JP2009215583A - Sm-Co-BASED ALLOY NANOPARTICLE, AND METHOD FOR PRODUCING THE SAME - Google Patents
Sm-Co-BASED ALLOY NANOPARTICLE, AND METHOD FOR PRODUCING THE SAME Download PDFInfo
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- JP2009215583A JP2009215583A JP2008058346A JP2008058346A JP2009215583A JP 2009215583 A JP2009215583 A JP 2009215583A JP 2008058346 A JP2008058346 A JP 2008058346A JP 2008058346 A JP2008058346 A JP 2008058346A JP 2009215583 A JP2009215583 A JP 2009215583A
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 118
- 239000000956 alloy Substances 0.000 title claims abstract description 118
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 94
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 75
- 239000002184 metal Substances 0.000 claims abstract description 74
- 239000002245 particle Substances 0.000 claims abstract description 70
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 22
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 claims description 137
- 150000003839 salts Chemical class 0.000 claims description 34
- 150000001216 Samarium Chemical class 0.000 claims description 24
- 150000001868 cobalt Chemical class 0.000 claims description 22
- 239000003638 chemical reducing agent Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 230000001603 reducing effect Effects 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000003223 protective agent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 229910010082 LiAlH Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000000243 solution Substances 0.000 description 23
- 238000006722 reduction reaction Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000696 magnetic material Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- BTOOAFQCTJZDRC-UHFFFAOYSA-N 1,2-hexadecanediol Chemical compound CCCCCCCCCCCCCCC(O)CO BTOOAFQCTJZDRC-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 4
- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 4
- 238000004611 spectroscopical analysis Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000000053 physical method Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 or Os Inorganic materials 0.000 description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- 229910004247 CaCu Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/52—Alloys
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
-
- 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
- H01F1/0551—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 in the form of particles, e.g. rapid quenched powders or ribbon flakes
-
- 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
- H01F1/0551—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0552—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 in the form of particles, e.g. rapid quenched powders or ribbon flakes with a protective layer
-
- 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
- H01F1/0553—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 obtained by reduction or by hydrogen decrepitation or embrittlement
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Abstract
Description
本発明は、ＳｍＣｏ系合金ナノ粒子及びその製造方法に関する。 The present invention relates to SmCo-based alloy nanoparticles and a method for producing the same.
磁気記録媒体や磁石などの分野において種々の磁性材料が用いられている。磁性材料の一つであるＳｍＣｏ系合金は、極めて高い保磁力及び一軸性の結晶磁気異方性を有し、ナノ粒子化しても高い磁気特性を示すことが知られている。このため、ＳｍＣｏ系合金は高密度記録を実現する磁気記録媒体をはじめとする様々な磁性材料に利用可能な魅力的な材料の一つである。 Various magnetic materials are used in fields such as magnetic recording media and magnets. It is known that an SmCo-based alloy, which is one of magnetic materials, has extremely high coercive force and uniaxial crystal magnetic anisotropy, and exhibits high magnetic properties even when it is made into nanoparticles. Therefore, SmCo-based alloys are one of attractive materials that can be used for various magnetic materials including magnetic recording media that realize high-density recording.
ＳｍＣｏ系合金粒子の合成方法については、物理学的手法であるスパッタでＳｍＣｏ５合金粒子を合成できることが知られている（例えば、非特許文献１参照）。また、別の方法として、クラスタ・ガンで気相凝縮させて、ＳｍＣｏ系合金粒子を製造する方法も提案されている（例えば、非特許文献２参照）。 The synthesis method of SmCo-based alloy particles, can be synthesized SmCo 5 alloy particles by sputtering a physical method are known (e.g., see Non-Patent Document 1). As another method, a method of producing SmCo-based alloy particles by vapor-phase condensation with a cluster gun has been proposed (see, for example, Non-Patent Document 2).
一方、化学的手法を用いたＳｍＣｏ系合金粒子の合成方法として、ポリオール還元法を用いて合成すること（例えば、特許文献１参照）、及びマイクロウエーブを用いたポリオール還元法を用いて合成すること（例えば、特許文献２参照）が提案されている。
しかしながら、本発明者らの検討によれば、非特許文献１及び２のような物理学的手法による合成方法により得られるＳｍＣｏ系粒子は、磁気特性が十分に高くないことがわかった。また、上記合成方法は、熱処理工程が必要であり、ＳｍＣｏ系粒子の収率も低いことから、工業的な量産化に不適であることがわかった。 However, according to the study by the present inventors, it has been found that the SmCo-based particles obtained by the synthesis method using physical methods such as Non-Patent Documents 1 and 2 do not have sufficiently high magnetic properties. In addition, the above synthesis method requires a heat treatment step, and the yield of SmCo-based particles is low. Therefore, it was found that the synthesis method is unsuitable for industrial mass production.
一方、特許文献１のＳｍＣｏ系合金粒子は、常温における保磁力（Ｈｃ）が５００Ｏｅと低い。また、特許文献２のＳｍＣｏ系合金ナノ粒子は、極低温で磁気特性が観察されているに過ぎない。このように特許文献１及び２のＳｍＣｏ系合金粒子の磁気特性が低いのは、サマリウム塩が還元し難い物質であるため、生成後のＳｍＣｏ系合金粒子が未反応のサマリウム塩等を多く含んでいることに起因していると考えられる。 On the other hand, the SmCo-based alloy particles of Patent Document 1 have a low coercivity (Hc) at a normal temperature of 500 Oe. In addition, the magnetic properties of the SmCo-based alloy nanoparticles of Patent Document 2 are only observed at extremely low temperatures. As described above, the magnetic properties of the SmCo-based alloy particles of Patent Documents 1 and 2 are low because the samarium salt is a substance that is difficult to reduce. Therefore, the SmCo-based alloy particles after generation contain a large amount of unreacted samarium salt and the like. This is thought to be due to the fact that
したがって、磁気特性が十分に優れ、且つ十分に小さい粒径を有するＳｍＣｏ系粒子が求められている。また、そのようなＳｍＣｏ系合金ナノ粒子を容易に量産できる製造方法が求められている。 Accordingly, there is a need for SmCo-based particles that have sufficiently good magnetic properties and a sufficiently small particle size. There is also a need for a production method that can easily mass-produce such SmCo-based alloy nanoparticles.
本発明は上記事情に鑑みてなされたものであり、十分に小さい粒径を有するとともに磁気特性に十分優れるＳｍＣｏ系合金ナノ粒子を提供すること、及びそのようなＳｍＣｏ系合金ナノ粒子を高収率で量産可能な製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and provides an SmCo-based alloy nanoparticle having a sufficiently small particle size and sufficiently excellent magnetic properties, and a high yield of such an SmCo-based alloy nanoparticle. It aims at providing the manufacturing method which can be mass-produced by.
上記目的を達成するため、本発明では、構成元素としてＳｍ及びＣｏを有するＳｍＣｏ系合金を主成分として含有し、ＳｍＣｏ系合金に対するＳｍ及びＣｏとは異なる金属元素の含有量が０．０５〜２０質量％であるＳｍＣｏ系合金ナノ粒子を提供する。 In order to achieve the above object, in the present invention, an SmCo-based alloy having Sm and Co as constituent elements is contained as a main component, and the content of a metal element different from Sm and Co in the SmCo-based alloy is 0.05-20. Provided is SmCo-based alloy nanoparticles of mass%.
