JP3562138B2 - Raw material alloy for manufacturing rare earth magnet powder - Google Patents
Raw material alloy for manufacturing rare earth magnet powder Download PDFInfo
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- JP3562138B2 JP3562138B2 JP14662796A JP14662796A JP3562138B2 JP 3562138 B2 JP3562138 B2 JP 3562138B2 JP 14662796 A JP14662796 A JP 14662796A JP 14662796 A JP14662796 A JP 14662796A JP 3562138 B2 JP3562138 B2 JP 3562138B2
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- 229910045601 alloy Inorganic materials 0.000 title claims description 65
- 239000000956 alloy Substances 0.000 title claims description 65
- 239000002994 raw material Substances 0.000 title claims description 47
- 239000000843 powder Substances 0.000 title claims description 41
- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 39
- 150000002910 rare earth metals Chemical class 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 150000004678 hydrides Chemical class 0.000 claims description 26
- 239000011246 composite particle Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 13
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000012798 spherical particle Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052735 hafnium 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
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 102220029472 rs149033995 Human genes 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 29
- 239000001257 hydrogen Substances 0.000 description 29
- 229910052739 hydrogen Inorganic materials 0.000 description 29
- 238000011282 treatment Methods 0.000 description 25
- 238000000034 method Methods 0.000 description 16
- 238000006356 dehydrogenation reaction Methods 0.000 description 9
- 229910000765 intermetallic Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 206010053759 Growth retardation Diseases 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 102000015933 Rim-like Human genes 0.000 description 1
- 108050004199 Rim-like Proteins 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y25/00—Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0579—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B with exchange spin coupling between hard and soft nanophases, e.g. nanocomposite spring magnets
Description
【０００１】
【発明の属する技術分野】
