範囲内の温度を保持しつつ、水素圧力を水素吸収・分解処理時の水素圧力の２０〜６０％の圧力の水素雰囲気中に保持する中間減圧熱処理を施すと、従来の水素吸収・分解処理後に不活性ガス雰囲気の中間熱処理を施すよりも残留磁束密度が向上する、
（ｂ）この中間減圧熱処理は、水素吸収・分解処理と同じ水素雰囲気であり、水素を排気して圧力を減らすだけであるから、不活性ガスを導入する従来の中間熱処理に比べて操作が簡単であり、量産に適した方法であるとともに、従来の製造方法で製造した希土類磁石粉末に比べて磁気異方性、特に残留磁束密度が一層向上する、という研究結果が得られたのである。
【０００５】
この発明は、かかる研究結果に基づいて成されたものであって、
（１）必要に応じて真空またはＡｒガス雰囲気中、温度：６００〜１２００℃に保持の条件で均質化処理した希土類磁石合金原料を圧力：１０〜１０００ｋＰａの水素ガス雰囲気中で室温から温度：５００℃未満までの温度に昇温、または昇温し保持することにより水素を吸収させる水素吸収処理を施し、
この水素吸収処理した前記希土類磁石合金原料を圧力：１０〜１０００ｋＰａの水素ガス雰囲気中で５００〜１０００℃の範囲内の温度に昇温し保持することにより前記希土類磁石合金原料にさらに水素を吸収させて分解する水素吸収・分解処理を施し、
引き続いて、水素吸収・分解処理を施した希土類磁石合金原料を５００〜１０００℃の範囲内の温度で水素吸収・分解処理時の圧力の２０〜６０％の圧力の水素雰囲気中に保持する中間減圧熱処理を施し、
引き続いて、５００〜１０００℃の範囲内の温度で圧力：０．６５〜１３ｋＰａでかつ中間減圧熱処理の圧力よりも低い圧力の水素雰囲気中に保持することにより希土類磁石合金原料に水素を一部残したまま減圧水素中熱処理を行い、
その後、５００〜１０００℃の範囲内の温度で到達圧：０．１３ｋＰａ以下の真空雰囲気に保持することにより希土類磁石合金原料から強制的に水素を放出させて相変態を促す脱水素処理を施し、ついで冷却し、粉砕する磁気異方性に優れた希土類磁石粉末の製造方法、に特徴を有するものである。
【０００６】
この発明で使用する希土類磁石合金原料は、
Ｒ：１０〜２０％、Ｂ：３〜２０％を含有し、残部がＦｅおよび不可避不純物からなる成分組成を有する希土類磁石合金原料、
Ｒ：１０〜２０％、Ｂ：３〜２０％、Ｍ：０．００１〜５％を含有し、残部がＦｅおよび不可避不純物からなる成分組成を有する希土類磁石合金原料、
Ｒ：１０〜２０％、Ｃｏ：０．１〜５０％、Ｂ：３〜２０％を含有し、残部がＦｅおよび不可避不純物からなる成分組成を有する希土類磁石合金原料、または、
Ｒ：１０〜２０％、Ｃｏ：０．１〜５０％、Ｂ：３〜２０％、Ｍ：０．００１〜５％を含有し、残部がＦｅおよび不可避不純物からなる成分組成を有する希土類磁石合金原料が好ましい。
【０００７】
次に、この発明で使用する希土類磁石合金原料の成分組成および製造条件を前述の如く限定した理由を説明する。
（Ａ）成分組成
Ｒ（Ｙを含む希土類元素）：
Ｒは、Ｎｄを主体とし、その他、Ｙ、Ｄｙ、Ｐｒ、Ｓｍ、Ｃｅ、Ｌａ、Ｔｂ、Ｅｒ、Ｅｕ、Ｇｄ、Ｔｍ、Ｙｂ、Ｌｕ、Ｈｏなどを微量含む希土類元素であるが、その含有量が１０％未満では保磁力が低下し、一方、２０％を越えて含有すると飽和磁化が低下していずれも希望の磁気特性が得られないので好ましくない。したがって、Ｒの含有量は１０〜２０％に定めた。
【０００８】
Ｂ：
Ｂの含有量は３％未満では保磁力が低下し、一方、２０％を越えて含有すると飽和磁化が低下していずれも希望の磁気特性が得られないので好ましくない。したがって、Ｂの含有量は３〜２０％に定めた。
【０００９】
Ｃｏ：
Ｃｏは希土類磁石合金の等方性化を阻止するために必要に応じて添加するが、その含有量が０．１％未満では所望の効果が得られず、一方、５０％を越えて含有すると、保磁力および飽和磁化が下がるので異方化しても高特性が得られない。したがって、この発明の希土類磁石粉末の製造方法で使用する希土類磁石合金原料に含まれるＣｏの含有量は０．１〜５０％（一層好ましくは、５〜３０％）に定めた。
【００１０】
Ｍ（Ｇａ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆ、Ｔａ、Ｗ、Ｎｉ、Ａｌ、Ｔｉ、Ｖ、Ｃｕ、Ｃｒ、Ｇｅ、ＣおよびＳｉの内の１種または２種以上）：
Ｍは、保磁力および残留磁束密度の一層の向上のために必要に応じて添加するが、その含有量が０．００１％未満では所望の効果が得られず、一方、５％を越えて添加すると、保磁力および残留磁束密度が低下するので好ましくない。したがってＭの含有量は０．００１〜５％に定めた。
【００１１】
（Ｂ）製造条件
希土類磁石合金原料は圧力：１０〜１０００ｋＰａの水素ガス雰囲気中で室温から温度：５００℃未満までの所定の温度に昇温、または昇温し５００℃未満までの所定の温度（例えば、１００℃）に保持することにより水素を吸収せしめる水素吸収処理を施す。この希土類磁石合金原料を圧力：１０〜１０００ｋＰａの水素ガス雰囲気中で室温から温度：５００℃未満までの所定の温度に昇温、または昇温する水素吸収処理は、従来から行われている処理である。
【００１２】