このようなＳｍＣｏ系合金ナノ粒子は、粒径が十分に小さいうえに、磁気特性に十分に優れているため、磁性材料として好適に用いることができる。このように、本発明のＳｍＣｏ系合金ナノ粒子が磁気特性に十分に優れている理由は、未反応成分が十分に低減され、主成分としてＳｍＣｏ系合金を含有しているためである。また、本発明のＳｍＣｏ系合金ナノ粒子は、Ｓｍ及びＣｏとは異なる金属元素の含有量を変えることによって、磁気特性や粒径を制御することができ、磁石や磁気記録媒体の設計の自由度を向上させることができる。 Such SmCo-based alloy nanoparticles have a sufficiently small particle size and are sufficiently excellent in magnetic properties, and thus can be suitably used as a magnetic material. Thus, the reason why the SmCo-based alloy nanoparticles of the present invention are sufficiently excellent in magnetic properties is that the unreacted components are sufficiently reduced and the SmCo-based alloy is contained as a main component. In addition, the SmCo-based alloy nanoparticles of the present invention can control the magnetic properties and particle size by changing the content of metal elements different from Sm and Co, and the degree of freedom in designing magnets and magnetic recording media. Can be improved.
本発明のＳｍＣｏ系合金ナノ粒子は、ＳｍＣｏ系合金に対して上記金属元素を０．０５〜１０質量％含有することが好ましい。このようなＳｍＣｏ系合金ナノ粒子は、一層優れた磁気特性を有する。 The SmCo-based alloy nanoparticles of the present invention preferably contain 0.05 to 10% by mass of the above metal element with respect to the SmCo-based alloy. Such SmCo-based alloy nanoparticles have more excellent magnetic properties.
本発明のＳｍＣｏ系合金ナノ粒子は、金属元素が、Ａｕ，Ａｇ，Ｐｔ，Ｐｄ，Ｒｈ，Ｒｕ，Ｉｒ，Ｏｓ，Ｃｕ，Ｎｉ，Ｃｒ，Ａｌ，Ｍｎからなる群より選ばれる少なくとも一つの元素を含有することが好ましい。金属元素として上記金属元素を含有するＳｍＣｏ系合金ナノ粒子は、一層優れた磁気特性を有する。 In the SmCo-based alloy nanoparticles of the present invention, the metal element is at least one element selected from the group consisting of Au, Ag, Pt, Pd, Rh, Ru, Ir, Os, Cu, Ni, Cr, Al, and Mn. It is preferable to contain. SmCo-based alloy nanoparticles containing the above metal element as a metal element have even more excellent magnetic properties.
本発明のＳｍＣｏ系合金ナノ粒子は、粒径が１〜３０ｎｍであることが好ましい。このようなＳｍＣｏ系合金ナノ粒子は、例えば高密度記録を実現するための磁気記録媒体に好適に用いられる。 The SmCo-based alloy nanoparticles of the present invention preferably have a particle size of 1 to 30 nm. Such SmCo-based alloy nanoparticles are suitably used for a magnetic recording medium for realizing high-density recording, for example.
本発明のＳｍＣｏ系合金ナノ粒子は、サマリウム塩、コバルト塩、及び金属元素の塩を含む有機溶媒に、強還元剤を加えて、サマリウム塩、コバルト塩、及び金属元素の塩を還元させる湿式合成により得られるものであることが好ましい。このようなＳｍＣｏ系合金ナノ粒子は、量産性に優れ且つ粒度分布も比較的良好なことから、磁性材料の原料として産業上、特に有用である。 The SmCo-based alloy nanoparticles of the present invention are prepared by wet synthesis in which a strong reducing agent is added to an organic solvent containing a samarium salt, a cobalt salt, and a metal element salt to reduce the samarium salt, the cobalt salt, and the metal element salt. It is preferable that it is obtained by. Such SmCo-based alloy nanoparticles are particularly useful industrially as raw materials for magnetic materials because of their excellent mass productivity and relatively good particle size distribution.
本発明のＳｍＣｏ系合金ナノ粒子は、コア部分と、該コア部分を覆うシェル部分とを有するコアシェル構造を備えており、コア部分におけるＳｍＣｏ系合金に対する上記金属元素の比率が、シェル部分の当該比率よりも大きいことが好ましい。 The SmCo-based alloy nanoparticles of the present invention have a core-shell structure having a core portion and a shell portion covering the core portion, and the ratio of the metal element to the SmCo-based alloy in the core portion is the ratio of the shell portion. Is preferably larger.
本発明ではまた、サマリウム塩、コバルト塩、Ｓｍ及びＣｏとは異なる金属元素の塩、並びに保護剤を含む原料を、還元性を有する有機溶媒とともに混合して混合液を得る混合工程と、混合液に、強還元剤を添加して加熱することにより、サマリウム塩、コバルト塩及び金属元素の塩を還元する還元工程とを有する、構成元素としてＳｍ及びＣｏを有するＳｍＣｏ系合金を主成分として含有するＳｍＣｏ系合金ナノ粒子の製造方法を提供する。 In the present invention, a mixing step of mixing a samarium salt, a cobalt salt, a salt of a metal element different from Sm and Co, and a raw material containing a protective agent together with a reducing organic solvent to obtain a mixed solution; And a SmCo-based alloy having Sm and Co as constituent elements, comprising a reduction step of reducing a samarium salt, a cobalt salt and a metal element salt by adding a strong reducing agent and heating. A method for producing SmCo-based alloy nanoparticles is provided.
上述のＳｍＣｏ系合金ナノ粒子の製造方法では、粒径が十分に小さく且つ十分に優れた磁気特性を有するＳｍＣｏ系合金ナノ粒子を高収率で製造することができる。かかる効果が得られる理由を、本発明者らは以下の通り推察する。すなわち、サマリウム塩やコバルト塩を還元させる際に、原料中に含まれるＳｍ及びＣｏとは異なる金属元素の塩が速やかに還元され、当該金属元素が結晶析出の核となってＳｍＣｏ系合金の結晶の析出を促進する、いわゆる触媒的な作用を奏すると考えられる。これによって、未反応物の含有量が十分に低減されたＳｍＣｏ系合金ナノ粒子を円滑に合成することが可能となる。また、金属元素の触媒的な作用によって、反応時間が十分に短縮されるため、生成したＳｍＣｏ系合金ナノ粒子の粒成長が抑制される。したがって、磁気特性に十分優れるとともに、粒径が十分に小さいＳｍＣｏ系合金ナノ粒子を合成することができる。また、本発明の製造方法は、原料を還元させてＳｍＣｏ系合金ナノ粒子を合成するという化学的手法を用いていることから、スパッタなどの物理的手法に比べて、高い収率でＳｍＣｏ系合金ナノ粒子を量産することが可能である。 In the above-described method for producing SmCo-based alloy nanoparticles, SmCo-based alloy nanoparticles having a sufficiently small particle size and sufficiently excellent magnetic properties can be produced in high yield. The present inventors infer the reason why such an effect is obtained as follows. That is, when reducing a samarium salt or a cobalt salt, a salt of a metal element different from Sm and Co contained in the raw material is rapidly reduced, and the metal element serves as a nucleus for crystal precipitation to form a crystal of the SmCo-based alloy. It is considered that there is a so-called catalytic action that promotes the precipitation of. This makes it possible to smoothly synthesize SmCo-based alloy nanoparticles in which the content of unreacted materials is sufficiently reduced. Moreover, since the reaction time is sufficiently shortened by the catalytic action of the metal element, the grain growth of the generated SmCo-based alloy nanoparticles is suppressed. Therefore, it is possible to synthesize SmCo-based alloy nanoparticles having a sufficiently excellent magnetic property and a sufficiently small particle size. In addition, since the production method of the present invention uses a chemical method of synthesizing SmCo-based alloy nanoparticles by reducing the raw material, the SmCo-based alloy is produced in a higher yield than physical methods such as sputtering. It is possible to mass-produce nanoparticles.