この発明は、希土類磁石粉末を製造するための原料合金に関するものである。
【０００２】
【従来の技術】
微細な希土類金属間化合物相の集合組織からなる希土類磁石粉末を製造するには、Ｒ２ Ｆ１４Ｂ金属間化合物相を５００〜１０００℃の水素中でＲ２ Ｆｅ１４Ｂ相に水素を吸蔵させて、ＲＨ２ ，ＦｅおよびＦｅ２ Ｂの３相に相変態させ、続けて同じ温度領域で脱水素を行うと、上記水素吸蔵により発生したＲＨ２ ，ＦｅおよびＦｅ２ Ｂの３相はＲ２ Ｆｅ１４Ｂ相に再変態し、微細なＲ２ Ｆｅ１４Ｂ金属間化合物の再結晶集合組織となり、優れた磁気特性を示すようになることは知られている［特開平３−１２９７０２号公報、日本金属学会秋季大会一般講演概要（１９８９，Ｐ３６７）などを参照］。
【０００３】
この製法は、Ｒ２ Ｆｅ１４Ｂ金属間化合物相の水素化（Ｈｙｄｒｏｇｅｎａｔｉｏｎ ）、相分解（Ｄｅｃｏｍｐｏｓｉｔｉｏｎ ）、脱水素化（Ｄｅｓｏｒｐｔｉｏｎ）および再結合（Ｒｅｃｏｍｂｉｎａｔｉｏｎ ）の工程からなるところからＨＤＤＲ処理法と呼ばれており、この方法は、Ｆｅの一部をＣｏ，Ｎｉ，Ａｌ，Ｇａ，Ｓｉ，Ｖ，Ｚｒ，Ｈｆのうちの１種または２種で置換した成分（以下、Ｔで示す）からなるＲ２ Ｔ１４Ｂ金属間化合物相についても、同様に５００〜１０００℃で水素化させて相変態させ、続けて同じ温度領域で脱水素を行うとＲ２ Ｔ１４Ｂ相に再変態し、磁気異方性に優れた再結晶集合組織が得られることも知られている（特開平３−１２９７０２号公報、特開平３−１２９７０３号公報参照）。
【０００４】
また、水素吸蔵処理により変態したＲＨ２ ，Ｔ，Ｔ２ Ｂの３相を脱水素処理することにより、一層安定かつ異方的にＲ２ Ｔ１４Ｂ相へ再変態させる方法として、Ｒ２ Ｔ１４Ｂ金属間化合物相を水素ガス雰囲気中、５００〜１０００℃に保持して水素を吸蔵せしめたのち、一旦１００℃以下まで冷却し、次いで、真空中にて５００〜１０００℃まで再加熱して脱水素する方法も知られている（特開平５−１６６６１７号公報参照）。
【０００５】
【発明が解決しようとする課題】
しかし、Ｒ２ Ｔ１４Ｂ金属間化合物がＲＨ２ ，ＴおよびＴ２ Ｂに相変態する５００℃〜１０００℃の温度範囲で水素吸蔵処理し、引き続きその温度範囲で脱水素処理すると、常に高温で処理されるために異常な粒成長が起こり、均一で微細な再結晶集合組織が得られない場合があり、したがって、に十分な磁気特性を有する希土類磁石粉末は得られない場合がある。
【０００６】
そのために、上記特開平５−１６６６１７号公報に見られるように、水素吸蔵処理したのち、一旦１００℃以下に急冷し、次いで真空中、５００〜１０００℃に再加熱して脱水素処理する方法はある程度の粒成長抑制効果はあるが、一旦１００℃以下に急冷して水素吸蔵した合金を真空中、５００〜１０００℃に再加熱すると脱水素後のＲ２ Ｆｅ１４Ｂ相の粒成長は著しく早くなる場合があり、したがって、すでに知られている５００〜１０００℃で水素吸蔵処理に続いて脱水素処理する方法に比べて、粒成長抑制効果は十分なものではなく、十分な磁気特性を有する希土類磁石粉末は得られない。さらに、従来の希土類磁石粉末を製造するための原料合金は、数時間程度の保管に対しては、酸化などの構造変化が起こらないが、それよりも長期間保管すると、酸化などの構造変化によって、原料合金から得られる磁石粉末の磁気特性が劣化することがあった。
【０００７】
【課題を解決するための手段】
そこで、本発明者等は、従来よりも一層磁気特性に優れた希土類磁石粉末を得るべく研究を行った結果、
従来よりも均一で微細な再結晶集合組織を有する一層磁気特性に優れた希土類磁石粉末を得るには、水素吸蔵処理した原料合金の組織が大きく影響を及ぼし、その水素吸蔵処理した原料合金は、
Ｒ：Ｙを含む希土類元素、
Ｔ：Ｆｅ、またはＦｅを主成分とし一部をＣｏ，Ｎｉで置換した成分、
Ｍ：Ｂ、またはＢのうちの一部をＣで置換した成分、
Ａ：Ａｌ，Ｇａ，Ｓｉ，Ｔｉ，Ｖ，Ｃｒ，Ｚｒ，Ｎｂ，Ｍｏ，Ｈｆ，Ｔａ，Ｗのうちの少なくとも１種以上とすると、
これらＲ，Ｔ，ＭおよびＡを含み、残部不可避不純物からなるＲ−Ｔ−Ｍ−Ａ系合金において、合金素地中に、少なくとも平均粒径：０．００２〜２０μｍを有する第１相とこの第１相の周囲を包囲するリム状の第２相からなる複合粒子が分散している組織を有し、この複合粒子を構成する上記第１相は、（Ｒ 1-x-y Ｍ x （Ｔ，Ａ） y ）Ｈ z （ただし、０．００１≦ｘ≦０．５、０＜ｙ≦０．３、ｘ＋ｙ≦０．７、０＜ｚ≦２．５）の組成を有するＭを含有するＲの粒状の水素化物（以下、Ｍを含有するＲの粒状の水素化物という）からなり、さらに上記第２相は、少なくとも一部または全部がＲ2 Ｔ14Ｍ型の正方晶構造を有する相からなる原料合金であることが好ましく、
この原料合金を温度：５００〜１０００℃で強制的な脱水素処理すると、粒成長が著しく抑制された、均一で微細なＡ成分を含有するＲ2 Ｔ14Ｍ相の再結晶集合組織を有する磁気異方性に優れた希土類磁石粉末が得られ、さらに原料合金を長期間保管後に上記脱水素処理を行っても、得られる磁石粉末の磁気特性劣化がほとんどないという知見を得たのである。
【０００８】
この発明は、かかる研究結果に基づいてなされたものであって、