この水素吸収処理した希土類磁石合金原料をさらに加熱し、圧力：１０〜１０００ｋＰａの水素ガス雰囲気中で温度：５００〜１０００℃の範囲内の所定の温度に保持する水素吸収・分解処理を施すことにより原料に水素を吸収させて相変態を促し分解させる。この水素吸収・分解処理工程における圧力：１０〜１０００ｋＰａの水素ガス雰囲気中で温度：５００〜１０００℃の範囲内の所定の温度に保持する条件はすでに知られている条件であり、特に新規な条件ではないのでその限定理由の説明は省略する。
【００１３】
かかる水素吸収・分解処理したのち、５００〜１０００℃の範囲内の温度で、水素吸収・分解処理時の水素圧力の２０〜６０％の圧力（具体的には、圧力：２〜６００ｋＰａでかつ水素吸収・分解処理時の水素圧力より相対的に低い圧力）の水素雰囲気中に保持する中間減圧熱処理を施す。この中間減圧熱処理は従来の不活性ガス雰囲気で行なう中間熱処理に代わる処理工程であり、水素吸収・分解処理したのち温度を５００〜１０００℃に保持したまま水素ガスを排気して減圧することにより所定の水素圧力に保持することができるから、不活性ガス雰囲気に交換する必要がなく、簡単な操作で中間減圧熱処理を施すことができ、しかも残留磁束密度を一層高める効果がある。
この中間減圧熱処理における水素圧力を水素吸収・分解処理時の水素圧力の２０〜６０％の圧力にした理由は、水素吸収・分解処理時の水素圧力の２０％未満の圧力に保持すると異方性化の反応速度が速すぎるために保持力が低下してしまうので好ましくなく、一方、水素吸収・分解処理時の水素圧力の６０％より高い水素圧力に保持すると、異方性化の反応がほとんど進まないので好ましくない。したがって、中間減圧熱処理における水素圧力を水素吸収・分解処理時の水素圧力の２０〜６０％の圧力に定めた。
【００１４】
この中間減圧熱処理を施した後、さらに減圧水素中熱処理を施す。この減圧水素中熱処理は、水素吸収・分解処理した希土類磁石合金原料を水素圧力：０．６５〜１３ｋＰａであって中間減圧熱処理の水素圧力よりも低い圧力の水素雰囲気中に保持する処理である。この減圧水素中熱処理を施すことにより保磁力および残留磁束密度を一層向上させることができる。
【００１５】
この中間減圧熱処理を施しさらに減圧水素中熱処理を施したのち脱水素処理を行う。脱水素処理は到達圧：０．１３ｋＰａ以下の真空雰囲気に保持することにより希土類磁石合金原料から強制的に水素を十分放出させ、それにより一層の相変態を促す処理である。０．１３ｋＰａを越える到達圧では十分に脱水素が行われないからである。
この脱水素処理後に行なう冷却は不活性ガス（Ａｒガス）を流すことにより室温まで冷却する。冷却した後は粉砕して希土類磁石粉末とする。この粉砕して得られた希土類磁石粉末は必要に応じて熱処理することにより残留内部応力を除去する。
【００１６】
【発明の実施の形態】
高周波真空溶解炉を用いて溶解し、得られた溶湯を鋳造して表１に示される成分組成の希土類磁石合金原料の鋳塊ａ〜ｈを製造した。これら鋳塊ａ〜ｈを不活性ガス雰囲気中で粉砕して１０ｍｍ以下のブロックを作製した。
【００１７】
【表１】
実施例１
表１の鋳塊ａ〜ｅのブロックに表２に示される条件の水素吸収処理を施した後、この水素吸収処理したブロックを表２に示される条件で水素吸収・分解処理を施し、引き続いて表２に示される条件で中間減圧熱処理を行い、さらに表３に示される条件で減圧水素中熱処理を行い、さらに表３に示される条件で脱水素処理を行った後、Ａｒガスで強制的に室温まで冷却し、３００μｍ以下に粉砕して希土類磁石粉末を製造することにより本発明法１〜５を実施した。
【００１９】
従来例１
表１の鋳塊ａ〜ｅのブロックを表２に示される実施例１と同じ条件の水素吸収処理を施した後、実施例１と同じ条件で水素吸収・分解処理を施し、引き続いて表２に示される条件でＡｒガス雰囲気の中間熱処理を行い、さらに表３に示される条件で減圧水素中熱処理を行い、さらに表３に示される条件で脱水素処理を行った後、Ａｒガスで強制的に室温まで冷却し、３００μｍ以下に粉砕して希土類磁石粉末を製造することにより従来法１〜５を実施した。
【００２０】
本発明法１〜５および従来法１〜５により得られた希土類磁石粉末にそれぞれ３質量％のエポキシ樹脂を加えて混練し、１．６ＭＡ／ｍの磁場中で圧縮成形して圧粉体を作製し、この圧粉体をオーブンで１５０℃、２時間熱硬化して、密度：６．０〜６．１ｇ／ｃｍ3のボンド磁石を作製し、得られたボンド磁石の磁気特性を表３に示した。
【００２１】
さらに、本発明法１〜５および従来法１〜５により得られた希土類磁石粉末を磁場中で圧縮成形して異方性圧粉体を作製し、この異方性圧粉体をホットプレス装置にセットし、磁場の印加方向が圧縮方向になるようにＡｒガス中、温度：７５０℃、圧力：５８．８ＭＰａ 、１分間保持の条件でホットプレスを行い、急冷して密度：７．５〜７．７ｇ／ｃｍ3 のホットプレス磁石を作製し、得られたホットプレス磁石の磁気特性を表３に示した。
【００２２】
【表２】
【表３】
表１、表２および表３に示される結果から、水素吸収処理を施し、水素吸収・分解処理を施したのち中間減圧熱処理する本発明法１〜５により得られた希土類磁石粉末で作製したボンド磁石およびホットプレス磁石の磁気特性は、水素吸収処理を施し、水素吸収・分解処理を施したのちＡｒガス雰囲気中で中間熱処理する従来法１〜５により得られた希土類磁石粉末で作製したボンド磁石およびホットプレス磁石の磁気特性に比べて、特に残留磁束密度が向上していることが分かる。
【００２５】
実施例２
