CN103890869B - 具有硬‑软磁性异质结构的核‑壳结构的纳米粒子、利用所述纳米粒子制备的磁体及它们的制备方法 - Google Patents
具有硬‑软磁性异质结构的核‑壳结构的纳米粒子、利用所述纳米粒子制备的磁体及它们的制备方法 Download PDFInfo
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- CN103890869B CN103890869B CN201380003534.3A CN201380003534A CN103890869B CN 103890869 B CN103890869 B CN 103890869B CN 201380003534 A CN201380003534 A CN 201380003534A CN 103890869 B CN103890869 B CN 103890869B
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- AJCDFVKYMIUXCR-UHFFFAOYSA-N oxobarium;oxo(oxoferriooxy)iron Chemical compound [Ba]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O AJCDFVKYMIUXCR-UHFFFAOYSA-N 0.000 claims description 10
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- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
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- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 2
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims 2
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- VEQVWMIWJMNBTL-UHFFFAOYSA-L dodecanoate;iron(2+) Chemical compound [Fe+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O VEQVWMIWJMNBTL-UHFFFAOYSA-L 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- HOIQWTMREPWSJY-GNOQXXQHSA-K iron(3+);(z)-octadec-9-enoate Chemical compound [Fe+3].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O HOIQWTMREPWSJY-GNOQXXQHSA-K 0.000 claims 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- YADLKQDEUNZTLC-UHFFFAOYSA-N [Fe].[Ba] Chemical compound [Fe].[Ba] YADLKQDEUNZTLC-UHFFFAOYSA-N 0.000 description 1
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- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical compound CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 description 1