Ｒ，Ｔ，ＭおよびＡを含むＲ−Ｔ−Ｍ−Ａ系合金の合金素地中に、少なくとも平均粒径：０．００２〜２０μｍを有する第１相とこの第１相の周囲を包囲するリム状の第２相からなる複合粒子が分散している組織を有し、この複合粒子を構成する上記第１相は、Ｍを含有するＲの粒状の水素化物からなり、さらに上記第２相は、少なくとも一部または全部がＲ2 Ｔ14Ｍ型の正方晶構造を有する相からなる希土類磁石粉末製造用原料合金に特徴を有するものである。
【０００９】
複合粒子を構成する上記第１相のＭを含有するＲの粒状の水素化物は、球形形状をした粒状（以下、球形粒状という）であったり、紡錘形形状をした粒状（以下、紡錘形粒状という）であったり、さらに球形粒状および紡錘形粒状が共存していたりしてもよい。
上記球形粒状および／または紡錘形状の第１相は、いずれもリム状の第２相で包囲されて複合粒子を形成している。
したがって、この発明の希土類磁石合金製造用原料合金は、（ａ）第１相のＭを含有するＲの球形粒状の水素化物をリム状の第２相で包囲した複合粒子が素地中に分散した組織、（ｂ）第１相のＭを含有するＲの紡錘形粒状の水素化物をリム状の第２相で包囲してなる複合粒子が素地中に分散した組織、並びに（ｃ）上記（ａ）および（ｂ）の組織が共存した組織を有することを特徴とするものである。
複合粒子を構成する第１相のＭを含有するＲの粒状の水素化物は、紡錘形粒状であることが最も好ましく、紡錘形粒状および球形粒状の共存が次に好ましく、球形粒状であることがその次に好ましい。
この発明の希土類磁石粉末製造用原料合金のＲ−Ｔ−Ｍ−Ａ系合金の合金素地中に存在する上記複合粒子以外に、平均粒径：０．００２〜２０μｍの棒状または紡錘状のＭを含有するＲの水素化物がリム状の第２相に包囲されることなく単独相で混在していることがある。この単独相で混在するＭを含有するＲの水素化物は微量である方が好ましく、その混在割合は１０％以下の微量であることが好ましいが、この単独相が複合粒子とともに分散している組織を有する希土類磁石粉末製造用原料合金もこの発明に含まれる。なお、この発明の希土類磁石粉末製造用原料合金には、合金素地中の相として、Ｍを含有するＲの水素化物相とリム状の第２相の他にＴ2 Ｍ型の相なども存在する。
【００１０】
複合粒子を構成する上記第１相のＭを含有するＲの水素化物の大きさは平均粒径：０．００２〜２０μｍ（好ましくは０．００２〜３μｍ、さらに好ましくは０．００２〜１μｍ）の範囲内にあり、微細であるほど好ましいが、平均粒径が０．００２μｍよりも小さいと第１相および第２相から複合粒子とならなくなるので好ましくない。複合粒子を構成する上記第１相のＭを含有するＲの水素化物は、Ｍ：０．１〜５０原子％を含むＲの水素化物であることが好ましく、Ｍ：０．１〜５０原子％を含みかつ３０原子％以下（０を含まず）のＴおよびＡを含むＲの水素化物であることが一層好ましく、さらに（Ｒ１−ｘ−ｙ Ｍｘ （Ｔ，Ａ）ｙ ）Ｈｚ （ただし、０．００１≦ｘ≦０．５、０＜ｙ≦０．３、ｘ＋ｙ≦０．７、０＜ｚ≦２．５）の組成を有する水素化物であることがさらに一層好ましい。上記第２相は、少なくとも一部がＲ２ Ｔ１４Ｍ型の正方晶構造を有する相であることが好ましいが、全部がＲ２ Ｔ１４Ｍ型の正方晶構造を有する相であることが一層好ましい。また、第２相のＲ２ Ｔ１４Ｍ型の正方晶構造を有する相は、成分としてＡを一部含有しても良く、水素化物であっても良い。合金素地はＴを主成分とする相であり、合金素地中には、上記第１相と第２相の他にＦｅ２ Ｂ型構造の相が存在してもよい。
【００１１】
この発明の希土類磁石粉末製造用原料合金のＲはＹを含む希土類元素のうち少なくとも１種以上であるが、希土類元素のうちでもＲはＮｄ，Ｐｒ，Ｄｙ，Ｌａ，Ｃｅが特に好ましく、さらにＡはＺｒ，Ｇａ，Ｈｆ，Ｎｂ，Ｔａ，Ａｌ，Ｓｉのうちの少なくとも１種以上であることが特に好ましい。
【００１２】
この発明の原料合金を５００〜１０００℃で脱水素すると、Ａ成分を含むＲ２ Ｔ１４ＭタイプのＣ軸方向が一定方向に揃った再結晶集合組織を有する優れた磁気異方性磁石粉末が得られる。
【００１３】
この発明の希土類磁石粉末製造用原料合金を製造するには、先ずＲ−Ｔ−Ｍ−Ａ系合金インゴットを用意し、必要に応じて９００〜１２００℃で均質化処理を行なう。このＲ−Ｔ−Ｍ−Ａ系合金インゴットを水素または水素と不活性ガスの混合雰囲気中、７５０〜１０００℃の範囲で水素吸蔵の第１処理を施したのち第１処理に続けて実質的にＡｒガス雰囲気中に保持して１００〜７００℃の範囲内の温度に冷却し、この１００〜７００℃に保持したのち昇温する第２処理を施し、この第２処理に続けて雰囲気を水素または水素と不活性ガスの混合雰囲気にし、第１処理と同じ条件の７５０〜１０００℃に保持した後、室温まで冷却する第３処理を施す方法により製造することができる。しかし、この発明はこの方法に限定されるものではない。
【００１４】
いずれにしても、水素または水素と不活性ガスの混合雰囲気中、温度：７５０〜１０００℃保持の第１処理を施したのち、実質的にＡｒガス雰囲気中、１００〜７００℃の範囲内の温度に保持し、さらに水素または水素と不活性ガスの混合雰囲気中、温度：７５０〜１０００℃保持の第３処理を施すことによりこの発明の希土類磁石粉末製造用原料合金を製造するすることができ、水素または水素と不活性ガスの混合雰囲気中、温度：７５０〜１０００℃保持の水素吸蔵処理の途中で、実質的にＡｒガス雰囲気中、温度：１００〜７００℃の範囲内の温度に保持することが必要である。この第２処理の雰囲気は、原料合金から放出される水素が若干含まれることがあるが、実質的にはＡｒ雰囲気である。１００℃未満あるいは７００℃を越えるとＭを含有するＲの水素化物あるいはリム状の第２相が形成され難いので好ましくない。上記１００〜７００℃に保持する時間は、原料の種類にもよるが、０．１〜２０時間（好ましくは１〜５時間）の範囲内である。