本発明の製造方法は、還元工程の前に、混合工程で得られた混合液を撹拌加熱して脱水し、冷却する脱水工程を有することが好ましい。これによって、還元工程の前に水分が十分に除去されるため、Ｓｍ及びＣｏの酸化を抑制し、サマリウム塩及びコバルト塩の還元反応を一層円滑に進めることができる。また、混合液を脱水後に室温付近まで冷却した後、強還元剤を添加し、その後再び撹拌加熱することで、還元反応が一気に進行することに伴う突沸の防止及び不純物生成の低減を図ることができる。すなわち、冷却した後に強還元剤を添加することにより、未反応物の含有量が一層低減され、ＳｍＣｏ系合金以外の不純物の含有量が一層低減された磁気特性に優れるＳｍＣｏ系合金ナノ粒子を高収率で製造することができる。 The production method of the present invention preferably has a dehydration step of dehydrating and cooling the mixed liquid obtained in the mixing step by stirring and heating before the reduction step. Accordingly, moisture is sufficiently removed before the reduction step, so that the oxidation of Sm and Co can be suppressed, and the reduction reaction of the samarium salt and the cobalt salt can proceed more smoothly. In addition, after cooling the mixed solution to near room temperature, a strong reducing agent is added, and then stirred and heated again, thereby preventing bumping and reducing impurity generation due to a rapid progress of the reduction reaction. it can. That is, by adding a strong reducing agent after cooling, the content of unreacted substances is further reduced, and the content of impurities other than SmCo alloys is further reduced. It can be produced in a yield.
また、本発明の製造方法は、金属元素が、Ａｕ，Ａｇ，Ｐｔ，Ｐｄ，Ｒｈ，Ｒｕ，Ｉｒ，Ｏｓ，Ｃｕ，Ｎｉ，Ｃｒ，Ａｌ，Ｍｎからなる群より選ばれる少なくとも一つの元素を含有することが好ましい。このような金属元素は、サマリウム塩やコバルト塩よりも還元され易いため、結晶生成の核として速やかに還元され、一層優れた触媒的作用を奏すると考えられる。したがって、サマリウム塩及びコバルト塩の還元反応を一層促進することができる。 In the production method of the present invention, the metal element contains at least one element selected from the group consisting of Au, Ag, Pt, Pd, Rh, Ru, Ir, Os, Cu, Ni, Cr, Al, and Mn. It is preferable to do. Since such a metal element is more easily reduced than samarium salt or cobalt salt, it is considered that the metal element is rapidly reduced as a nucleus of crystal formation and exhibits a more excellent catalytic action. Therefore, the reduction reaction of samarium salt and cobalt salt can be further promoted.
また、本発明の製造方法は、強還元剤が、ＬｉＡｌＨ４、ＮａＢＨ４、Ｎ２Ｈ４、Ｂ２Ｈ６、ＬｉＢＨ（Ｃ２Ｈ５）３からなる群より選ばれる少なくとも一つを含有することが好ましい。これによって、未反応のサマリウム塩やコバルト塩の残存量が一層低減されたＳｍＣｏ系合金ナノ粒子を得ることができる。 In the production method of the present invention, the strong reducing agent contains at least one selected from the group consisting of LiAlH 4 , NaBH 4 , N 2 H 4 , B 2 H 6 , and LiBH (C 2 H 5 ) 3. It is preferable. Thereby, SmCo-based alloy nanoparticles in which the remaining amount of unreacted samarium salt or cobalt salt is further reduced can be obtained.
本発明によれば、十分に小さい粒径を有するとともに磁気特性に十分優れるＳｍＣｏ系合金ナノ粒子を提供すること、及びそのようなＳｍＣｏ系合金ナノ粒子を高収率で量産可能な製造方法を提供することができる。 According to the present invention, an SmCo-based alloy nanoparticle having a sufficiently small particle size and sufficiently excellent magnetic properties is provided, and a production method capable of mass-producing such an SmCo-based alloy nanoparticle at a high yield is provided. can do.
以下、場合により図面を参照して、本発明の好適な実施形態について説明する。 In the following, preferred embodiments of the present invention will be described with reference to the drawings as the case may be.
本実施形態のＳｍＣｏ系合金ナノ粒子は、１〜３０ｎｍの平均粒径を有する。このように、ナノサイズの粒径を有するＳｍＣｏ系合金ナノ粒子は、磁気特性に優れるうえに粒径が十分に小さいことから、磁気記録媒体の磁性粉末として用いることにより記録密度を向上させることができる。ＳｍＣｏ系合金ナノ粒子の粒径は、透過型電子顕微鏡（ＴＥＭ）で観察することにより測定することができる。 The SmCo-based alloy nanoparticles of this embodiment have an average particle size of 1 to 30 nm. As described above, the SmCo-based alloy nanoparticles having a nano-sized particle size are excellent in magnetic properties and have a sufficiently small particle size, so that the recording density can be improved by using as a magnetic powder of a magnetic recording medium. it can. The particle size of the SmCo-based alloy nanoparticles can be measured by observing with a transmission electron microscope (TEM).
ＳｍＣｏ系合金ナノ粒子の主成分であるＳｍＣｏ系合金の好適な組成は、ＳｍＣｏ５である。図１（ａ）は、本実施形態のＳｍＣｏ５を主成分として含有するＳｍＣｏ系合金ナノ粒子の高分解能ＴＥＭ写真であり、図１（ｂ）は本実施形態のＳｍＣｏ５を主成分として含有するＳｍＣｏ系合金ナノ粒子の電子線回折像である。このような組成のＳｍＣｏ系合金ナノ粒子は優れた保磁力（Ｈｃ）及び磁化量を有している。ＳｍＣｏ系合金ナノ粒子の組成は、ＩＣＰ発光分光分析などによって確認することができる。なお、ＳｍＣｏ５は、ＣａＣｕ５型の結晶構造を有することから、Ｘ線回折（ＸＲＤ）によっても同定することができる。 Preferred composition of which is the main component SmCo-based alloy of SmCo-based alloy nanoparticles are SmCo 5. FIG. 1A is a high-resolution TEM photograph of SmCo-based alloy nanoparticles containing SmCo 5 of this embodiment as a main component, and FIG. 1B contains SmCo 5 of this embodiment as a main component. 2 is an electron diffraction image of SmCo-based alloy nanoparticles. The SmCo-based alloy nanoparticles having such a composition have excellent coercive force (Hc) and magnetization. The composition of the SmCo-based alloy nanoparticles can be confirmed by ICP emission spectroscopic analysis or the like. Since SmCo 5 has a CaCu 5 type crystal structure, it can also be identified by X-ray diffraction (XRD).
本実施形態のＳｍＣｏ系合金ナノ粒子は、ＳｍＣｏ系合金を主成分として含有し、Ｓｍ及びＣｏとは異なる金属元素（以下、「第３金属元素」という。）を、ＳｍＣｏ系合金全体に対して０．０５〜２０質量％含有する。なお、第３金属元素は、ＳｍＣｏ系合金ナノ粒子に金属単体として含まれていてもよく、金属化合物として含まれていてもよい。 The SmCo-based alloy nanoparticles of the present embodiment contain an SmCo-based alloy as a main component, and a metal element different from Sm and Co (hereinafter referred to as “third metal element”) with respect to the entire SmCo-based alloy. It contains 0.05 to 20% by mass. The third metal element may be included in the SmCo-based alloy nanoparticles as a single metal or may be included as a metal compound.