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- 239000013626 chemical specie Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 239000011817 metal compound particle Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- WQQPDTLGLVLNOH-UHFFFAOYSA-M sodium;4-hydroxy-4-oxo-3-sulfobutanoate Chemical class [Na+].OC(=O)CC(C([O-])=O)S(O)(=O)=O WQQPDTLGLVLNOH-UHFFFAOYSA-M 0.000 description 1
- VAVPGQSSOJBZIP-UHFFFAOYSA-N sodium;iron(3+) Chemical compound [Na+].[Fe+3] VAVPGQSSOJBZIP-UHFFFAOYSA-N 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
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- 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
- H01F1/06—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 in the form of particles, e.g. powder
- H01F1/08—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 in the form of particles, e.g. powder pressed, sintered, or bound together
-
- 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
- H01F1/0302—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity characterised by unspecified or heterogeneous hardness or specially adapted for magnetic hardness transitions
- H01F1/0311—Compounds
- H01F1/0313—Oxidic compounds
- H01F1/0315—Ferrites
-
- 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
- H01F1/0302—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity characterised by unspecified or heterogeneous hardness or specially adapted for magnetic hardness transitions
- H01F1/0306—Metals or alloys, e.g. LAVES phase alloys of the MgCu2-type
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- 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
- H01F1/0536—Alloys characterised by their composition containing rare earth metals sintered
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