【００１５】
この発明の希土類磁石粉末製造用原料合金を製造するための第１処理、第２処理および第３処理を含む水素吸蔵処理パターンを図１示した。
【００１６】
この発明の希土類磁石粉末製造用原料合金を製造するための出発原料としては、鋳造合金、焼結合金、超急冷合金、アトマイズ合金、一部あるいは全部非晶質合金、メカニカルアロイ合金、共還元粉末などいずれの合金を用いてもよいが、この中でも鋳造合金、一部あるいは全部非晶質合金またはメカニカルアロイ合金を用いることが特に好ましい。
【００１７】
このようにして得られたこの発明の希土類磁石合金製造用原料合金の組織は、素地中にＭを含有するＲの粒状の水素化物からなる第１相とこの第１相の周囲を包囲するリム状の第２相からなる複合粒子が分散しており、この複合粒子の第１相はＭを含有するＲの粒状の水素化物、第２相は少なくとも一部または全部が全体がＲ２ Ｔ１４Ｍ型の正方晶構造を有する相からなるものである。この複合組織により希土類磁石粉末を製造するための原料合金として長期保管することができると考えられる。
【００１８】
なお、図１において、この発明の希土類磁石粉末製造用原料合金を製造するための第１処理、第２処理および第３処理を含む水素吸蔵処理パターンを示したが、この発明の水素吸蔵処理パターンは上記図１に限定されるものではなく、種々に変形した水素吸蔵処理パターンを採用することができる。
【００１９】
【発明の実施の形態】
実施例１
表１の成分組成を有する合金Ａ〜Ｊを用意し、この合金Ａ〜ＪをＡｒ雰囲気のプラズマアーク溶解炉にて溶解した。上記合金Ａ〜Ｊの溶湯のうち合金Ａ〜Ｊの溶湯を鋳造してインゴットを作製し、このインゴットを表１に示される条件で均質化処理し、ついで粉砕して表１に示される寸法のブロックまたは粉末を作製した。
【００２０】
得られた表１に示される合金Ａ〜Ｊのブロックまたは粉末を、表２に示される条件で第１処理、第２処理および第３処理を施すことにより本発明希土類磁石粉末製造用原料合金（以下、本発明原料という）１〜１０および比較希土類磁石粉末製造用原料合金（以下、比較原料という）１〜３を作製した。
【００２１】
さらに、表１に示される合金Ａのブロックを表２に示される条件で水素吸蔵処理することにより従来希土類磁石粉末製造用原料合金（以下、従来原料という）を作製した。
【００２２】
これら本発明原料１〜１０、比較原料１〜３および従来原料を透過電子顕微鏡で組織観察を行い、Ｍを含有するＲの水素化物からなる第１相の平均粒径、および形状の観察を行い、その結果を表３に示した。さらに、分析透過電子顕微鏡にて第１相の定量分析を行い、第１相を包囲したリム状のＲ２ Ｔ１４Ｍ型の正方晶構造を少なくとも一部または全部有する第２相の有無を調べ、その結果を表３に示した。また、原料合金の水素量を分析して（Ｒ１−ｘ−ｙ Ｍｘ （Ｔ，Ａ）ｙ ）Ｈｚ の形で表した水素量比Ｈｚ を算出し、（Ｒ１−ｘ−ｙ Ｍｘ （Ｔ，Ａ）ｙ ）Ｈｚ におけるｘ、ｙおよびｚを表３に示した。
【００２３】
【表１】
【表２】
【表３】
表３に示される本発明原料１〜１０、比較原料１〜３および従来原料を大気中、温度：３０℃、湿度：５０％にて６０日保管した後、１×１０−５ｔｏｒｒの真空雰囲気になるまで、表４および表５に示される条件で脱水素処理を行い、急冷し、ついで粉砕して磁石粉末とした。これら磁石粉末の組織を観察したところ、再結晶粒が集合した再結晶集合組織を有しており、この磁石粉末を１５ＫＯｅの磁場中で配向させ残留磁化および保磁力（ｉＨｃ）を振動試料型磁束計で測定し、その結果についても表４および表５に示した。
【００２７】
【表４】
【表５】
表２〜表５に示される結果から、平均粒径：０．００２〜２０μｍの第１相をリム状の第２相で包囲している複合粒子が分散した組織を有する本発明原料１〜１０を脱水素処理して得られた希土類磁石粉末は優れた磁気特性を示すことがわかる。しかし第２処理の温度が１００℃未満で処理した比較原料１、第２処理の温度が７００℃を越えた条件で処理した比較原料２および第２処理の雰囲気を水素雰囲気で行った比較原料３、並びに通常の水素吸蔵処理した従来原料をそれぞれ脱水素処理して得られた希土類磁石粉末の磁気特性は劣化していることがわかる。
【００３０】
【発明の効果】
上述のように、この発明の方法で製造した希土類磁石粉末製造用原料合金は、長期保管しておいて、必要量だけ脱水素処理することにより優れた磁気特性を有する希土類磁石粉末を得ることができるなど産業上すぐれた効果を奏するものである。
【図面の簡単な説明】
【図１】この発明の希土類磁石粉末製造用原料合金を製造するための水素吸蔵処理パターンである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a raw material alloy for producing a rare earth magnet powder.