表１の鋳塊ｆ〜ｈのブロックに表４に示される条件の水素吸収処理を施した後、この水素吸収処理したブロックを表４に示される条件で水素吸収・分解処理を施し、引き続いて表４に示される条件で中間減圧熱処理を行い、さらに表５に示される条件で減圧水素中熱処理を行い、さらに表５に示される条件で脱水素処理を行った後、Ａｒガスで強制的に室温まで冷却し、３００μｍ以下に粉砕して希土類磁石粉末を製造することにより本発明法６〜８を実施した。
【００２６】
従来例２
表１の鋳塊ｆ〜ｈのブロックを表４に示される実施例２と同じ条件の水素吸収処理を施した後、実施例２と同じ条件で水素吸収・分解処理を施し、引き続いて表４に示される条件でＡｒガス雰囲気の中間熱処理を行い、さらに表５に示される条件で減圧水素中熱処理を行い、さらに表５に示される条件で脱水素処理を行った後、Ａｒガスで強制的に室温まで冷却し、３００μｍ以下に粉砕して希土類磁石粉末を製造することにより従来法６〜８を実施した。
【００２７】
本発明法６〜８および従来法６〜８により得られた希土類磁石粉末にそれぞれ３質量％のエポキシ樹脂を加えて混練し、１．６ＭＡ／ｍの磁場中で圧縮成形して圧粉体を作製し、この圧粉体をオーブンで１５０℃、２時間熱硬化して、密度：６．０〜６．１ｇ／ｃｍ3のボンド磁石を作製し、得られたボンド磁石の磁気特性を表５に示した。
【００２８】
さらに、本発明法６〜８および従来法６〜８により得られた希土類磁石粉末を磁場中で圧縮成形して異方性圧粉体を作製し、この異方性圧粉体をホットプレス装置にセットし、磁場の印加方向が圧縮方向になるようにＡｒガス中、温度：７５０℃、圧力：５８．８ＭＰａ 、１分間保持の条件でホットプレスを行い、急冷して密度：７．５〜７．７ｇ／ｃｍ3 のホットプレス磁石を作製し、得られたホットプレス磁石の磁気特性を表５に示した。
【００２９】
【表４】
【表５】
表１、表４および表５に示される結果から、水素吸収処理を施し、水素吸収・分解処理を施したのち中間減圧熱処理する本発明法６〜８により得られた希土類磁石粉末で作製したボンド磁石およびホットプレス磁石の磁気特性は、水素吸収処理を施し、水素吸収・分解処理を施したのちＡｒガス雰囲気中で中間熱処理する従来法６〜８により得られた希土類磁石粉末で作製したボンド磁石およびホットプレス磁石の磁気特性に比べて、特に残留磁束密度が向上していることが分かる。
【００３２】
【発明の効果】
（ｉ）希土類磁石合金原料を水素吸収処理→水素吸収・分解処理→中間減圧熱処理→減圧水素中熱処理→脱水素処理の順序で施すこの発明の希土類磁石粉末の製造方法により作製した希土類磁石粉末は、水素吸収処理→水素吸収・分解処理→中間熱処理→減圧水素中熱処理→脱水素処理の順序で施す従来の希土類磁石粉末の製造方法により作製した希土類磁石粉末に比べて磁気異方性に優れている、
(ii)この発明の希土類磁石粉末の製造方法は、不活性ガスの導入は最後の冷却工程だけであって、その他の工程では水素ガスの導入および排出の圧力条件だけで制御することができるので製造コストを大幅に削減することができ、一層優れた希土類磁石粉末を安価に提供することができる、
など産業上優れた効果を奏するものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a rare earth magnet powder having excellent magnetic anisotropy, particularly a rare earth magnet powder having further excellent residual magnetic flux density.
[0002]
[Prior art]
R (where R represents a rare earth element including Y. The same applies hereinafter), M (where M is Ga, Zr, Nb, Mo, Hf, Ta, W, Ni, Al, Ti, V, Cu, Cr, Assuming one or more of Ge, C and Si (hereinafter the same), in atomic% (hereinafter,% indicates atomic%), R: 10-20%, Co: 0-50% , B: 3 to 20%, M: 0 to 5%, and the rare earth magnet alloy raw material having a composition composed of Fe and inevitable impurities in the balance is maintained at a temperature of 600 to 1200 ° C. in an Ar gas atmosphere. After homogenization or without homogenization, the temperature is increased from room temperature to a predetermined temperature of less than 500 ° C. in a hydrogen atmosphere, or the temperature is increased and held, and then hydrogen absorption treatment is performed.