本发明涉及一种具有硬‑软异质结构的核‑壳结构的纳米粒子、由所述纳米粒子制备的磁体及它们的制备方法。本发明的具有硬‑软磁性异质结构的核‑壳结构的纳米粒子具有很多优点,如不受稀土元素的资源供应问题影响且价格低,并能够克服常规铁氧体单相材料所具有的物理和磁性限制。
Description
技术领域
本发明涉及一种具有硬-软磁性异质结构的核-壳结构的纳米粒子、利用所述纳米粒子制备的磁体及它们的制备方法。
背景技术
钕磁体是包含钕(Nd)、氧化铁(Fe)和硼(B)作为主要组分的烧结产物,其特征是非常优异的磁性性质。尽管对这种高性质的钕大块磁体的需求增加,但是稀土元素的需求和供应的失衡阻碍了下一代工业所必需的高性能电动机的供应。
包含钐和钴作为主要组分的钐钴磁体已知具有仅次于与钕磁体的非常优异的磁性性质,但作为一种稀土元素的钐的需求和供应的问题也造成制造成本的升高。
铁氧体磁体是在不需要强磁力时使用的具有稳定磁性性质的低价磁体。铁氧体磁体通常通过粉末冶金制造,并通常呈黑色。铁氧体磁体的化学形式为XO+Fe2O3,其中根据其用途X可以为钡或锶。铁氧体磁体,根据其制造方法分为干加工的或湿加工的铁氧体磁体,或者根据其磁方向分为各向同性或各向异性的铁氧体磁体。所述铁氧体磁体是由氧化物组成的化合物,因此,即使使其在高频率磁场中运行,其仍为绝缘体并几乎没有高频率的损失如过大电流损失。各向同性的磁体具有比各向异性的磁体更低的磁力,但具有几种优点如低价格和自由连接。铁氧体磁体已经用于多种应用如直流电动机、罗盘、电话、转速计、扬声器、速度计、电视机、簧片开关和钟机芯,并具有几种优点如其重量轻且价格低。然而,铁氧体磁体还具有其不显示足以取代高价钕大块磁体的优异磁性性质的劣势。
同时,核-壳结构的纳米粒子是指具有其中壳物质包围位于中心的核物质的结构的材料。由于核-壳结构的纳米粒子根据包含在各层中的物质的性质而提供具有至少两种(2)性质的多功能纳米材料,所以通过提供金属-金属、金属-陶瓷、金属-有机物以及有机物-有机物结构的不同组合而存在针对核-壳结构的纳米粒子的许多研究和开发。已知的是,核-壳结构的纳米粒子由于其磁性性质、荧光性质、抗酸性质和抗磨损性质的组合功能性而对各种领域具有高应用性。
至今,对包含在核或壳结构中的物质一直存在限制,且大部分研究仅针对这些受限物质进行。在这种状况下,认为在通过探索目前为止常规研究的物质之外的新物质以研究和开发新型核-壳结构的纳米粒子,并将这些材料组合,由此提供新性质方面存在巨大的未来可能性。
用于得到核-壳结构的纳米粒子粉末的方法包括共沉淀、喷雾、电解和溶胶-凝胶法以及反胶束法。
例如,美国专利7,547,400号使用反胶束法制备纳米级镍-锌铁氧体且韩国专利申请10-2010-0029428号使用溶胶-凝胶法制备纳米铁粉末。
其中,韩国专利申请10-2010-0029428号实现了一种核-壳双重结构,但与常规软磁性材料类似,该发明显示了受限的物理和磁性性质,因为核和壳两者都仅由软磁性物质组成。
在整个本申请中,参考几个专利和公开并提供引用。将这些专利和公开的内容并入本申请中以更全面地说明本发明和本发明所属的领域的状况。
发明内容
技术问题
本发明的发明人进行了研究并尝试开发具有能够代替昂贵的稀土元素大块磁体的高性能的惰性磁性材料,并通过成功地制备具有硬-软磁性异质结构的核-壳结构的纳米粒子而完成了本发明。因此,本发明的目的是提供一种具有硬-软磁性异质结构的惰性核-壳结构的纳米粒子。
本发明的另一个目的是提供一种制备上述具有硬-软磁性异质结构的核-壳结构的纳米粒子的方法。
本发明的另一个目的是提供一种通过使用上述具有硬-软磁性异质结构的核-壳结构的纳米粒子制备的磁体。
根据下文中提供的详细说明,本申请的应用性的其他范围变得更明显。然而,应理解,尽管指示本发明的优选实施方案,但是详细说明和具体实例是仅出于示例性目的而给出的,因为根据所述详细说明,本发明的主旨和范围内的各种变化和修改对本领域技术人员变得明显。
解决问题的技术方案
本发明的目的是提供一种具有硬-软磁性异质结构的核-壳结构的纳米粒子,其中软磁性壳包围硬磁性核。