当該第３金属元素の含有量は、ＳｍＣｏ系合金全体に対して０．０５〜２０質量％であることが好ましく、０．０５〜１０質量％であることがより好ましい。第３金属元素の含有量は、ＩＣＰ発光分光分析などによって確認することができる。 The content of the third metal element is preferably 0.05 to 20% by mass and more preferably 0.05 to 10% by mass with respect to the entire SmCo-based alloy. The content of the third metal element can be confirmed by ICP emission spectral analysis or the like.
ＳｍＣｏ系合金ナノ粒子の製造時において、第３金属元素の添加量が得られるＳｍＣｏ系合金ナノ粒子に対して０．０５質量％未満の場合、第３金属元素による改善効果が十分に得られず、ＳｍＣｏ系合金ナノ粒子の収率が低下するとともに未反応物の含有率が高くなり、磁気特性が低下する。一方、第３金属元素の含有量が２０質量％より多いと、磁気特性に寄与するＳｍＣｏ系合金の割合が少なくなるため、磁気特性が低下する。 When the SmCo-based alloy nanoparticles are produced, if the amount of the third metal element added is less than 0.05% by mass with respect to the obtained SmCo-based alloy nanoparticles, the improvement effect by the third metal element cannot be obtained sufficiently. In addition, the yield of SmCo-based alloy nanoparticles decreases, the unreacted content increases, and the magnetic properties decrease. On the other hand, when the content of the third metal element is more than 20% by mass, the ratio of the SmCo-based alloy that contributes to the magnetic characteristics decreases, and the magnetic characteristics deteriorate.
第３金属元素としては、Ａｕ，Ａｇ，Ｐｔ，Ｐｄ，Ｒｈ，Ｒｕ，Ｉｒ，Ｏｓなどの貴金属元素、またはＣｕ，Ｎｉ，Ｃｒ，Ｍｎなどの遷移金属元素が好ましい。また、これら以外の第３金属元素として、Ａｌを例示することができる。 As the third metal element, a noble metal element such as Au, Ag, Pt, Pd, Rh, Ru, Ir, or Os, or a transition metal element such as Cu, Ni, Cr, or Mn is preferable. Moreover, Al can be illustrated as a 3rd metal element other than these.
本実施形態のＳｍＣｏ系合金ナノ粒子は、主成分として第３金属元素を有するコア部分と、該コア部分の周囲を覆うように設けられる、主成分としてＳｍＣｏ系合金を有するシェル部分とからなるコアシェル構造を有していてもよい。 The SmCo-based alloy nanoparticles of the present embodiment include a core shell including a core portion having a third metal element as a main component and a shell portion having an SmCo-based alloy as a main component provided so as to cover the periphery of the core portion. You may have a structure.
図２は、本発明におけるＳｍＣｏ系合金ナノ粒子の微細構造の一例を示す電界放射型透過電子顕微鏡（ＦＥ−ＴＥＭ、日本電子株式会社製、商品名：ＪＥＭ−２０１０Ｆ）の写真である。図２に示す通り、１つのＳｍＣｏ系合金ナノ粒子にはコントラストの異なる領域が存在している。また、このＳｍＣｏ系合金ナノ粒子は多結晶体であり、コア部分（中心部分）とシェル部分（外殻部分）との干渉縞は互いに異なっている。このように、図２に示すＳｍＣｏ系合金ナノ粒子は、組成が互いに異なるコア部分とシェル部分とからなるコアシェル構造を有している。 FIG. 2 is a photograph of a field emission transmission electron microscope (FE-TEM, manufactured by JEOL Ltd., trade name: JEM-2010F) showing an example of the microstructure of the SmCo-based alloy nanoparticles in the present invention. As shown in FIG. 2, one SmCo-based alloy nanoparticle has regions having different contrasts. The SmCo-based alloy nanoparticles are polycrystalline, and interference fringes between the core portion (center portion) and the shell portion (outer shell portion) are different from each other. As described above, the SmCo-based alloy nanoparticles shown in FIG. 2 have a core-shell structure including a core portion and a shell portion having different compositions.
図３は、図２に示すＳｍＣｏ系合金ナノ粒子の走査型透過電子顕微鏡（ＳＴＥＭ）の写真である。元素分析をエネルギー分散型Ｘ線分析（ＥＤＳ、ＮＯＲＡＮ社製、商品名：ＮＯＲＡＮ−ＵＴＷ）により行ったところ、図３に示す通り、ＳｍＣｏ系合金ナノ粒子のコア部分（図３の領域１）には、第３金属元素（Ａｕ）が主成分として存在しており、シェル部分（図３の領域２）には、ＳｍＣｏ系合金が主成分として存在していることを確認した。 FIG. 3 is a scanning transmission electron microscope (STEM) photograph of the SmCo-based alloy nanoparticles shown in FIG. When elemental analysis was performed by energy dispersive X-ray analysis (EDS, manufactured by NORAN, trade name: NORAN-UTW), as shown in FIG. 3, the core portion of SmCo-based alloy nanoparticles (region 1 in FIG. 3) Confirmed that the third metal element (Au) was present as the main component, and that the SmCo-based alloy was present as the main component in the shell portion (region 2 in FIG. 3).
次に、本実施形態のＳｍＣｏ系合金ナノ粒子の製造方法について以下に説明する。本実施形態のＳｍＣｏ系合金ナノ粒子の製造方法は、サマリウム塩、コバルト塩、第３金属元素の塩を、それぞれ還元性を有する有機溶媒に溶解させて溶液を作成する準備工程と、サマリウム塩を含む溶液、コバルト塩を含む溶液及び第３金属元素の塩を含む溶液を混合して混合液を得る混合工程と、混合工程で得られた混合液に保護剤を添加する添加工程と、保護剤を添加した混合液を加熱して脱水する脱水工程と、脱水後の混合液に強還元剤を添加してサマリウム塩、コバルト塩及び第３金属元素の塩を還元することにより第３金属元素を含有するＳｍＣｏ系合金ナノ粒子を得る還元工程とを有する。以下、各工程の詳細について説明する。 Next, a method for producing the SmCo-based alloy nanoparticles of this embodiment will be described below. The method for producing SmCo-based alloy nanoparticles according to the present embodiment includes a samarium salt, a cobalt salt, and a third metal element salt dissolved in a reducing organic solvent to prepare a solution, and a samarium salt A mixing step of mixing a solution containing, a solution containing a cobalt salt, and a solution containing a salt of a third metal element to obtain a mixed solution, an adding step of adding a protective agent to the mixed solution obtained in the mixing step, and a protective agent A dehydration step of heating and dehydrating the mixed solution, and adding a strong reducing agent to the dehydrated mixed solution to reduce the samarium salt, cobalt salt, and third metal element salt, thereby reducing the third metal element. And a reduction step for obtaining SmCo-based alloy nanoparticles contained therein. Details of each step will be described below.