Hydrogen pressure: Hydrogen absorption that promotes decomposition by phase transformation by allowing the rare earth magnet alloy raw material to absorb hydrogen by raising the temperature to a predetermined temperature within a range of 500 to 1000 ° C. and holding it in a hydrogen atmosphere of 10 to 1000 kPa. Disassembling,
Subsequently, the rare earth magnet alloy raw material subjected to the hydrogen absorption / decomposition treatment is kept in an inert gas atmosphere at a predetermined temperature within a range of inert gas pressure: 10 to 1000 kPa and temperature: 500 to 1000 ° C. Heat treatment,
Further subsequently, if necessary, the rare earth magnet alloy raw material subjected to the intermediate heat treatment at a predetermined temperature within a range of 500 to 1000 ° C. in a hydrogen atmosphere having an absolute pressure of less than 0.65 to 10 kPa or a hydrogen partial pressure: : Holding in a mixed gas atmosphere of hydrogen and inert gas of less than 0.65 to 10 kPa, heat treatment in reduced-pressure hydrogen is performed while leaving some hydrogen in the rare earth magnet alloy raw material,
Thereafter, a dehydrogenation treatment is performed to forcibly release hydrogen by maintaining a vacuum atmosphere at a predetermined temperature within a range of 500 to 1000 ° C. under an ultimate pressure of 0.13 kPa or less to promote phase transformation, followed by cooling. A method for producing a rare earth magnet powder excellent in magnetic anisotropy comprising a pulverizing step is known (see JP-A-2000-21614).
[0003]
[Problems to be solved by the invention]
In recent years, there has been a demand for rare earth magnet powders that are more excellent in magnetic anisotropy and cheaper in the electric and electronic industries, and can be used to efficiently and inexpensively produce rare earth magnet powders that are more magnetic anisotropy and cheaper. R & D has been done.
[0004]
[Means for Solving the Problems]
Therefore, the present inventors have also studied to develop a method capable of efficiently producing a rare earth magnet powder having further excellent magnetic anisotropy at low cost. as a result,
(A) Supplying an inert gas after the hydrogen absorption / decomposition treatment in the conventional method for producing a rare earth magnet powder having excellent magnetic anisotropy, and providing an inert gas pressure of 10 to 1000 kPa and a temperature of 500 to 1000 ° C. In place of the intermediate heat treatment held in the inert gas atmosphere at a predetermined temperature, the hydrogen pressure is maintained at a temperature in the range of 500 to 1000 ° C., and the hydrogen pressure is 20 to 60 of the hydrogen pressure during the hydrogen absorption / decomposition treatment. When the intermediate reduced pressure heat treatment held in the hydrogen atmosphere at a pressure of% is applied, the residual magnetic flux density is improved as compared with the conventional intermediate heat treatment in the inert gas atmosphere after the hydrogen absorption / decomposition treatment.
(B) This intermediate vacuum heat treatment has the same hydrogen atmosphere as the hydrogen absorption / decomposition treatment, and only exhausts the hydrogen to reduce the pressure. Therefore, the operation is simpler than the conventional intermediate heat treatment in which an inert gas is introduced. In addition to the method suitable for mass production, the magnetic anisotropy, particularly the residual magnetic flux density, was further improved as compared with the rare earth magnet powder produced by the conventional production method.
[0005]
The present invention has been made based on such research results,
(1) If necessary, a rare earth magnet alloy raw material homogenized in a vacuum or Ar gas atmosphere at a temperature of 600 to 1200 ° C. in a hydrogen gas atmosphere at a pressure of 10 to 1000 kPa and a temperature of 500 to 500 ° C. Perform a hydrogen absorption treatment that absorbs hydrogen by raising the temperature to less than ℃,
The rare earth magnet alloy raw material that has been subjected to the hydrogen absorption treatment is further heated to a temperature within a range of 500 to 1000 ° C. in a hydrogen gas atmosphere at a pressure of 10 to 1000 kPa, thereby holding the rare earth magnet alloy raw material further absorbing hydrogen. Hydrogen absorption and decomposition treatment that decomposes,
Subsequently, intermediate pressure reduction is performed in which the rare earth magnet alloy raw material subjected to hydrogen absorption / decomposition treatment is held in a hydrogen atmosphere at a temperature within a range of 500 to 1000 ° C. and a pressure of 20 to 60% of the pressure during hydrogen absorption / decomposition treatment. Heat treatment,
Subsequently, a part of hydrogen is left in the rare earth magnet alloy raw material by holding it in a hydrogen atmosphere at a temperature in the range of 500 to 1000 ° C. and a pressure of 0.65 to 13 kPa and lower than the pressure of the intermediate vacuum heat treatment. Heat treatment in reduced pressure hydrogen
Thereafter, dehydrogenation treatment is performed to force the phase transformation by forcibly releasing hydrogen from the rare earth magnet alloy raw material by maintaining in a vacuum atmosphere of a pressure of 0.13 kPa or less at a temperature in the range of 500 to 1000 ° C., It is characterized by a method for producing a rare earth magnet powder excellent in magnetic anisotropy that is then cooled and pulverized.
[0006]
The rare earth magnet alloy raw material used in this invention is
R: 10 to 20%, B: 3 to 20%, the rare earth magnet alloy raw material having a component composition of the balance consisting of Fe and inevitable impurities,
R: 10 to 20%, B: 3 to 20%, M: 0.001 to 5%, rare earth magnet alloy raw material having a component composition with the balance consisting of Fe and inevitable impurities,
R: 10 to 20%, Co: 0.1 to 50%, B: 3 to 20%, rare earth magnet alloy raw material having a component composition consisting of Fe and inevitable impurities, or
R: 10 to 20%, Co: 0.1 to 50%, B: 3 to 20%, M: 0.001 to 5%, and the rare earth magnet alloy having a composition composed of Fe and inevitable impurities. Raw materials are preferred.
[0007]
Next, the reason why the component composition and production conditions of the rare earth magnet alloy raw material used in the present invention are limited as described above will be described.