本发明的发明人已经进行了研究并尝试开发一种高性能磁性材料,所述高性能磁性材料通过实现高矫顽力和高饱和通量密度两者而超过现有的铁氧体磁性材料。在上述方法中,本发明人集中于如下要点:当将硬磁性纳米粉末如铁氧体与包含金属如铁、钴和镍的软磁性纳米粉末进行简单混合时,得到如图3中所示的2相磁性图而不是同时实现良好的矫顽力和饱和通量密度两者,并对如何将上述两种磁性材料之间的界面进行平稳连接进行了研究。结果,通过成功地制备具有硬-软异质结构的核-壳结构的纳米粒子以在纳米粒子内同时实现硬磁性材料和软磁性材料两者,本发明人完成了本发明。
本发明的上述纳米粒子的特征在于,与硬和软磁性纳米粉末的常规简单混合不同,如图2中所示的同时实现良好的矫顽力和饱和通量密度两者。
在本发明的具有硬-软异质结构的核-壳结构的纳米粒子中,上述核的特征在于,包含至少1种硬磁性材料,优选包含铁氧体作为其主要成分,其具有优点如高的居里温度、矫顽力、化学稳定性和抗腐蚀性以及低的价格。
在优选实施方案中,上述铁氧体可使用纳米级磁体铅矿(M型)晶体结构或W型钡铁氧体、锶铁氧体、钴铁氧体或其组合。
在本发明的具有硬-软异质结构的核-壳结构的纳米粒子中,上述壳的特征在于,包含至少1种软磁性材料,且例如可以包含至少一种金属或金属化合物。
在实施方案中,上述软磁性壳的特征在于,包含选自如下的至少一种金属或金属化合物:Fe、Co、Ni、Fe3B、FeCo、Fe16N2、FeNi、Fe3O4、FeSi和CoNi。
在本发明中,根据上述硬磁性核和软磁性壳在整个纳米粒子内的比例能够适当控制磁性性质。例如,当硬磁性核在本发明的整个纳米粒子内的比例提高时,矫顽力进一步提高,但可能的饱和通量密度下降。相反,当软磁性壳在整个纳米粒子内的比例提高时,产生的矫顽力下降,但饱和通量密度提高。
在本发明的优选实施方案中,上述软壳以5~80重量%的含量包含在整个纳米粒子中。
根据将多少硬磁性成分和软磁性成分包含在最终的溶液中以制备本发明的纳米粒子,能够容易地控制硬磁性核与软磁性壳之间的这些含量比。
本发明的复合纳米粒子的直径小于1000nm,优选为10~1000nm,更优选为70~500nm。
在优选实施方案中,本发明的复合纳米粒子的特征在于具有核-壳结构,其中α铁壳包围选自如下的至少一种硬磁性铁氧体核:钡铁氧体、锶铁氧体和钴铁氧体。
本发明的另一个目的是提供一种通过使用溶胶-凝胶法制备具有硬-软异质结构的核-壳结构的纳米粒子的方法,所述方法的特征在于包括如下步骤:(i)获得包含选自如下的至少一种材料和铁氧体纳米粉末的浆料状态的溶液的步骤:金属络合物、金属盐、金属化合物和金属纳米粒子;(ii)通过使得上述溶液的溶剂蒸发而将其改变为粘稠的凝胶的步骤;以及(iii)通过对上述凝胶进行加热以制造纳米粒子的步骤。
上述溶胶-凝胶法是经历溶胶→凝胶→纳米粒子的工艺,其中溶胶是指不会沉淀的分散胶体悬浮体,其由尺寸为约1~1000nm的粒子构成并具有可忽略的引力或重力作用,从而主要受范德华力或表面电荷的影响。这种溶胶通过水解和浓缩而变为凝胶。与溶胶不同,通过对凝胶进行加热以损失其流动性而得到纳米粒子。使用溶胶-凝胶法的材料的这种制备具有一些优点:可以制备具有均匀组成的材料并通过调节其组成和微结构而得到期望的形式。
为了制备本发明的具有硬-软磁性异质结构的纳米粒子,要求在上述步骤(i)中,将硬和软磁性材料两者一起分散在最终溶液中,所述最终溶液为浆料或悬浮液。
例如,浆料状态的上述最终溶液可以包含选自钡铁氧体、锶铁氧体和钴铁氧体中的至少一种铁氧体纳米粒子作为上述硬磁性材料且包含选自金属络合物、金属盐、金属化合物和金属纳米粉末中的至少一种材料作为上述软磁性材料,并优选可包含选自Fe-油酸盐和Fe-十二烷酸盐中的至少一种金属络合物。
可以根据上述最终溶液中涉及的硬磁性物质和软磁性物质各自的含量来调节构成最终制备的纳米粒子的硬磁性核与软磁性壳之间的含量比并适当控制由纳米粒子实现的磁性性质。
在本发明中,通过经由浆料状态的溶液的剧烈搅拌并加热以使其缓慢蒸发而将全体溶液改变为粘稠凝胶型的方法,能够实施上述步骤(ii)。
上述步骤(iii)是使得溶剂完全蒸发并使得涂布材料被完全吸收的步骤,所述步骤能够通过使得溶剂在空气中受热并燃烧以形成粉末的方法实施。
通过这种溶胶-凝胶法制备的本发明的纳米粉末能够具有核-壳结构,其中所述软磁性壳包围所述硬磁性核并实现高矫顽力和高饱和通量密度两者。