（準備工程）
本実施形態に用いられるＳｍ（サマリウム）塩としては、サマリウムアセチルアセトナート水和物（［ＣＨ３ＣＯＣＨ＝Ｃ（Ｏ−）ＣＨ３］３Ｓｍ・ｘＨ２Ｏ）、Ｃｏ（コバルト）塩としては、コバルトアセチルアセトナート（［ＣＨ３ＣＯＣＨ＝Ｃ（Ｏ−）ＣＨ３］３Ｃｏ）を例示できる。これらの塩は、有機溶媒に溶解し易く、且つ比較的還元され易いため、粒径が小さく純度の高いＳｍＣｏ系合金ナノ粒子を得る観点から、好ましく用いることができる。
(Preparation process)
Examples of the Sm (samarium) salt used in the present embodiment include samarium acetylacetonate hydrate ([CH 3 COCH═C (O—) CH 3 ] 3 Sm · xH 2 O) and Co (cobalt) salt. And cobalt acetylacetonate ([CH 3 COCH═C (O—) CH 3 ] 3 Co). Since these salts are easily dissolved in an organic solvent and relatively easily reduced, they can be preferably used from the viewpoint of obtaining SmCo-based alloy nanoparticles having a small particle size and high purity.
第３金属元素の塩としては、アセチルアセトナート塩を例示することができる。アセチルアセトナート塩は有機溶媒に溶解しやすいことから好適に用いることができる。 As the salt of the third metal element, an acetylacetonate salt can be exemplified. An acetylacetonate salt can be suitably used because it is easily dissolved in an organic solvent.
サマリウム塩、コバルト塩、第３金属元素の塩を溶解させる有機溶媒は、高沸点のものを好ましく用いることができる。具体的には、１，２−ヘキサデカンジオールを例示することができる。この１，２−ヘキサデカンジオールは、還元作用を有する。 As the organic solvent for dissolving the samarium salt, the cobalt salt, and the salt of the third metal element, those having a high boiling point can be preferably used. Specifically, 1,2-hexadecanediol can be exemplified. This 1,2-hexadecanediol has a reducing action.
準備工程では、１，２−ヘキサデカンジオールにサマリウム塩、コバルト塩、第３金属元素の塩を溶解させることによって、サマリウム塩を含む溶液、コバルト塩を含む溶液、及び第３金属元素の塩を含む溶液を得ることができる。なお、Ｓｍ，Ｃｏ，第３金属元素の酸化を防止するために、準備工程は、窒素またはアルゴンなどの不活性ガス雰囲気下で行うことが好ましい。 In the preparation step, a solution containing a samarium salt, a solution containing a cobalt salt, and a salt of a third metal element are included by dissolving a samarium salt, a cobalt salt, and a salt of a third metal element in 1,2-hexadecanediol. A solution can be obtained. In order to prevent oxidation of Sm, Co, and the third metal element, it is preferable that the preparatory process is performed in an inert gas atmosphere such as nitrogen or argon.
（混合工程）
混合工程では、上述の通り調製した各溶液を混合する。混合する順番に特に制限はなく、３つの溶液を同時に混合してもよいし、２つの溶液を混合した後に、残りの溶液を混合して混合液を得てもよい。
(Mixing process)
In the mixing step, the solutions prepared as described above are mixed. There is no restriction | limiting in particular in the order of mixing, Three solutions may be mixed simultaneously, and after mixing two solutions, the remaining solution may be mixed and a liquid mixture may be obtained.
第３金属元素の塩の溶液を混合する量としては、サマリウム塩及びコバルト塩にそれぞれ含まれるサマリウム元素及びコバルト元素の合計１ｍｏｌに対し、第３金属元素に換算して０．０１〜０．５ｍｏｌとすることが好ましい。 The amount of the salt solution of the third metal element to be mixed is 0.01 to 0.5 mol in terms of the third metal element with respect to a total of 1 mol of samarium element and cobalt element contained in the samarium salt and cobalt salt, respectively. It is preferable that
混合工程は、Ｓｍ，Ｃｏ，第３金属元素の酸化を防止するために、窒素またはアルゴンなどの不活性ガス雰囲気下で行うことが好ましい。 The mixing step is preferably performed in an inert gas atmosphere such as nitrogen or argon in order to prevent oxidation of Sm, Co, and the third metal element.
（添加工程）
混合工程で得られた混合液に保護剤を添加する工程である。保護剤は、生成するＳｍＣｏ系合金ナノ粒子を保護する機能を有するものであり、オレイン酸、オレイルアミン、ポリビニルピロリドン、ポリビニルアルコール等を好適に用いることができる。この保護剤は、例えばエーテル類などの有機溶媒に溶解させて用いてもよい。
(Addition process)
In this step, a protective agent is added to the liquid mixture obtained in the mixing step. The protective agent has a function of protecting the produced SmCo-based alloy nanoparticles, and oleic acid, oleylamine, polyvinyl pyrrolidone, polyvinyl alcohol, and the like can be suitably used. This protective agent may be used by dissolving in an organic solvent such as ethers.
保護剤の添加量は、使用するサマリウム塩及びコバルト塩にそれぞれ含まれるサマリウム元素及びコバルト元素の合計１ｍｏｌに対し、０．１〜２０ｍｏｌとすることが好ましい。 The addition amount of the protective agent is preferably 0.1 to 20 mol with respect to 1 mol in total of the samarium element and cobalt element contained in the samarium salt and cobalt salt to be used, respectively.
（脱水工程）
脱水工程は、不活性ガスフロー下または不活性ガス置換後の減圧下で混合液を撹拌加熱して脱水する工程である。混合液に含まれる水分を十分に低減することによって、還元されたＳｍやＣｏ等が酸化されるのを十分に抑制することができる。したがって、一層高い収率でＳｍＣｏ系合金ナノ粒子を得ることが可能となる。
(Dehydration process)
The dehydration step is a step of dehydrating the mixed liquid by stirring and heating under an inert gas flow or under reduced pressure after the inert gas replacement. By sufficiently reducing the moisture contained in the mixed solution, it is possible to sufficiently suppress the reduction of the reduced Sm, Co and the like. Therefore, it is possible to obtain SmCo-based alloy nanoparticles with a higher yield.
混合液の加熱は、１１０〜２２０℃で１〜２４時間行なうことが好ましい。その後、混合液を室温まで冷却することが好ましく、１０〜３０℃に冷却することがより好ましい。これによって、次に説明する還元工程における強還元剤による還元反応を確実に行うことができ、純度の高いＳｍＣｏ系合金ナノ粒子を得ることができる。一方、ここで冷却せずに、温度が高い状態（例えば５０℃以上）で強還元剤の添加を行うと、強還元剤による還元反応が一気に進んでしまうため、例えばコバルト単体（Ｃｏ金属）などのＳｍＣｏ系合金以外の不純物が生成し、ＳｍＣｏ系合金の含有量が減少する傾向がある。 The mixture is preferably heated at 110 to 220 ° C. for 1 to 24 hours. Then, it is preferable to cool a liquid mixture to room temperature, and it is more preferable to cool to 10-30 degreeC. As a result, a reduction reaction with a strong reducing agent in the reduction step described below can be performed reliably, and high-purity SmCo-based alloy nanoparticles can be obtained. On the other hand, if a strong reducing agent is added at a high temperature (for example, 50 ° C. or higher) without cooling, the reduction reaction by the strong reducing agent proceeds at a stretch. For example, cobalt alone (Co metal) or the like Impurities other than the SmCo-based alloy are generated, and the content of the SmCo-based alloy tends to decrease.
（還元工程）
還元工程は、脱水工程後の混合液に強還元剤を添加した後、撹拌加熱することで、Ｓｍ塩、Ｃｏ塩及び第３金属元素の塩を十分に還元して、第３金属元素を含有するＳｍＣｏ系合金ナノ粒子を製造する工程である。
(Reduction process)
In the reduction step, a strong reducing agent is added to the mixed solution after the dehydration step, followed by stirring and heating, thereby sufficiently reducing the Sm salt, the Co salt, and the salt of the third metal element to contain the third metal element. This is a process for producing SmCo-based alloy nanoparticles.