[0002]
[Prior art]
In order to produce a rare earth magnet powder having a texture of a fine rare earth intermetallic compound phase, the R 2 F 14 B intermetallic compound phase is caused to absorb hydrogen in the R 2 Fe 14 B phase in hydrogen at 500 to 1000 ° C. Then, when the phase is transformed into three phases of RH 2 , Fe and Fe 2 B and then dehydrogenated in the same temperature range, the three phases of RH 2 , Fe and Fe 2 B generated by the above-mentioned hydrogen absorption become R 2 It is known that it re-transforms into a Fe 14 B phase, becomes a recrystallized texture of a fine R 2 Fe 14 B intermetallic compound, and exhibits excellent magnetic properties [Japanese Patent Application Laid-Open No. 3-129702, General Lecture Summary of the Japan Institute of Metals Autumn Meeting (1989, P367)].
[0003]
This method is called the HDDR treatment method because it comprises the steps of hydrogenation, phase decomposition, dehydrogenation (Desorption), and recombination (Recombination) of the R 2 Fe 14 B intermetallic compound phase. In this method, R 2 is composed of a component in which a part of Fe is replaced with one or two of Co, Ni, Al, Ga, Si, V, Zr, and Hf (hereinafter, referred to as T). The T 14 B intermetallic compound phase is similarly hydrogenated at 500 to 1000 ° C. to undergo phase transformation, and subsequently dehydrogenated in the same temperature range, re-transforms into the R 2 T 14 B phase, and has a magnetic anisotropy. It is also known that a recrystallized texture having excellent properties can be obtained (see JP-A-3-129702 and JP-A-3-129703).
[0004]
As a method for more stably and anisotropically retransforming into the R 2 T 14 B phase by subjecting the three phases RH 2 , T and T 2 B transformed by the hydrogen storage treatment to dehydrogenation treatment, R 2 T The 14B intermetallic compound phase is kept at 500 to 1000 ° C. in a hydrogen gas atmosphere to absorb hydrogen, then cooled once to 100 ° C. or lower, and then reheated to 500 to 1000 ° C. in vacuum. A method for dehydrogenation is also known (see JP-A-5-166617).
[0005]
[Problems to be solved by the invention]
However, when the R 2 T 14 B intermetallic compound undergoes a hydrogen storage treatment at a temperature in the range of 500 ° C. to 1000 ° C. where the R 2 T 14 B intermetallic compound transforms into RH 2 , T and T 2 B, and then a dehydrogenation treatment in that temperature range, it is always high temperature Due to the treatment, abnormal grain growth may occur, and a uniform and fine recrystallized texture may not be obtained. Therefore, a rare earth magnet powder having sufficient magnetic properties may not be obtained.
[0006]
For this purpose, as described in JP-A-5-166617, a method of dehydrogenating by hydrogen absorbing treatment, then rapidly cooling to 100 ° C. or lower, and then reheating to 500 to 1000 ° C. in vacuum. Although there is a certain degree of grain growth suppression effect, once the alloy that has been quenched and cooled rapidly to 100 ° C. or less and re-heated to 500 to 1000 ° C. in vacuum, the grain growth of the R 2 Fe 14 B phase after dehydrogenation is extremely fast Therefore, the effect of suppressing grain growth is not sufficient as compared with the already known method of performing a hydrogen storage treatment at 500 to 1000 ° C. followed by a dehydrogenation treatment, and a rare earth element having sufficient magnetic properties No magnet powder is obtained. Furthermore, conventional raw material alloys for producing rare earth magnet powder do not undergo structural changes such as oxidation when stored for several hours, but when stored for a longer period of time, due to structural changes such as oxidation. In some cases, the magnetic properties of the magnet powder obtained from the raw material alloy deteriorated.
[0007]
[Means for Solving the Problems]
Therefore, the present inventors have conducted research to obtain a rare earth magnet powder having more excellent magnetic properties than before, and as a result,
In order to obtain a rare-earth magnet powder having a more uniform and fine recrystallized texture and a more excellent magnetic property than before, the structure of the hydrogen-absorbed raw material alloy has a great effect.
R: a rare earth element containing Y,
T: Fe or a component mainly composed of Fe and partially substituted with Co or Ni;
M: B or a component obtained by substituting a part of B with C;
A: If at least one of Al, Ga, Si, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W,
In the R-T-M-A alloy containing R, T, M and A and the balance of unavoidable impurities, a first phase having at least an average particle diameter of 0.002 to 20 μm and It has a structure in which composite particles composed of a rim-shaped second phase surrounding the periphery of one phase are dispersed, and the first phase constituting the composite particles is (R 1-xy M x (T, A ) Y ) H z (where 0.001 ≦ x ≦ 0.5, 0 <y ≦ 0.3, x + y ≦ 0.7, 0 <z ≦ 2.5) The second phase is a raw material alloy comprising a granular hydride (hereinafter, referred to as a granular hydride of R containing M) , and at least part or all of which is a phase having a tetragonal structure of R2 T14M type. Is preferably
When this raw material alloy is forcibly dehydrogenated at a temperature of 500 to 1000 ° C., a magnetic anisotropy having a recrystallized texture of an R2 T14 M phase containing a uniform and fine A component, in which grain growth is significantly suppressed. It has been found that even when the above-mentioned dehydrogenation treatment is carried out after storing the raw material alloy for a long period of time, the magnetic properties of the obtained magnet powder are hardly deteriorated.