在这种制备的纳米粒子中壳由金属化合物构成的情况中,添加通过热还原将金属化合物还原的步骤具有如下优点:可以确保更好的饱和磁性性质。由此,在优选实施方案中描述的本发明的方法的特征在于包括对在上述步骤(iii)中制备的纳米粒子另外实施热还原的步骤。通过将上述制备的纳米粒子在高温氢气条件下培养特定时间并然后对其进行退火,能够实施上述热还原。
本发明的另一个目的是提供一种通过使用反胶束法制备具有硬-软异质结构的核-壳结构的纳米粒子的方法,所述方法的特征在于包括如下步骤:(i)获得并搅拌包含金属盐、铁氧体纳米粉末、表面活性剂、烃和蒸馏水的混合物的步骤;和(ii)通过对上述经搅拌的溶液快速干燥以形成纳米粒子的步骤。
作为表面化学所涉及领域的反胶束(RM)法是使用表面活性剂的物理化学性质制备纳米粒子的方法。当利用非极性溶剂(有机溶剂)增溶水溶液时,形成反胶束(RM)并在其内部还形成水池,其中RM溶液形成透明的、各向同性的且热稳定的微乳液。在上述RM溶液中,水溶液层以分散状态存在到纳米级水池中且所述水池由于其尺寸和水性条件而提供制备纳米粒子所必要的微环境。当使用这种反胶束法时,可以根据其组成的实验条件而合成具有不同形式的纳米级金属微粒。与其类似,考虑将RM应用于各种领域以作为物质的分离、传输、化学和酶反应的反应器并积极用于制备纳米粒子。
为了制备本发明的具有硬-软磁性异质结构的纳米粒子,要求在上述步骤(i)中,将硬和软磁性材料两者一起分散在上述混合物中。
优选地,可以将铁氧体纳米粉末用作上述硬磁性物质并将各种金属盐如铁(Fe)-硝酸盐、单钠铁(Ⅲ)(monosodium ferric)、硫酸亚铁、硫酸铁、硝酸钴、碳酸镍和硫酸镍用作软磁性物质。
可以根据用于上述步骤(i)中使用的上述混合物中涉及的硬磁性物质和软磁性物质各自的含量来调节构成最终制备的纳米粒子的硬磁性核与软磁性壳之间的含量比,从而适当控制由纳米粒子实现的磁性性质。
根据上述使用的表面活性剂的成分能够改善水池的微环境。例如,可以将选自如下的至少一种物质用作上述表面活性剂的成分:二(2-乙基己基)磺基琥珀酸钠、聚氧乙烯壬基苯基醚、壬基酚乙氧基化物和二辛基磺基琥珀酸钠。
上述烃是通过增溶水溶液而形成反胶束的溶剂且非极性溶剂(有机溶剂)足以无限制地使用。例如,可以将选自如下的至少一种材料用作上述烃:环己烷、三甲基戊烷、庚烷、辛烷、异辛烷、癸烷、四氯化碳和苯。
上述步骤(iii)是通过快速干燥来消除水分并除去有机物质的工艺,其可通过例如喷雾干燥法来实施。
在这种制备的纳米粒子中壳由金属化合物构成的情况中,添加通过热还原将金属化合物还原的步骤具有如下优点:可以确保更好的饱和磁性性质。由此,在本发明的优选实施方案中,反胶束法可以另外包括在上述步骤(ii)之后对纳米粒子实施热还原的步骤。
本发明的另一个目的是提供一种利用上面所述的具有硬-软磁性异质结构的核-壳结构的纳米粒子制备的磁体。
在本发明的实施方案中,上述磁体可以为烧结磁体或粘结磁体。通过对具有硬-软磁性异质结构的核-壳结构的纳米粒子进行烧结能够制备上述烧结磁体。
上述粘结磁体称作树脂磁体且能够通过将本发明的具有硬-软磁性异质结构的纳米粒子与树脂混合并然后通过挤出或注射进行成型而制备。
通过在磁场成型之后对具有硬-软磁性异质结构的纳米粒子进行烧结的2步工艺能够制备上述烧结磁体。为了制备烧结磁体,可以应用磁场成型和烧结的一体化工艺以及上述的2步工艺。
有益效果
本发明的具有其中软磁性壳包围硬磁性核的硬-软磁性异质结构的核-壳结构的纳米粒子具有一些优点如不受稀土元素的供应问题影响且价格低并能够克服常规铁氧体单相材料所具有的的物理和磁性限制。
附图说明
附图显示了示例性实施方案并与说明书一起用于解释本发明的原理,所述附图是为了提供本发明的进一步说明而包含的并将其并入且构成本说明书的一部分。
在附图中:
图1是根据本发明制备的具有硬-软磁性异质结构的核-壳结构的纳米粒子的TEM(透射电子显微镜)图像。
图2是得自根据本发明制备的具有硬-软磁性异质结构的核-壳结构的纳米粒子的磁性测量的图。
图3是通过对硬和软磁性粉末之间的简单混合物进行磁性测量而得到的图。
图4是显示如下原理的图:根据本发明制备的具有硬-软磁性异质结构的核-壳结构的纳米粒子同时具有良好的矫顽力值和饱和磁通量密度值两者。