強還元剤としては、ＬｉＡｌＨ４、ＮａＢＨ４、Ｎ２Ｈ４、Ｂ２Ｈ６、ＬｉＢＨ（Ｃ２Ｈ５）３からなる群より選ばれる少なくとも一つを用いることができる。なお、これらの強還元剤は、アルコールなどの有機溶媒に溶解させて混合液に添加することが好ましい。 As the strong reducing agent, at least one selected from the group consisting of LiAlH 4 , NaBH 4 , N 2 H 4 , B 2 H 6 , and LiBH (C 2 H 5 ) 3 can be used. These strong reducing agents are preferably dissolved in an organic solvent such as alcohol and added to the mixed solution.
強還元剤を添加した後、油浴やマントルヒータを用いて、混合液を１５０〜３２０℃、好ましくは２５０〜２８０℃に保ち、１〜３時間加熱還流させて、強還元剤と還元作用を有する有機溶媒とによる還元反応を行うことにより、反応液を得ることができる。この還元反応によって、Ｓｍ塩、Ｃｏ塩及び第３金属元素の塩が還元される。得られた反応液から、溶媒を除去することによって、第３金属元素を含有するＳｍＣｏ系合金ナノ粒子が得られる。 After adding the strong reducing agent, the mixture is kept at 150 to 320 ° C., preferably 250 to 280 ° C. using an oil bath or a mantle heater, and heated to reflux for 1 to 3 hours to reduce the strong reducing agent and reducing action. A reaction solution can be obtained by performing a reduction reaction with an organic solvent. By this reduction reaction, the Sm salt, the Co salt, and the salt of the third metal element are reduced. By removing the solvent from the obtained reaction solution, SmCo-based alloy nanoparticles containing the third metal element can be obtained.
なお、上述の還元反応において、Ｓｍ塩及びＣｏ塩よりも第３金属元素の塩が還元されやすい性質を有する場合、Ｓｍ塩及びＣｏ塩よりも先に還元される傾向がある。このため、第３金属元素が核となり、その核を起点として、ＳｍＣｏ系合金が析出すると考えられる。このような、第３金属元素の存在によって、Ｓｍ塩及びＣｏ塩が一層円滑に還元されて、不純物の含有量が十分に低減された第３金属元素を含有するＳｍＣｏ系合金ナノ粒子を得ることができる。 In the above reduction reaction, when the salt of the third metal element is more easily reduced than the Sm salt and the Co salt, there is a tendency to reduce the salt earlier than the Sm salt and the Co salt. For this reason, it is considered that the third metal element becomes a nucleus, and the SmCo-based alloy is precipitated from the nucleus. By the presence of the third metal element, the Sm salt and the Co salt are more smoothly reduced, and the SmCo-based alloy nanoparticles containing the third metal element in which the impurity content is sufficiently reduced are obtained. Can do.
上述の第３金属元素を含有するＳｍＣｏ系合金ナノ粒子は、十分に小さい粒径と優れた磁気特性とを併せ持つことから、磁性材料として好適に用いることができる。なお、ＳｍＣｏ系合金ナノ粒子の粒径は、保護剤の添加量や第３金属元素の含有量を本発明の範囲内で変化させたり、還元工程における加熱還流の温度・時間を変えたりすることによって調整することができる。 The SmCo-based alloy nanoparticles containing the third metal element described above can be suitably used as a magnetic material because they have both a sufficiently small particle size and excellent magnetic properties. In addition, the particle size of the SmCo-based alloy nanoparticles may change the amount of the protective agent added or the content of the third metal element within the scope of the present invention, or change the temperature and time of heating and reflux in the reduction process. Can be adjusted by.
本実施形態に係る製造方法によれば、第３金属を含有するＳｍＣｏ系合金ナノ粒子を高い収率で合成することができる。なお、本実施形態の製造方法によって得られるナノ粒子は、第３元素を含有しないＳｍＣｏ系合金を主成分とするナノ粒子や、第３金属元素のナノ粒子を含んでいてもよい。 According to the manufacturing method according to the present embodiment, SmCo-based alloy nanoparticles containing a third metal can be synthesized with high yield. Note that the nanoparticles obtained by the production method of the present embodiment may include nanoparticles mainly composed of an SmCo-based alloy that does not contain a third element, or nanoparticles of a third metal element.
以上、本発明の好適な実施形態について説明したが、本発明は上記実施形態に何ら限定されるものではない。 The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.
以下、実施例及び比較例に基づき本発明をさらに具体的に説明するが、本発明は以下の実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.
（実施例１〜８）
［ＳｍＣｏ系合金ナノ粒子の合成］
サマリウムアセチルアセトナート水和物（［ＣＨ３ＣＯＣＨ＝Ｃ（Ｏ−）ＣＨ３］３Ｓｍ・ｘＨ２Ｏ）０．３３ｍｍｏｌと、表１に示す第３金属の塩０．０２〜０．５ｍｍｏｌとを１，２−ヘキサデカンジオール（ＣＨ３（ＣＨ２）１３ＣＨ（ＯＨ）ＣＨ２ＯＨ）２ｍｌに窒素雰囲気下で溶解させて第１の溶液を作製した。
(Examples 1-8)
[Synthesis of SmCo-based alloy nanoparticles]
Samarium acetylacetonate hydrate ([CH 3 COCH═C (O—) CH 3 ] 3 Sm · xH 2 O) 0.33 mmol, third metal salt 0.02 to 0.5 mmol shown in Table 1, Was dissolved in 2 ml of 1,2-hexadecanediol (CH 3 (CH 2 ) 13 CH (OH) CH 2 OH) under a nitrogen atmosphere to prepare a first solution.
上記溶液とは別に、コバルトアセチルアセトナート（［ＣＨ３ＣＯＣＨ＝Ｃ（Ｏ−）ＣＨ３］３Ｃｏ）１．６７ｍｍｏｌを、１，２ヘキサデカンジオール２ｍｌに窒素雰囲気下で溶解させ、第２の溶液を作製した。 Separately from the above solution, 1.67 mmol of cobalt acetylacetonate ([CH 3 COCH═C (O—) CH 3 ] 3 Co) was dissolved in 2 ml of 1,2 hexadecandiol under a nitrogen atmosphere to obtain a second solution. Was made.
オクチルエーテル（［ＣＨ３（ＣＨ２）７］２Ｏ）４０ｍｌに、オレイン酸（ＣＨ３（ＣＨ２）７ＣＨ＝ＣＨ（ＣＨ２）７ＣＯＯＨ）３．０ｍｍｏｌと、オレイルアミン（ＣＨ３（ＣＨ２）７ＣＨ＝ＣＨ（ＣＨ２）８ＮＨ２）３．０ｍｍｏｌとを不活性気体（例えば、窒素、アルゴン）雰囲気下で溶解させ、第３の溶液を作製した。 To 40 ml of octyl ether ([CH 3 (CH 2 ) 7 ] 2 O), 3.0 mmol of oleic acid (CH 3 (CH 2 ) 7 CH═CH (CH 2 ) 7 COOH) and oleylamine (CH 3 (CH 2) ) 7 CH═CH (CH 2 ) 8 NH 2 ) (3.0 mmol) was dissolved in an inert gas (eg, nitrogen, argon) atmosphere to prepare a third solution.