(A) Component composition R (rare earth elements including Y):
R is a rare earth element mainly composed of Nd and containing trace amounts of Y, Dy, Pr, Sm, Ce, La, Tb, Er, Eu, Gd, Tm, Yb, Lu, Ho, and the like. If the content is less than 10%, the coercive force is lowered. On the other hand, if the content exceeds 20%, the saturation magnetization is lowered and none of the desired magnetic properties can be obtained. Therefore, the content of R is set to 10 to 20%.
[0008]
B:
If the B content is less than 3%, the coercive force is lowered. On the other hand, if it exceeds 20%, the saturation magnetization is lowered and none of the desired magnetic properties can be obtained. Therefore, the content of B is set to 3 to 20%.
[0009]
Co:
Co is added as necessary in order to prevent the rare-earth magnet alloy from being isotropic. However, if the content is less than 0.1%, the desired effect cannot be obtained. Since the coercive force and the saturation magnetization are lowered, high characteristics cannot be obtained even if anisotropic. Therefore, the content of Co contained in the rare earth magnet alloy raw material used in the method for producing rare earth magnet powder of the present invention is set to 0.1 to 50% (more preferably 5 to 30%).
[0010]
M (one or more of Ga, Zr, Nb, Mo, Hf, Ta, W, Ni, Al, Ti, V, Cu, Cr, Ge, C, and Si):
M is added as necessary to further improve the coercive force and the residual magnetic flux density, but if the content is less than 0.001%, the desired effect cannot be obtained, while adding over 5%. This is not preferable because the coercive force and the residual magnetic flux density are lowered. Therefore, the content of M is set to 0.001 to 5%.
[0011]
(B) Production conditions The rare earth magnet alloy raw material is heated to a predetermined temperature from room temperature to a temperature of less than 500 ° C. in a hydrogen gas atmosphere having a pressure of 10 to 1000 kPa, or is heated to a predetermined temperature of less than 500 ° C. ( For example, a hydrogen absorption treatment for absorbing hydrogen by holding at 100 ° C. is performed. This rare earth magnet alloy raw material is heated to a predetermined temperature from room temperature to a temperature of less than 500 ° C. in a hydrogen gas atmosphere at a pressure of 10 to 1000 kPa, or a hydrogen absorption process for increasing the temperature is a conventional process. is there.
[0012]
By further heating the rare earth magnet alloy raw material subjected to the hydrogen absorption treatment, a hydrogen absorption / decomposition treatment is performed in a hydrogen gas atmosphere at a pressure of 10 to 1000 kPa and a temperature maintained at a predetermined temperature within a range of 500 to 1000 ° C. The raw material absorbs hydrogen to promote phase transformation and decompose. In this hydrogen absorption / decomposition treatment step, the pressure is maintained in a hydrogen gas atmosphere of 10 to 1000 kPa, and the temperature is maintained at a predetermined temperature in the range of 500 to 1000 ° C. is a known condition, and particularly a new condition Therefore, the explanation of the reason for the limitation is omitted.
[0013]
After such hydrogen absorption / decomposition treatment, at a temperature in the range of 500-1000 ° C., a pressure of 20-60% of the hydrogen pressure during hydrogen absorption / decomposition treatment (specifically, pressure: 2-600 kPa and hydrogen An intermediate reduced pressure heat treatment is carried out in a hydrogen atmosphere at a pressure relatively lower than the hydrogen pressure during the absorption / decomposition treatment. This intermediate reduced pressure heat treatment is a treatment step that replaces the conventional intermediate heat treatment performed in an inert gas atmosphere. After hydrogen absorption / decomposition treatment, the hydrogen gas is exhausted and reduced in pressure while the temperature is maintained at 500 to 1000 ° C. Therefore, it is not necessary to replace the inert gas atmosphere, and an intermediate pressure reduction heat treatment can be performed with a simple operation, and the residual magnetic flux density is further increased.
The reason why the hydrogen pressure in this intermediate reduced pressure heat treatment is set to 20 to 60% of the hydrogen pressure during the hydrogen absorption / decomposition treatment is that anisotropy is maintained at a pressure less than 20% of the hydrogen pressure during the hydrogen absorption / decomposition treatment. It is not preferable because the holding power is reduced because the reaction rate of the hydrogenation is too high. On the other hand, if the hydrogen pressure is kept higher than 60% of the hydrogen pressure during the hydrogen absorption / decomposition treatment, the anisotropy reaction is hardly Since it does not advance, it is not preferable. Therefore, the hydrogen pressure in the intermediate reduced pressure heat treatment is set to 20 to 60% of the hydrogen pressure during the hydrogen absorption / decomposition treatment.
[0014]
After performing this intermediate reduced pressure heat treatment, a further reduced pressure hydrogen heat treatment is performed. This heat treatment in hydrogen under reduced pressure is a treatment in which the rare earth magnet alloy raw material subjected to the hydrogen absorption / decomposition treatment is held in a hydrogen atmosphere at a hydrogen pressure of 0.65 to 13 kPa and lower than the hydrogen pressure in the intermediate vacuum heat treatment. By performing the heat treatment in hydrogen under reduced pressure, the coercive force and the residual magnetic flux density can be further improved.
[0015]
After this intermediate reduced pressure heat treatment is performed and further a heat treatment in reduced pressure hydrogen is performed, dehydrogenation treatment is performed. The dehydrogenation treatment is a treatment that forcibly releases hydrogen sufficiently from the rare earth magnet alloy raw material by maintaining a vacuum atmosphere at an ultimate pressure of 0.13 kPa or less, thereby promoting further phase transformation. This is because dehydrogenation is not sufficiently performed at an ultimate pressure exceeding 0.13 kPa.