图5是显示通过使用溶胶-凝胶涂布法制备具有硬-软磁性异质结构的核-壳结构的纳米粒子的方法的图。
图6是显示通过使用反胶束法制备具有硬-软磁性异质结构的核-壳结构的纳米粒子的方法的图。
上述实施方案和优点只是示例性的且不应解释为限制本发明。本发明的教导能够容易地应用于其他类型的设备。本说明书旨在是示例性的,且不限制权利要求书的范围。许多替代、变体和变化对于本领域技术人员是明显的。本文中所述的示例性实施方案的特征、结构、方法和其他特性可以以各种方式组合以获得另外和/或替代性的示例性实施方案。
具体实施方式
现在将通过实施例对本发明进行更详细地说明。对于本领域技术人员明显的是,这些实施例旨在为更具体地说明性的且附属权利要求书中提出的本发明的范围不能限制为所述实施例或不能由所述实施例限制。
实施例
使用溶胶凝胶涂布法制备具有硬-软磁性异质结构的核-壳结构的纳米粒子
根据图5中所示的方案,通过使用溶胶凝胶法制备了具有硬-软磁性异质结构的核-壳结构的纳米粒子。
具体地,通过将2.16g的Fe-油酸盐(SIGMA-ALDRICH)添加到25mL的乙醇中并对它们进行搅拌,制备了混合物溶液。然后,添加20mL蒸馏水和2.7g铁氧体纳米粉末(SIGMA-ALDRICH)并搅拌以制备浆料状态的溶液。
在搅拌期间在70℃下对这些制备的浆料状态的溶液进行加热以蒸发溶剂,从而使得溶液变为粉末。为了完成涂布材料的吸收,在60℃的空气中将其加热并干燥12小时以形成粉末。
然后,在氩气(Ar)气氛下将温度以10℃/分钟从室温升至450℃之后,通过在450℃的氢气气氛下培养1小时来实施还原工艺以将形成小室(cell)的氧化铁还原成铁。然后,通过对前体粉末进行退火而得到核-壳结构的钡铁氧体铁纳米粉末。
使用反胶束法制备具有硬-软磁性异质结构的核-壳结构的纳米粒子
根据图6中所示的方案,通过使用反胶束法制备了具有硬-软磁性异质结构的核-壳结构的纳米粒子。
具体地,通过将以2:5的质量比包含异辛烷和蒸馏水的溶液(蒸馏水3g,异辛烷22.5g)与表面活性剂混合,制备了第一溶液,所述表面活性剂优选为磺酸盐(二(2-乙基己基)磺基琥珀酸钠)(ALTA AESAR),其中将蒸馏水与表面活性剂之间的浓度比[(蒸馏水)/(表面活性剂)]调节为5。
与上述第一溶液分离,将0.1g钡铁氧体悬浮至浆料状态以制备3mL的第二溶液。
然后,通过向3g蒸馏水中添加0.1g要涂布的Fe-硝酸盐(SIGMA-ALDRICH)并搅拌,制备了第三溶液。
通过如下得到最终的溶液:将第二溶液添加到第一溶液中;使用超声发生器(SONICS,VCX-750)对其进行搅拌;添加第三溶液并然后再次使用超声发生器对其进行搅拌。
从最终的溶液,通过如下得到粉末:在300℃和10℃/分钟的升温速率的条件下热风干燥1小时,从而通过快速干燥除去水并通过热处理除去有机物质(AOT),随后除去有机材料并吸收涂布材料。
然后,在氩气(Ar)气氛下将温度以10℃/分钟的速率从室温升至450℃之后,通过在450℃的氢气气氛下培养1小时来实施还原工艺以将形成小室的氧化铁还原成铁。然后,通过对前体粉末进行退火而得到核-壳结构的钡铁氧体铁纳米粉末。
使用TEM(透射电子显微镜法)进行分析
使用TEM(Jeol,JEM2010),对核-壳结构的钡铁氧体-铁纳米粉末的形状和尺寸进行测量。
在将制备的核-壳钡铁氧体-铁纳米粉末置入乙醇中并使用超声发生器对其进行分散之后,在铜网上滴加少量分散液。然后,在空气中对其进行干燥以制备要利用TEM观察的样品并使用TEM对其形状和尺寸进行测量。
图1是显示TEM图像的照片,其中可以确认,由于由铁构成的涂布材料良好地吸收在钡铁氧体核上,所以完全形成了核-壳结构且测得其直径为70~500nm。
测量磁性
使用VSM(振动样品磁强计,Toei,VSM-5)对制备的核-壳结构的钡铁氧体铁纳米粉末的磁性进行测量并将其结果示于图2中。
如图2中所示,制备的核-壳结构的钡铁氧体-铁纳米粉末的矫顽力和饱和磁化强度值分别为4130Oe和82emu/g,且确认,纳米粉末具有硬磁相的高矫顽力和软磁相的高饱和通量密度两者。
制备磁体
本发明还提供一种通过使用具有硬-软磁性异质结构的核-壳结构的纳米粒子制备磁体的方法,在所述纳米粒子中软磁性壳包围硬磁性核。