[0008]
The present invention has been made based on such research results,
A first phase having at least an average particle size of 0.002 to 20 μm and a rim surrounding the first phase in an RTMA-based alloy containing R, T, M and A Having a structure in which composite particles composed of a second phase are dispersed, the first phase constituting the composite particles is composed of a granular hydride of R containing M, and the second phase is , Characterized in that it is a raw material alloy for producing a rare earth magnet powder, at least partially or wholly of a phase having a tetragonal structure of the R2 T14 M type.
[0009]
The granular hydride of R containing M of the first phase constituting the composite particles may be spherical granular (hereinafter referred to as spherical granular) or spindle-shaped granular (hereinafter referred to as spindle granular). Or spherical and spindle-shaped granules may coexist.
Each of the spherical granular and / or spindle-shaped first phases is surrounded by the rim-shaped second phase to form composite particles.
Therefore, in the raw material alloy for producing a rare earth magnet alloy of the present invention, (a) composite particles in which a spherical spherical hydride of R containing M of the first phase is surrounded by a rim-shaped second phase are dispersed in the matrix. Structure, (b) a structure in which composite particles comprising a spindle-shaped granular hydride of R containing M of the first phase surrounded by a rim-shaped second phase are dispersed in a matrix, and (c) the above (a) And (b) have a coexisting tissue.
The granular hydride of R containing M of the first phase constituting the composite particles is most preferably spindle-shaped granules, the spindle-shaped particles and the spherical particles preferably coexist, and the spherical particles next. Preferred.
In addition to the above composite particles present in the alloy base material of the RTMA-based alloy as the raw material alloy for producing a rare earth magnet powder of the present invention, a rod-shaped or spindle-shaped M having an average particle diameter of 0.002 to 20 μm is used. The contained hydride of R may be mixed in a single phase without being surrounded by the rim-shaped second phase. It is preferable that the hydride of M containing M mixed in the single phase is trace amount, and the mixing ratio is preferably a trace amount of 10% or less, but the structure in which the single phase is dispersed together with the composite particles is preferred. The present invention also includes a raw alloy for producing a rare earth magnet powder having the following. In the raw material alloy for producing a rare earth magnet powder according to the present invention, as a phase in the alloy base, a T2M type phase and the like exist in addition to the R hydride phase containing M and the second rim phase. .
[0010]
The size of the hydride of R containing M of the first phase constituting the composite particles has an average particle diameter of 0.002 to 20 μm (preferably 0.002 to 3 μm, more preferably 0.002 to 1 μm). It is preferable that the average particle diameter is smaller than 0.002 μm because the first phase and the second phase do not form composite particles. The hydride of R containing M of the first phase constituting the composite particles is preferably a hydride of R containing M: 0.1 to 50 at%, and M: 0.1 to 50 at%. More preferably, it is a hydride of R containing 30 atomic% or less (not including 0) of T and A, and furthermore, (R 1-xy M x (T, A) y ) H z ( However, a hydride having a composition of 0.001 ≦ x ≦ 0.5, 0 <y ≦ 0.3, x + y ≦ 0.7, and 0 <z ≦ 2.5) is still more preferable. The second phase, at least partially, but preferably a phase having a tetragonal structure of R 2 T 14 M-type, more that all of a phase having a tetragonal structure of R 2 T 14 M type preferable. Further, the second phase having an R 2 T 14 M-type tetragonal structure may partially contain A as a component, or may be a hydride. The alloy base is a phase containing T as a main component, and a phase having an Fe 2 B type structure may be present in the alloy base in addition to the first phase and the second phase.
[0011]
R of the raw material alloy for producing a rare earth magnet powder of the present invention is at least one or more of the rare earth elements containing Y, and among the rare earth elements, R is particularly preferably Nd, Pr, Dy, La, Ce, and more preferably A Is particularly preferably at least one of Zr, Ga, Hf, Nb, Ta, Al and Si.
[0012]
When the raw material alloy of the present invention is dehydrogenated at 500 to 1000 ° C., an excellent magnetic anisotropic magnet powder having a recrystallized texture in which the C axis direction of the R 2 T 14 M type containing the A component is aligned in a certain direction is obtained. can get.
[0013]
In order to produce the raw material alloy for producing a rare earth magnet powder of the present invention, first, an RTMA-based alloy ingot is prepared and, if necessary, homogenized at 900 to 1200 ° C. This RTMA-based alloy ingot is subjected to a first treatment of hydrogen storage in a range of 750 to 1000 ° C. in an atmosphere of hydrogen or a mixed atmosphere of hydrogen and an inert gas, and subsequently, the first treatment is substantially continued. A second process of maintaining the temperature in an Ar gas atmosphere and cooling to a temperature in the range of 100 to 700 ° C., maintaining the temperature in the range of 100 to 700 ° C., and then raising the temperature is performed. It can be manufactured by a method in which a mixed atmosphere of hydrogen and an inert gas is used, the temperature is maintained at 750 to 1000 ° C. under the same conditions as in the first process, and then a third process is performed to cool to room temperature. However, the invention is not limited to this method.