The cooling performed after the dehydrogenation is performed by flowing an inert gas (Ar gas) to room temperature. After cooling, it is pulverized into rare earth magnet powder. The rare earth magnet powder obtained by pulverization is subjected to heat treatment as necessary to remove residual internal stress.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Ingots a to h of the rare earth magnet alloy raw materials having the component compositions shown in Table 1 were produced by melting using a high-frequency vacuum melting furnace and casting the obtained molten metal. These ingots a to h were pulverized in an inert gas atmosphere to produce blocks of 10 mm or less.
[0017]
[Table 1]
Example 1
After the blocks of ingots a to e in Table 1 were subjected to hydrogen absorption treatment under the conditions shown in Table 2 , the blocks subjected to the hydrogen absorption treatment were subjected to hydrogen absorption / decomposition treatment under the conditions shown in Table 2 , and then perform intermediate vacuum heat treatment under the conditions shown in Table 2, after further performs vacuo hydrogen annealing under the conditions shown in Table 3 were subjected to dehydrogenation treatment further conditions shown in Table 3, forced by Ar gas This invention method 1-5 was implemented by cooling to room temperature and grind | pulverizing to 300 micrometers or less, and manufacturing rare earth magnet powder.
[0019]
Conventional Example 1
The blocks of ingots a to e in Table 1 were subjected to hydrogen absorption treatment under the same conditions as in Example 1 shown in Table 2 , and then subjected to hydrogen absorption / decomposition treatment under the same conditions as in Example 1 , followed by Table 2. Is subjected to an intermediate heat treatment in an Ar gas atmosphere under the conditions shown in FIG. 3 , and further subjected to a heat treatment in hydrogen under reduced pressure under the conditions shown in Table 3 , followed by a dehydrogenation treatment under the conditions shown in Table 3 , and then forcedly performed with Ar gas. Conventional methods 1 to 5 were carried out by cooling to room temperature and grinding to 300 μm or less to produce rare earth magnet powder.
[0020]
The rare earth magnet powders obtained by the present invention methods 1 to 5 and the conventional methods 1 to 5 are each mixed with 3% by mass of an epoxy resin and kneaded and compression molded in a magnetic field of 1.6 MA / m to obtain a green compact. The green compact was then heat-cured in an oven at 150 ° C. for 2 hours to produce a bonded magnet having a density of 6.0 to 6.1 g / cm 3. The magnetic properties of the obtained bonded magnet are shown in Table 3. It was shown to.
[0021]
Further, the rare earth magnet powders obtained by the present invention methods 1 to 5 and the conventional methods 1 to 5 are compression molded in a magnetic field to produce an anisotropic green compact, and this anisotropic green compact is hot-pressed. In Ar gas, temperature: 750 ° C., pressure: 58.8 MPa so that the direction of magnetic field application is the compression direction Hot pressing was performed under the condition of holding for 1 minute, followed by rapid cooling to produce a hot pressed magnet having a density of 7.5 to 7.7 g / cm 3. Table 3 shows the magnetic properties of the obtained hot pressed magnet. .
[0022]
[Table 2]
[Table 3]
From the results shown in Table 1, Table 2 and Table 3 , the bond produced with the rare earth magnet powder obtained by the present invention methods 1 to 5 is subjected to hydrogen absorption treatment, subjected to hydrogen absorption / decomposition treatment, and then subjected to intermediate vacuum heat treatment. Magnetic properties of magnets and hot-pressed magnets are as follows: Bond magnets made from rare earth magnet powders obtained by conventional methods 1-5, which are subjected to hydrogen absorption treatment, hydrogen absorption / decomposition treatment, and then intermediate heat treatment in an Ar gas atmosphere It can be seen that the residual magnetic flux density is particularly improved as compared with the magnetic characteristics of the hot-press magnet.
[0025]
Example 2
After the blocks of ingots f to h in Table 1 are subjected to hydrogen absorption treatment under the conditions shown in Table 4 , the blocks subjected to the hydrogen absorption treatment are subjected to hydrogen absorption / decomposition treatment under the conditions shown in Table 4 , and subsequently perform intermediate vacuum heat treatment under the conditions shown in Table 4, further performed in vacuo hydrogen annealing under the conditions shown in Table 5, after further dehydrogenation process under the conditions shown in Table 5, forced by the Ar gas The present invention methods 6 to 8 were carried out by cooling to room temperature and grinding to 300 μm or less to produce rare earth magnet powder.
[0026]
Conventional example 2
After the blocks of the ingots f to h in Table 1 were subjected to hydrogen absorption treatment under the same conditions as in Example 2 shown in Table 4 , hydrogen absorption / decomposition treatment was performed under the same conditions as in Example 2, and subsequently Table 4 Is subjected to an intermediate heat treatment in an Ar gas atmosphere under the conditions shown in FIG. 5 , further subjected to a heat treatment in hydrogen under reduced pressure under the conditions shown in Table 5 , and further subjected to a dehydrogenation treatment under the conditions shown in Table 5 , and then forcedly performed with Ar gas. Conventional methods 6 to 8 were carried out by cooling to room temperature and grinding to 300 μm or less to produce rare earth magnet powder.
[0027]
The rare earth magnet powders obtained by the present invention methods 6 to 8 and the conventional methods 6 to 8 are each mixed with 3% by mass of an epoxy resin and kneaded and compression molded in a magnetic field of 1.6 MA / m to obtain a green compact. The green compact was heat-cured in an oven at 150 ° C. for 2 hours to produce a bonded magnet having a density of 6.0 to 6.1 g / cm 3. The magnetic properties of the obtained bonded magnet are shown in Table 5. It was shown to.