(1)制备粘结磁体
具体地,通过包括如下步骤的方法制备粘结磁体:(i)通过对具有硬-软磁性异质结构的核-壳结构的纳米粒子进行分散而制备粉末;(ii)通过将热固性或热塑性合成树脂与上述粉末进行混合而制备混合物;以及(iii)通过对上述混合物进行挤出或注射而形成粘结磁体。
(2)制备烧结磁体
通过包括如下步骤的方法制备烧结磁体:(i)对根据上述制备方法制备的具有硬-软磁性异质结构的核-壳结构的纳米粒子实施磁场成型;和(ii)对上述成型体进行烧结。或者,可以应用将与上述步骤(i)和(ii)相对应的磁场成型和烧结一体化的一个步骤的工艺。当实施磁场成型时,外部磁场的施加方向可以为水平或竖直方向。关于烧结工艺,可以从如下选择至少一种技术并加以应用:炉烧结、火花等离子体烧结以及微波烧结和热压。
Claims (15)
1.一种具有硬-软磁性异质结构的核-壳结构的纳米粒子,其中α铁壳包围硬磁性核,所述α铁壳占整个纳米粒子的5重量%~80重量%,
其中所述硬磁性核包含选自如下的至少一种铁氧体:钡铁氧体、锶铁氧体和钴铁氧体,
其中所述核-壳结构的纳米粒子的直径为70nm~500nm。
2.一种通过使用溶胶-凝胶法制备具有硬-软异质结构的核-壳结构的纳米粒子的方法,所述方法包括如下步骤:
(i)获得浆料状态的溶液,所述溶液包含铁氧体纳米粉末和选自如下的至少一种物质:金属络合物、金属盐和金属化合物;
(ii)通过使所述溶液的溶剂蒸发而将所述溶液变为粘稠的凝胶;
(iii)通过对所述凝胶进行加热而形成纳米粒子;以及
(iv)对制备的纳米粒子实施热还原,
其中所述核-壳结构的纳米粒子包含5重量%~80重量%的α铁壳,并具有70nm~500nm的直径,
其中所述铁氧体纳米粉末包含选自如下的至少一种铁氧体:钡铁氧体、锶铁氧体和钴铁氧体。
3.一种通过使用反胶束法制备具有硬-软异质结构的核-壳结构的纳米粒子的方法,所述方法包括如下步骤:
(i)获得并混合包含铁盐、铁氧体纳米粉末、表面活性剂、烃和蒸馏水的溶液;
(ii)通过对所述溶液快速干燥而形成纳米粒子;以及
(iii)对制备的纳米粒子实施热还原,
其中所述核-壳结构的纳米粒子包含5重量%~80重量%的α铁壳,并具有70nm~500nm的直径,
其中所述铁氧体纳米粉末包含选自如下的至少一种铁氧体:钡铁氧体、锶铁氧体和钴铁氧体。
4.如权利要求2所述的方法,其中所述浆料状态的溶液包含铁氧体纳米粉末和选自如下的至少一种金属络合物:铁-油酸盐(Fe-油酸盐)和铁-十二烷酸盐(Fe-十二烷酸盐)。
5.如权利要求3所述的方法,其中所述表面活性剂为选自如下的至少一种:二(2-乙基己基)磺基琥珀酸钠、聚氧乙烯壬基苯基醚、壬基酚乙氧基化物和二辛基磺基琥珀酸钠。
6.如权利要求3所述的方法,其中所述烃为选自如下的至少一种:环己烷、三甲基戊烷、庚烷、辛烷、异辛烷、癸烷、四氯化碳和苯。
7.一种磁体,其由权利要求1的纳米粒子制备。
8.如权利要求7所述的磁体,其中所述磁体为烧结磁体或粘结磁体。
9.一种合成粘结磁体的方法,包括如下步骤:
(i)制备粉末,所述粉末包含权利要求1的具有硬-软磁性异质结构的核-壳结构的纳米粒子;
(ii)通过将所述粉末与热固性或热塑性合成树脂进行混合而制备混合物;以及
(iii)通过对所述混合物进行挤出或注射以形成粘结磁体。
10.一种粘结磁体,其包含权利要求1的具有硬-软磁性异质结构的核-壳结构的纳米粒子。
11.一种制备烧结磁体的方法,包括如下步骤:
(i)对权利要求1的具有硬-软磁性异质结构的核-壳结构的纳米粒子实施磁场成型;以及
(ii)对成型体进行烧结。
12.如权利要求11所述的方法,其中通过在水平轴或竖直轴的方向上施加外部磁场而实施所述磁场成型。
13.如权利要求11所述的方法,其中通过选自如下的至少一种来实施所述烧结:炉烧结、火花等离子体烧结、微波烧结和热压。
14.如权利要求11所述的方法,其中同时实施所述步骤(i)和(ii)。
15.一种通过权利要求11的方法制备的烧结磁体,其由所述具有硬-软磁性异质结构的核-壳结构的纳米粒子制备。
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