[0014]
In any case, after performing the first treatment at a temperature of 750 to 1000 ° C. in an atmosphere of hydrogen or a mixture of hydrogen and an inert gas, a temperature substantially in the range of 100 to 700 ° C. in an Ar gas atmosphere. , And further subjected to a third treatment at a temperature of 750 to 1000 ° C. in an atmosphere of hydrogen or a mixture of hydrogen and an inert gas, whereby the raw material alloy for producing a rare earth magnet powder of the present invention can be produced. In the course of hydrogen storage at a temperature of 750 to 1000 ° C. in an atmosphere of hydrogen or a mixture of hydrogen and an inert gas, the temperature is substantially maintained in a range of 100 to 700 ° C. in an Ar gas atmosphere. is necessary. The atmosphere of the second treatment may contain some hydrogen released from the raw material alloy, but is substantially an Ar atmosphere. If the temperature is lower than 100 ° C. or higher than 700 ° C., it is not preferable because a hydride of R containing M or a rim-like second phase is difficult to be formed. The time for maintaining the temperature at 100 to 700 ° C. depends on the type of the raw material, but is in the range of 0.1 to 20 hours (preferably 1 to 5 hours).
[0015]
FIG. 1 shows a hydrogen storage treatment pattern including a first treatment, a second treatment, and a third treatment for producing a raw material alloy for producing a rare earth magnet powder according to the present invention.
[0016]
Starting materials for producing the raw material alloy for producing a rare earth magnet powder of the present invention include a cast alloy, a sintered alloy, a super-quenched alloy, an atomized alloy, a partially or entirely amorphous alloy, a mechanical alloy alloy, and a co-reduced powder. Although any of these alloys may be used, it is particularly preferable to use a cast alloy, a partially or entirely amorphous alloy or a mechanical alloy alloy.
[0017]
The structure of the raw material alloy for producing a rare earth magnet alloy of the present invention thus obtained is composed of a first phase composed of granular hydride of R containing M in the base material and a rim surrounding the first phase. Composite particles composed of a second phase are dispersed. The first phase of the composite particles is a granular hydride of R containing M, and the second phase is at least partially or wholly entirely composed of R 2 T 14. It is composed of a phase having an M-type tetragonal structure. It is considered that this composite structure enables long-term storage as a raw material alloy for producing rare earth magnet powder.
[0018]
FIG. 1 shows a hydrogen storage pattern including a first process, a second process, and a third process for manufacturing a raw material alloy for manufacturing a rare earth magnet powder according to the present invention. Is not limited to FIG. 1 described above, and variously modified hydrogen storage processing patterns can be adopted.
[0019]
BEST MODE FOR CARRYING OUT THE INVENTION
Example 1
Alloys A to J having the component compositions shown in Table 1 were prepared, and the alloys A to J were melted in a plasma arc melting furnace in an Ar atmosphere. Of the alloys A to J, the melts of the alloys A to J were cast to produce ingots, and the ingots were homogenized under the conditions shown in Table 1 and then pulverized to obtain the dimensions shown in Table 1. A block or powder was made.
[0020]
By subjecting the obtained blocks or powders of the alloys A to J shown in Table 1 to the first treatment, the second treatment and the third treatment under the conditions shown in Table 2, the raw material alloy for producing the rare earth magnet powder of the present invention ( Hereinafter, raw materials of the present invention (referred to as “raw materials of the present invention”) 1 to 10 and raw material alloys (hereinafter, referred to as comparative raw materials) 1 to 3 for producing comparative rare earth magnet powders were prepared.
[0021]
Further, a block of alloy A shown in Table 1 was subjected to hydrogen occlusion treatment under the conditions shown in Table 2 to prepare a raw material alloy for producing a rare earth magnet powder (hereinafter, referred to as a conventional raw material).
[0022]
The structure of these raw materials 1 to 10 of the present invention, comparative raw materials 1 to 3 and conventional raw materials is observed with a transmission electron microscope, and the average particle size and shape of the first phase composed of a hydride of R containing M are observed. Table 3 shows the results. Further, quantitative analysis of the first phase is performed by an analytical transmission electron microscope, and the presence or absence of the second phase having at least a part or all of a rim-shaped R 2 T 14 M tetragonal structure surrounding the first phase is examined. Table 3 shows the results. Further, by analyzing the hydrogen content of the material alloy (R 1-x-y M x (T, A) y) was calculated hydrogen amount ratio H z, expressed in the form of H z, (R 1-x -y Table 3 shows x, y, and z of M x (T, A) y ) H z .