[0028]
Further, the rare earth magnet powder obtained by the present invention method 6-8 and the conventional method 6-8 is compression molded in a magnetic field to produce an anisotropic green compact, and this anisotropic green compact is hot-pressed. In Ar gas, temperature: 750 ° C., pressure: 58.8 MPa so that the direction of magnetic field application is the compression direction Hot pressing was performed under the condition of holding for 1 minute, followed by rapid cooling to produce a hot pressed magnet having a density of 7.5 to 7.7 g / cm 3. Table 5 shows the magnetic characteristics of the obtained hot pressed magnet. .
[0029]
[Table 4]
[Table 5]
From the results shown in Table 1, Table 4 and Table 5 , the bond produced with the rare earth magnet powder obtained by the present invention method 6 to 8 which is subjected to hydrogen absorption treatment, subjected to hydrogen absorption / decomposition treatment and then subjected to intermediate vacuum heat treatment Magnetic properties of magnets and hot-pressed magnets are as follows: Bond magnets made of rare earth magnet powders obtained by conventional methods 6-8 , which are subjected to hydrogen absorption treatment, hydrogen absorption / decomposition treatment, and then intermediate heat treatment in an Ar gas atmosphere It can be seen that the residual magnetic flux density is particularly improved as compared with the magnetic characteristics of the hot-press magnet.
[0032]
【The invention's effect】
(I) The rare earth magnet powder produced by the method for producing a rare earth magnet powder according to the present invention in which the rare earth magnet alloy raw material is treated in the order of hydrogen absorption treatment → hydrogen absorption / decomposition treatment → intermediate vacuum heat treatment → heat treatment in reduced pressure hydrogen → dehydrogenation treatment. , Superior in magnetic anisotropy compared to rare earth magnet powders produced by conventional methods for producing rare earth magnet powders in the order of hydrogen absorption treatment → hydrogen absorption / decomposition treatment → intermediate heat treatment → heat treatment under reduced pressure hydrogen → dehydrogenation treatment Yes,
(ii) In the method for producing a rare earth magnet powder according to the present invention, the introduction of the inert gas is performed only in the last cooling step, and the other steps can be controlled only by the pressure conditions for introducing and discharging the hydrogen gas. The production cost can be greatly reduced, and more excellent rare earth magnet powder can be provided at a low cost.
Etc. that have excellent industrial effects.
Claims (3)
この粉砕処理した前記希土類磁石合金原料を圧力：１０〜１０００ｋＰａの水素ガス雰囲気中で５００〜１０００℃の範囲内の温度に昇温し保持することにより前記希土類磁石合金原料にさらに水素を吸収させて分解する水素吸収・分解処理を施し、
引き続いて、水素吸収・分解処理を施した希土類磁石合金原料を５００〜１０００℃の範囲内の温度に保持しながら水素圧力を水素吸収・分解処理時の水素圧力の２０〜６０％の圧力の水素雰囲気中に保持する中間減圧熱処理を施し、
引き続いて、５００〜１０００℃の範囲内の温度で圧力：０．６５〜１３ｋＰａでかつ中間減圧熱処理の圧力よりも低い圧力の水素雰囲気中に保持することにより希土類磁石合金原料に水素を一部残したまま減圧水素中熱処理を行い、
その後、５００〜１０００℃の範囲内の温度で到達圧：０．１３ｋＰａ以下の真空雰囲気に保持することにより希土類磁石合金原料から強制的に水素を放出させて相変態を促す脱水素処理を施し、ついで冷却し、粉砕することを特徴とする磁気異方性に優れた希土類磁石粉末の製造方法。A rare earth magnet alloy raw material is subjected to a hydrogen absorption treatment in which hydrogen is absorbed by raising the temperature to a predetermined temperature from room temperature to less than 500 ° C. in a hydrogen gas atmosphere of pressure: 10 to 1000 kPa,
The pulverized rare earth magnet alloy raw material is heated to a temperature in the range of 500 to 1000 ° C. in a hydrogen gas atmosphere having a pressure of 10 to 1000 kPa to hold the rare earth magnet alloy raw material to further absorb hydrogen. Apply hydrogen absorption and decomposition treatment to decompose,
Subsequently, while maintaining the rare earth magnet alloy raw material subjected to the hydrogen absorption / decomposition treatment at a temperature in the range of 500 to 1000 ° C., the hydrogen pressure is 20 to 60% of the hydrogen pressure during the hydrogen absorption / decomposition treatment. Apply intermediate vacuum heat treatment to keep in the atmosphere,
Subsequently, a part of hydrogen is left in the rare earth magnet alloy raw material by holding it in a hydrogen atmosphere at a temperature in the range of 500 to 1000 ° C. and a pressure of 0.65 to 13 kPa and lower than the pressure of the intermediate vacuum heat treatment. Heat treatment in reduced pressure hydrogen
Thereafter, dehydrogenation treatment is performed to force the phase transformation by forcibly releasing hydrogen from the rare earth magnet alloy raw material by maintaining in a vacuum atmosphere of a pressure of 0.13 kPa or less at a temperature in the range of 500 to 1000 ° C., Next, a method for producing a rare earth magnet powder excellent in magnetic anisotropy, characterized by cooling and grinding.