次に、第１の溶液、第２の溶液及び第３の溶液を、メカニカルスターラーを使用して窒素雰囲気下で約１２時間混合し、混合液を得た。 Next, the first solution, the second solution, and the third solution were mixed for about 12 hours under a nitrogen atmosphere using a mechanical stirrer to obtain a mixed solution.
混合液中に含まれる水を除去するため、窒素気流下で、混合液の入った３口フラスコを油浴中で２００℃に加熱して約１時間維持し、その後、室温（約２０℃）まで冷却した。そして、冷却した混合液に、強還元剤であるナトリウムボロン水素化物（ＮａＢＨ４）６ｍｍｏｌを溶解させた無水エタノールを添加した。 In order to remove water contained in the mixed solution, a three-necked flask containing the mixed solution was heated to 200 ° C. in an oil bath and maintained for about 1 hour under a nitrogen stream, and then room temperature (about 20 ° C.). Until cooled. Then, absolute ethanol in which 6 mmol of sodium boron hydride (NaBH 4 ) as a strong reducing agent was dissolved was added to the cooled mixture.
その後、油浴の温度を上げて反応溶液を２５０〜２８０℃に保ち、１〜３時間加熱還流させた。室温まで冷却後、ウルトラフィルターを用いて濾過して脱水エタノール等で溶液変換と粒子の洗浄を行った。その後、エバポレータを用いて粒子に付着している溶媒を留去し、４０℃で真空乾燥を１０時間以上行って、実施例１〜８の粒子を得た。 Thereafter, the temperature of the oil bath was raised, the reaction solution was kept at 250 to 280 ° C., and heated to reflux for 1 to 3 hours. After cooling to room temperature, the solution was filtered using an ultrafilter and subjected to solution conversion and particle washing with dehydrated ethanol or the like. Then, the solvent adhering to particle | grains was distilled off using the evaporator, and it vacuum-dried at 40 degreeC for 10 hours or more, and obtained the particle | grains of Examples 1-8.
［粒子の評価］
得られた実施例１〜８の粒子の高分解能ＴＥＭ（日本電子株式会社製、商品名：ＪＥＭ−３０１０）観察（３，０００，０００倍）を行った。そして、電子顕微鏡画像からランダムに１００個の粒子を抽出し、平均粒径を算出した。その結果、合成した粒子の平均粒径は表１に示すとおりであった。
[Evaluation of particles]
The particles of Examples 1 to 8 thus obtained were observed (3,000,000 times) by high-resolution TEM (manufactured by JEOL Ltd., trade name: JEM-3010). Then, 100 particles were randomly extracted from the electron microscope image, and the average particle size was calculated. As a result, the average particle diameter of the synthesized particles was as shown in Table 1.
得られた粒子のＸ線回折（ＸＲＤ）測定及びＩＣＰ発光分光分析を行った。図４は、合成した粒子のＸＲＤ測定結果であり、上段のチャートは実施例２で得られた粒子のＸＲＤチャートである。ＸＲＤの測定結果から、合成した実施例２の粒子は、酸化物などの不純物の量が十分に低減されたＳｍＣｏ５を主成分とする粒子（ＳｍＣｏ５粒子）であることが確認できた。また、高分解能ＴＥＭを用いた電子線回折像の解析結果においても、合成された粒子はＳｍＣｏ５であることが確認された。 The obtained particles were subjected to X-ray diffraction (XRD) measurement and ICP emission spectroscopic analysis. FIG. 4 shows the XRD measurement results of the synthesized particles, and the upper chart is the XRD chart of the particles obtained in Example 2. From the measurement results of XRD, the particles synthesized in Example 2, it was confirmed that the particles composed mainly of SmCo 5 in which the amount of impurities such as oxides is sufficiently reduced (SmCo 5 particles). Also in the analysis result of the electron beam diffraction image with high resolution TEM, it was confirmed synthesized particles are SmCo 5.
実施例１及び実施例３〜８の粒子も、酸化物などの不純物の量が十分に低減されたＳｍＣｏ５粒子であることがＸＲＤ及び高分解能ＴＥＭで確認できた。また、ＩＣＰ発光分光分析により求められた実施例１〜８の粒子における第３金属元素の含有量は、表１に示すとおりであった。 It was confirmed by XRD and high-resolution TEM that the particles of Example 1 and Examples 3 to 8 were SmCo 5 particles in which the amount of impurities such as oxides was sufficiently reduced. Further, the content of the third metal element in the particles of Examples 1 to 8 obtained by ICP emission spectroscopic analysis was as shown in Table 1.
実施例１〜８におけるＳｍＣｏ５粒子の収率は、表１に示すとおりであった。なお、当該収率は、Ｓｍ及びＣｏの使用量から算出されるＳｍＣｏ５の理論生成質量に対する、ＩＣＰ発行分光分析によって測定されたＳｍ元素及びＣｏ元素の合計質量の比率である。 The yield of SmCo 5 particles in Examples 1 to 8 was as shown in Table 1. The yield is the ratio of the total mass of Sm element and Co element measured by ICP emission spectroscopic analysis to the theoretically generated mass of SmCo 5 calculated from the amounts of Sm and Co used.
以上の評価結果から、第３金属元素を含有するＳｍＣｏ５ナノ粒子が高収率で得られることが確認された。 From the above evaluation results, it was confirmed that SmCo 5 nanoparticles containing the third metal element were obtained in high yield.
［磁気特性の評価］
実施例１〜８のＳｍＣｏ５ナノ粒子の保磁力（Ｈｃ）を、ＶＳＭ（振動試料型磁力計）（東英工業株式会社製、商品名：ＶＳＭ−５）を用いて、印加磁場２０ｋＯｅ、２５℃の条件で測定した。保磁力の測定結果は表１に示すとおりであった。図５は、実施例２のＳｍＣｏ５ナノ粒子の磁気特性を示すグラフである。実施例１及び実施例３〜８のＳｍＣｏ５ナノ粒子も、実施例２のＳｍＣｏ５ナノ粒子と同様に十分優れた磁気特性を示した。
[Evaluation of magnetic properties]
The coercive force (Hc) of the SmCo 5 nanoparticles of Examples 1 to 8 was measured using an applied magnetic field of 20 kOe, 25 using a VSM (vibrating sample magnetometer) (trade name: VSM-5, manufactured by Toei Kogyo Co., Ltd.). It measured on the conditions of (degreeC). The measurement results of the coercive force were as shown in Table 1. FIG. 5 is a graph showing the magnetic properties of the SmCo 5 nanoparticles of Example 2. The SmCo 5 nanoparticles of Example 1 and Examples 3 to 8 also exhibited sufficiently excellent magnetic properties as the SmCo 5 nanoparticles of Example 2.
（実施例９）
強還元剤として、ナトリウムボロン水素化物の代わりに、水素化アルミニウムリチウム（ＬｉＡｌＨ４）を用いたこと以外は、実施例２と同様にして合成を行い、粒子を得た。実施例２と同様にして粒子の評価及び磁気特性の評価を行ったところ、磁気特性に優れ、第３金属元素としてＣｕを含有するＳｍＣｏ５ナノ粒子が高収率で得られたことが分かった。ＳｍＣｏ５ナノ粒子の粒径、第３金属元素の含有量、収率及び保磁力（Ｈｃ）の測定結果は、表１に示すとおりであった。
Example 9
Synthesis was performed in the same manner as in Example 2 except that lithium aluminum hydride (LiAlH 4 ) was used instead of sodium boron hydride as a strong reducing agent, thereby obtaining particles. Particle evaluation and magnetic property evaluation were performed in the same manner as in Example 2. As a result, it was found that SmCo 5 nanoparticles having excellent magnetic properties and containing Cu as the third metal element were obtained in high yield. . The measurement results of the particle size of SmCo 5 nanoparticles, the content of the third metal element, the yield and the coercive force (Hc) were as shown in Table 1.
（比較例１）
第３金属の塩（パラジウムアセチルアセトナート）及びナトリウムボロン水素化物を用いなかったこと以外は実施例１と同様にして、ＳｍＣｏ５ナノ粒子の合成を行った。実施例１と同様にして粒子の評価及び磁気特性の評価を行った。図４の下段のチャートは比較例１で得られた粒子のＸＲＤチャートである。この分析結果より、粒子にはＳｍＣｏ系合金以外の化合物（Ｓｍ酸化物及びＣｏ酸化物など）が大量に含まれており、ＳｍＣｏ系合金を主成分とする粒子ではないことが確認された。得られた粒子の粒径、収率及び保磁力（Ｈｃ）は、表１に示すとおりであった。
(Comparative Example 1)
SmCo 5 nanoparticles were synthesized in the same manner as in Example 1 except that the third metal salt (palladium acetylacetonate) and sodium boron hydride were not used. In the same manner as in Example 1, evaluation of particles and evaluation of magnetic properties were performed. The lower chart of FIG. 4 is an XRD chart of the particles obtained in Comparative Example 1. From this analysis result, it was confirmed that the particles contained a large amount of compounds (Sm oxide, Co oxide, etc.) other than the SmCo-based alloy, and were not particles mainly composed of the SmCo-based alloy. The particle diameter, yield, and coercive force (Hc) of the obtained particles were as shown in Table 1.
（比較例２）
ナトリウムボロン水素化物を用いなかったこと以外は実施例１と同様にして合成を行い、粒子を得た。実施例１と同様にして粒子の評価及び磁気特性の評価を行った。図４の中段のチャートは比較例２で得られた粒子のＸＲＤ分析結果である。この分析結果より、粒子にはＳｍＣｏ系合金以外の化合物（Ｓｍ酸化物及びＣｏ酸化物など）が含まれており、ＳｍＣｏ系合金を主成分とする粒子ではないことが確認された。得られた粒子の粒径、粒子の第３金属元素の含有量、収率及び保磁力（Ｈｃ）は、表１に示すとおりであった。
(Comparative Example 2)
Synthesis was performed in the same manner as in Example 1 except that sodium boron hydride was not used to obtain particles. In the same manner as in Example 1, evaluation of particles and evaluation of magnetic properties were performed. The middle chart of FIG. 4 shows the results of XRD analysis of the particles obtained in Comparative Example 2. From this analysis result, it was confirmed that the particles contain compounds other than the SmCo-based alloy (such as Sm oxide and Co oxide) and are not particles mainly composed of the SmCo-based alloy. Table 1 shows the particle diameter of the obtained particles, the content of the third metal element in the particles, the yield, and the coercive force (Hc).
（比較例３）
第３金属元素の塩（パラジウムアセチルアセトナート）を用いなかったこと以外は実施例１と同様にして合成を行い、粒子を得た。粒子の粒径、収率及び保磁力（Ｈｃ）は、表１に示すとおりであった。比較例３の粒子の保磁力（Ｈｃ）は、実施例１〜９の第３金属元素を含有するＳｍＣｏ５ナノ粒子に比べて低くなっていた。
(Comparative Example 3)
Synthesis was performed in the same manner as in Example 1 except that the salt of the third metal element (palladium acetylacetonate) was not used to obtain particles. The particle size, yield and coercive force (Hc) of the particles were as shown in Table 1. The coercive force (Hc) of the particles of Comparative Example 3 was lower than that of the SmCo 5 nanoparticles containing the third metal element of Examples 1-9.
Claims (10)
前記ＳｍＣｏ系合金に対するＳｍ及びＣｏとは異なる金属元素の含有量が０．０５〜２０質量％であるＳｍＣｏ系合金ナノ粒子。 Containing an SmCo-based alloy having Sm and Co as constituent elements as a main component;
SmCo-based alloy nanoparticles in which the content of a metal element different from Sm and Co in the SmCo-based alloy is 0.05 to 20% by mass.
前記コア部分における前記ＳｍＣｏ系合金に対する前記金属元素の比率が、前記シェル部分の当該比率よりも大きい請求項１〜５のいずれか一項に記載のＳｍＣｏ系合金ナノ粒子。 A core shell structure having a core portion and a shell portion covering the core portion;
The SmCo-based alloy nanoparticles according to any one of claims 1 to 5, wherein a ratio of the metal element to the SmCo-based alloy in the core part is larger than the ratio of the shell part.
前記混合液に、強還元剤を添加して加熱することにより、前記サマリウム塩、前記コバルト塩及び前記金属元素の塩を還元する還元工程と、を有する、
構成元素としてＳｍ及びＣｏを有するＳｍＣｏ系合金を主成分として含有するＳｍＣｏ系合金ナノ粒子の製造方法。 A mixing step of mixing a samarium salt, a cobalt salt, a salt of a metal element different from Sm and Co, and a raw material containing a protective agent together with a reducing organic solvent to obtain a mixed solution;
A reduction step of reducing the samarium salt, the cobalt salt, and the salt of the metal element by adding a strong reducing agent to the mixed solution and heating.
A method for producing SmCo-based alloy nanoparticles containing, as a main component, an SmCo-based alloy having Sm and Co as constituent elements.
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| US12/397,786 US20090257907A1 (en) | 2008-03-07 | 2009-03-04 | SmCo-BASED ALLOY NANOPARTICLES AND PROCESS FOR THEIR PRODUCTION |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102366832A (en) * | 2011-06-30 | 2012-03-07 | 燕山大学 | Preparation method of anisotropic samarium-cobalt/cobalt nano-composite magnet |
| JP2017120868A (en) * | 2015-04-20 | 2017-07-06 | 株式会社セルモエンターティメントジャパン | Magnetic material, and eye glasses, lens and accessory for eye glasses, each arranged by use of the magnetic material |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8211205B1 (en) * | 2009-07-28 | 2012-07-03 | Ut Dots, Inc. | Method of controlled synthesis of nanoparticles |
| US20120019341A1 (en) * | 2010-07-21 | 2012-01-26 | Alexandr Gabay | Composite permanent magnets made from nanoflakes and powders |
| CN102416483B (en) * | 2011-11-28 | 2013-02-13 | 中国科学院宁波材料技术与工程研究所 | Method for preparing double-phase composite samarium cobalt-iron powder |
| CN108335900B (en) * | 2018-03-21 | 2020-08-25 | 重庆科技学院 | Preparation of SmCo7Method for manufacturing/Co composite permanent magnet and magnet thereof |
| CN109817405B (en) * | 2019-03-29 | 2020-08-04 | 南京工程学院 | Preparation method of nano magnetic particles |
-
2008
- 2008-03-07 JP JP2008058346A patent/JP2009215583A/en not_active Withdrawn
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102366832A (en) * | 2011-06-30 | 2012-03-07 | 燕山大学 | Preparation method of anisotropic samarium-cobalt/cobalt nano-composite magnet |
| CN102366832B (en) * | 2011-06-30 | 2013-07-03 | 燕山大学 | Preparation method of anisotropic samarium-cobalt/cobalt nano-composite magnet |
| JP2017120868A (en) * | 2015-04-20 | 2017-07-06 | 株式会社セルモエンターティメントジャパン | Magnetic material, and eye glasses, lens and accessory for eye glasses, each arranged by use of the magnetic material |
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