[0023]
[Table 1]
[Table 2]
[Table 3]
The raw materials 1 to 10 of the present invention, the comparative raw materials 1 to 3 and the conventional raw materials shown in Table 3 were stored in the air at a temperature of 30 ° C. and a humidity of 50% for 60 days, and then a vacuum atmosphere of 1 × 10 −5 torr was obtained. , A dehydrogenation treatment was performed under the conditions shown in Tables 4 and 5, followed by rapid cooling, followed by pulverization to obtain magnet powder. Observation of the structure of these magnet powders revealed that they had a recrystallized texture in which recrystallized grains were aggregated. This magnet powder was oriented in a magnetic field of 15 KOe, and the remanent magnetization and coercive force (iHc) were measured using a vibrating sample type magnetic flux. The results were shown in Tables 4 and 5.
[0027]
[Table 4]
[Table 5]
From the results shown in Tables 2 to 5, the raw materials 1 to 10 of the present invention having a structure in which the composite particles surrounding the first phase having an average particle size of 0.002 to 20 μm with the rim-shaped second phase are dispersed. It can be seen that the rare earth magnet powder obtained by dehydrogenation shows excellent magnetic properties. However, comparative raw material 1 processed at a temperature of the second processing lower than 100 ° C., comparative raw material 2 processed at a temperature of the second processing exceeding 700 ° C., and comparative raw material 3 processed at a second processing atmosphere in a hydrogen atmosphere It can be seen that the magnetic properties of the rare earth magnet powder obtained by dehydrogenating the conventional raw materials subjected to the ordinary hydrogen storage treatment and the conventional hydrogen storage treatment are degraded.
[0030]
【The invention's effect】
As described above, the rare-earth magnet powder-producing raw material alloy produced by the method of the present invention can be stored for a long period of time, and a rare-earth magnet powder having excellent magnetic properties can be obtained by dehydrogenating only a required amount. It has excellent industrial effects.
[Brief description of the drawings]
FIG. 1 is a hydrogen storage pattern for producing a raw alloy for producing a rare earth magnet powder according to the present invention.
Claims (5)
Ｔ：Ｆｅ、またはＦｅを主成分とし一部をＣｏ、Ｎｉで置換した成分、
Ｍ：Ｂ、またはＢのうち一部をＣで置換した成分、
Ａ：Ａｌ，Ｇａ，Ｓｉ，Ｔｉ，Ｖ，Ｃｒ，Ｚｒ，Ｎｂ，Ｍｏ，Ｈｆ，Ｔａ，Ｗのうちの少なくとも１種以上とすると、
これらＲ，Ｔ，ＭおよびＡを含み、残部不可避不純物からなるＲ−Ｔ−Ｍ−Ａ系合金において、合金素地中に、少なくとも平均粒径：０．００２〜２０μｍを有する第１相とこの第１相の周囲を包囲するリム状の第２相からなる複合粒子が分散している組織を有し、この複合粒子を構成する上記第１相は、（Ｒ 1-x-y Ｍ x （Ｔ，Ａ） y ）Ｈ z （ただし、０．００１≦ｘ≦０．５、０＜ｙ≦０．３、ｘ＋ｙ≦０．７、０＜ｚ≦２．５）の組成を有するＭを含有するＲの粒状の水素化物（以下、Ｍを含有するＲの粒状の水素化物という）からなり、さらに上記第２相は、少なくとも一部または全部がＲ2 Ｔ14Ｍ型の正方晶構造を有する相からなることを特徴とする希土類磁石粉末製造用原料合金。R: a rare earth element containing Y,
T: Fe or a component mainly composed of Fe and partially substituted with Co or Ni;
M: B or a component in which a part of B is substituted with C,
A: If at least one of Al, Ga, Si, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W,
In the R-T-M-A alloy containing R, T, M and A and the balance of unavoidable impurities, a first phase having at least an average particle diameter of 0.002 to 20 μm and It has a structure in which composite particles composed of a rim-shaped second phase surrounding the periphery of one phase are dispersed, and the first phase constituting the composite particles is (R 1-xy M x (T, A ) Y ) H z (where 0.001 ≦ x ≦ 0.5, 0 <y ≦ 0.3, x + y ≦ 0.7, 0 <z ≦ 2.5) The second phase is composed of a granular hydride (hereinafter, referred to as a granular hydride of R containing M) , and the second phase is at least partially or entirely composed of a phase having a tetragonal structure of R2 T14M type. Alloy for the production of rare earth magnet powder.
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| JP14662796A JP3562138B2 (en) | 1996-05-16 | 1996-05-16 | Raw material alloy for manufacturing rare earth magnet powder |
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| Application Number | Priority Date | Filing Date | Title |
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| JP14662796A JP3562138B2 (en) | 1996-05-16 | 1996-05-16 | Raw material alloy for manufacturing rare earth magnet powder |
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| Publication Number | Publication Date |
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| JPH09310102A JPH09310102A (en) | 1997-12-02 |
| JP3562138B2 true JP3562138B2 (en) | 2004-09-08 |
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| EP1115125A3 (en) * | 2000-01-06 | 2002-05-02 | Seiko Epson Corporation | Magnetic powder and isotropic bonded magnet |
| JP2001267111A (en) | 2000-01-14 | 2001-09-28 | Seiko Epson Corp | Magnet powder and isotropic bonded magnet |
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