Ｒ（但し、ＲはＹを含む希土類元素を示す。以下同じ）：１０〜２０％、Ｂ：３〜２０％を含有し、残部がＦｅおよび不可避不純物からなる成分組成を有する希土類磁石合金原料、
Ｒ：１０〜２０％、Ｂ：３〜２０％、Ｍ（但し、ＭはＧａ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆ、Ｔａ、Ｗ、Ｎｉ、Ａｌ、Ｔｉ、Ｖ、Ｃｕ、Ｃｒ、Ｇｅ、ＣおよびＳｉの内の１種または２種以上を示す。以下同じ）：０．００１〜５％を含有し、残部がＦｅおよび不可避不純物からなる成分組成を有する希土類磁石合金原料、
Ｒ：１０〜２０％、Ｃｏ：０．１〜５０％、Ｂ：３〜２０％を含有し、残部がＦｅおよび不可避不純物からなる成分組成を有する希土類磁石合金原料、または、
Ｒ：１０〜２０％、Ｃｏ：０．１〜５０％、Ｂ：３〜２０％、Ｍ：０．００１〜５％を含有し、残部がＦｅおよび不可避不純物からなる成分組成を有する希土類磁石合金原料であることを特徴とする磁気異方性に優れた希土類磁石粉末の製造方法。The rare earth magnet alloy raw material according to claim 1 is atomic% (hereinafter,% indicates atomic%),
R (provided that R represents a rare earth element including Y. The same shall apply hereinafter): 10 to 20%, B: 3 to 20%, with the balance being a rare earth magnet alloy raw material having a composition composed of Fe and inevitable impurities,
R: 10-20%, B: 3-20%, M (where M is Ga, Zr, Nb, Mo, Hf, Ta, W, Ni, Al, Ti, V, Cu, Cr, Ge, C and 1 type or 2 types or more of Si. The same shall apply hereinafter): Rare earth magnet alloy raw material containing 0.001 to 5%, the balance being composed of Fe and inevitable impurities,
R: 10 to 20%, Co: 0.1 to 50%, B: 3 to 20%, rare earth magnet alloy raw material having a component composition consisting of Fe and inevitable impurities, or
R: 10 to 20%, Co: 0.1 to 50%, B: 3 to 20%, M: 0.001 to 5%, and the rare earth magnet alloy having a composition composed of Fe and inevitable impurities. A method for producing a rare earth magnet powder having excellent magnetic anisotropy, which is a raw material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003013312A JP4076017B2 (en) | 2003-01-22 | 2003-01-22 | Method for producing rare earth magnet powder with excellent magnetic anisotropy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003013312A JP4076017B2 (en) | 2003-01-22 | 2003-01-22 | Method for producing rare earth magnet powder with excellent magnetic anisotropy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004228283A JP2004228283A (en) | 2004-08-12 |
| JP4076017B2 true JP4076017B2 (en) | 2008-04-16 |
Family
ID=32901674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003013312A Expired - Fee Related JP4076017B2 (en) | 2003-01-22 | 2003-01-22 | Method for producing rare earth magnet powder with excellent magnetic anisotropy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4076017B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114523100B (en) * | 2022-03-08 | 2022-10-28 | 西北有色金属研究院 | High-pressure reduction preparation method of molybdenum-hafnium-carbon alloy powder containing hafnium hydride |
-
2003
- 2003-01-22 JP JP2003013312A patent/JP4076017B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004228283A (en) | 2004-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5892139B2 (en) | Rare earth anisotropic magnet and manufacturing method thereof | |
| JP4702546B2 (en) | Rare earth permanent magnet | |
| CN1898757B (en) | Preparation method of rare earth permanent magnet material | |
| JP4840606B2 (en) | Rare earth permanent magnet manufacturing method | |
| JP5856953B2 (en) | Rare earth permanent magnet manufacturing method and rare earth permanent magnet | |
| JP5288277B2 (en) | Manufacturing method of RTB-based permanent magnet | |
| JP2009123968A (en) | POROUS MATERIAL FOR R-Fe-B BASED PERMANENT MAGNET, AND MANUFACTURING METHOD THEREOF | |
| KR20140141509A (en) | METHOD FOR PREPARING R-Fe-B BASED SINTERED MAGNET | |
| JP5288276B2 (en) | Manufacturing method of RTB-based permanent magnet | |
| KR102589893B1 (en) | Method for preparing sintered magnet and sintered magnet | |
| JPS63255902A (en) | R-b-fe sintered magnet and manufacture thereof | |
| EP3845335B1 (en) | Method for preparing ndfeb magnet powder | |
| JP4482861B2 (en) | Rare earth magnet powder excellent in magnetic anisotropy and thermal stability and method for producing the same | |
| JP2012195392A (en) | Method of manufacturing r-t-b permanent magnet | |
| JPH1131610A (en) | Method for producing rare earth magnet powder excellent in magnetic anisotropy | |
| JP4314244B2 (en) | Magnetic material powder manufacturing method and bonded magnet manufacturing method | |
| JP4076017B2 (en) | Method for producing rare earth magnet powder with excellent magnetic anisotropy | |
| JP3597615B2 (en) | Method for producing RTB based anisotropic bonded magnet | |
| JPS62181402A (en) | R-b-fe sintered magnet and manufacture thereof | |
| JP2003243211A (en) | Method for producing rare earth magnet powder excellent in magnetic anisotropy | |
| JP2004218042A (en) | Method for producing rare earth magnet powder excellent in magnetic anisotropy and thermal stability | |
| JP3178848B2 (en) | Manufacturing method of permanent magnet | |
| JP2000021614A (en) | Method for producing rare earth magnet powder excellent in magnetic anisotropy | |
| JPS62141704A (en) | R-b-fe system sintered magnet and manufacture thereof | |
| JPS62128504A (en) | R-b-fe group sintered magnet and manufacture thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050318 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20060125 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20060214 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20070528 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20071031 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20071218 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20071217 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20080123 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20080123 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110208 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110208 Year of fee payment: 3 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110208 Year of fee payment: 3 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110208 Year of fee payment: 3 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313532 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110208 Year of fee payment: 3 |
|
| R370 | Written measure of declining of transfer procedure |
Free format text: JAPANESE INTERMEDIATE CODE: R370 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110208 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |