JP2008179842A - Method for producing nickel-iron-zinc alloy nanoparticle and nickel-iron-zinc alloy nanoparticle, and method for producing planar nickel-iron-zinc alloy nanoparticle and planar nickel-iron-zinc alloy nanoparticle - Google Patents
Method for producing nickel-iron-zinc alloy nanoparticle and nickel-iron-zinc alloy nanoparticle, and method for producing planar nickel-iron-zinc alloy nanoparticle and planar nickel-iron-zinc alloy nanoparticle Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 165
- RFIJBZKUGCJPOE-UHFFFAOYSA-N [Fe].[Ni].[Zn] Chemical compound [Fe].[Ni].[Zn] RFIJBZKUGCJPOE-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 152
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 53
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000007864 aqueous solution Substances 0.000 claims abstract description 47
- 229910052742 iron Inorganic materials 0.000 claims abstract description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 35
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- -1 iron ions Chemical class 0.000 claims abstract description 23
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 22
- 150000003751 zinc Chemical class 0.000 claims abstract description 17
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004033 plastic Substances 0.000 claims abstract description 16
- 150000002505 iron Chemical class 0.000 claims abstract description 15
- 150000002815 nickel Chemical class 0.000 claims abstract description 14
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 28
- 230000005415 magnetization Effects 0.000 claims description 11
- 230000001603 reducing effect Effects 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 14
- 239000011701 zinc Substances 0.000 abstract description 14
- 229910052759 nickel Inorganic materials 0.000 abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052725 zinc Inorganic materials 0.000 abstract description 11
- 238000009835 boiling Methods 0.000 abstract description 6
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000002245 particle Substances 0.000 description 18
- 229910045601 alloy Inorganic materials 0.000 description 17
- 239000000956 alloy Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002923 metal particle Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000035699 permeability Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000013078 crystal Substances 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000000805 composite resin Substances 0.000 description 7
- 239000002905 metal composite material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 229960002089 ferrous chloride Drugs 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 3
- 229910000952 Be alloy Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910018619 Si-Fe Inorganic materials 0.000 description 1
- 229910008289 Si—Fe Inorganic materials 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000012762 magnetic filler Substances 0.000 description 1
- 238000010299 mechanically pulverizing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 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
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 229910000889 permalloy Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229910000702 sendust Inorganic materials 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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- Powder Metallurgy (AREA)
Abstract
Description
本発明は、ニッケル―鉄―亜鉛合金ナノ粒子の製造方法およびニッケル―鉄―亜鉛合金ナノ粒子、並びに、平板状ニッケル―鉄―亜鉛合金ナノ粒子の製造方法および平板状ニッケル―鉄―亜鉛合金ナノ粒子に関し、さらに詳しくは、厚みが薄く、高アスペクト比を有し、分散性に優れた高透磁率の平板状ニッケル―鉄―亜鉛合金ナノ粒子の原料となるニッケル―鉄―亜鉛合金ナノ粒子の製造方法、および、このニッケル―鉄―亜鉛合金ナノ粒子の製造方法によって製造されたニッケル―鉄―亜鉛合金ナノ粒子、並びに、このニッケル―鉄―亜鉛合金ナノ粒子を原料として平板状ニッケル―鉄―亜鉛合金ナノ粒子を製造する平板状ニッケル―鉄―亜鉛合金ナノ粒子の製造方法、および、この平板状ニッケル―鉄―亜鉛合金ナノ粒子の製造方法によって製造された平板状ニッケル―鉄―亜鉛合金ナノ粒子に関する。 The present invention relates to a method for producing nickel-iron-zinc alloy nanoparticles, nickel-iron-zinc alloy nanoparticles, a method for producing tabular nickel-iron-zinc alloy nanoparticles, and plate-like nickel-iron-zinc alloy nanoparticles. More specifically, the nickel-iron-zinc alloy nanoparticles, which are the raw materials for the thin-plate, nickel-iron-zinc alloy nanoparticles with high permeability, high permeability, and high magnetic permeability, have a high aspect ratio. Nickel-iron-zinc alloy nanoparticles produced by the production method, nickel-iron-zinc alloy nanoparticles production method, and plate-like nickel-iron- A method for producing tabular nickel-iron-zinc alloy nanoparticles for producing zinc alloy nanoparticles and a method for producing these tabular nickel-iron-zinc alloy nanoparticles Tabular nickel produced me - about zinc alloy nanoparticles - iron.
近年、軟磁性金属粒子は、有機バインダーに磁性顔料として分散して塗料を調製し、この塗料を基材などに塗布して塗膜を形成したり、樹脂中に磁性フィラーとして分散して軟磁性金属／樹脂複合体を形成するなど、様々な分野で用いられている。
軟磁性金属粒子を用いた塗膜としては、磁気シールド膜が挙げられる。この磁気シールド膜は、電気機器の電子回路や電子部品を外部磁界から保護したり、電気機器から生じる磁界が外部へ漏洩するのを防止するために用いられている。また、この磁気シールド膜は、クレジットカードなどの磁気カードにおいても、データの偽造や変造を防止する目的で用いられている。さらに、この磁気シールド膜は、ＩＣタグ（ＲＦＩＤシステム）においても、軟磁性金属の高透磁率による磁界収束効果を応用し、電磁シールド膜として用いられている。
一方、軟磁性金属／樹脂複合体は、電子回路の消費電力の低下が可能であることから、高周波電子回路基板に用いられている。
In recent years, soft magnetic metal particles are dispersed as a magnetic pigment in an organic binder to prepare a paint, and this paint is applied to a substrate to form a coating film, or dispersed as a magnetic filler in a resin to form a soft magnetism. It is used in various fields such as forming metal / resin composites.
Examples of the coating film using soft magnetic metal particles include a magnetic shield film. This magnetic shield film is used to protect electronic circuits and electronic components of electric equipment from an external magnetic field and to prevent a magnetic field generated from the electric equipment from leaking to the outside. This magnetic shield film is also used for the purpose of preventing forgery and alteration of data even in a magnetic card such as a credit card. Further, this magnetic shield film is also used as an electromagnetic shield film in an IC tag (RFID system) by applying the magnetic field convergence effect due to the high magnetic permeability of soft magnetic metal.
On the other hand, soft magnetic metal / resin composites are used for high-frequency electronic circuit boards because the power consumption of electronic circuits can be reduced.
このような軟磁性金属としては、センダストと称されるＡｌ―Ｓｉ―Ｆｅ系合金（例えば、特許文献１参照）やパーマロイと称されるＮｉ―Ｆｅ系合金（例えば、特許文献２参照）などの高透磁率合金が用いられている。
また、軟磁性金属粒子としては、厚みが１μｍ以下の平板状であることが求められており、具体的には、扁平状、鱗片状、フレーク状など、様々な形状のものが提案されている（例えば、特許文献１〜３参照）。
Examples of such soft magnetic metals include an Al—Si—Fe based alloy called sendust (for example, see Patent Document 1) and a Ni—Fe based alloy called permalloy (for example, see Patent Document 2). A high permeability alloy is used.
Further, the soft magnetic metal particles are required to have a flat plate shape with a thickness of 1 μm or less, and specifically, various shapes such as a flat shape, a scale shape, and a flake shape have been proposed. (For example, see Patent Documents 1 to 3).
これらの平板状の軟磁性金属粒子は、塗膜や軟磁性金属／樹脂複合体の表面の平滑性を高めることができる。また、平板状の軟磁性金属粒子は、塗料を塗布する際、あるいは、軟磁性金属／樹脂複合体を成形する際に外部磁場をかけることにより、特定方向に平行に整列（配向）するので、塗膜あるいは軟磁性金属／樹脂複合体の面方向の反磁場係数を低くすると共に、軟磁性金属粒子の配向方向の透磁率を高めることができる。
また、平板状の軟磁性金属粒子は、厚みが１μｍ以下であるから、表皮効果により交流電流を透過させることができるので、渦電流による損失を低減することができる。
これらの平板状の軟磁性金属粒子は、アトマイズ法により作製した不定形状粒子を機械的に粉砕あるいは塑性変形することにより作製される。
In addition, since the flat soft magnetic metal particles have a thickness of 1 μm or less, an alternating current can be transmitted by the skin effect, so that a loss due to an eddy current can be reduced.
These tabular soft magnetic metal particles are produced by mechanically crushing or plastically deforming irregularly shaped particles produced by an atomizing method.
ところで、従来の機械的に粉砕あるいは塑性変形する方法では、Ｆｅ―Ｎｉ系合金などの塑性変形し難い合金にあっては、１０時間以上の長期間にわたって機械的応力を加え続けるか、もしくは、極めて強い機械的応力を加えなくてはならないため、工業的には極めて生産性が悪かった。また、従来の機械的に粉砕あるいは塑性変形する方法では、軟磁性金属粒子の塑性変形と粉砕が同時に起こるため、平板状の軟磁性金属粒子と共に大量の微細な粒子を生成し易いという問題があった。 By the way, in the conventional mechanical pulverization or plastic deformation method, in the case of an alloy that is difficult to plastically deform, such as an Fe-Ni alloy, mechanical stress is continuously applied over a long period of 10 hours or more, or extremely Since strong mechanical stress had to be applied, the productivity was extremely poor industrially. In addition, the conventional method of mechanically pulverizing or plastically deforming involves the problem that since the plastic deformation and pulverization of the soft magnetic metal particles occur simultaneously, a large amount of fine particles are likely to be generated together with the flat soft magnetic metal particles. It was.
上記のような問題を解決する方法としては、軟磁性金属粒子を塑性変形させるために、この金属粒子に加える機械的応力を小さくすることが考えられる。軟磁性金属粒子に加える機械的応力を小さくするためには、例えば、Ｆｅ―Ｎｉ系合金粒子に低ヤング率の金属を添加し、この合金粒子のヤング率を低下させて、機械的応力を加えた際の合金粒子の変形量を大きくする方法が考えられる。
しかしながら、従来の合金粒子の製造方法であるアトマイズ法では、一旦、合金成分の金属を溶融しなければならないため、合金成分の金属の融点や沸点などの物質固有の物性値によっては、合金を製造できないことがあった。例えば、ヤング率がニッケルや鉄の半分程度である亜鉛は、沸点がニッケルや鉄の融点以下であるため、通常の方法では、ニッケル、鉄および亜鉛からなる合金を製造することはできなかった。
As a method for solving the above problems, it is conceivable to reduce the mechanical stress applied to the metal particles in order to plastically deform the soft magnetic metal particles. In order to reduce the mechanical stress applied to the soft magnetic metal particles, for example, a metal having a low Young's modulus is added to the Fe-Ni alloy particles, and the Young's modulus of the alloy particles is reduced to apply mechanical stress. It is conceivable to increase the amount of deformation of the alloy particles during the process.
However, in the atomizing method, which is a conventional method for producing alloy particles, the metal of the alloy component must be once melted. Therefore, depending on the physical property values such as the melting point and boiling point of the metal of the alloy component, the alloy is produced. There was something I couldn't do. For example, zinc whose Young's modulus is about half that of nickel or iron has a boiling point lower than the melting point of nickel or iron. Therefore, an alloy made of nickel, iron and zinc cannot be produced by a normal method.
本発明は、上記の課題を解決するためになされたものであって、融点や沸点が大きく異なるニッケルおよび鉄と、亜鉛とを用いて、塑性変形能に優れたニッケル―鉄―亜鉛合金ナノ粒子を得るニッケル―鉄―亜鉛合金ナノ粒子の製造方法、および、このニッケル―鉄―亜鉛合金ナノ粒子の製造方法によって製造されたニッケル―鉄―亜鉛合金ナノ粒子、並びに、このニッケル―鉄―亜鉛合金ナノ粒子を原料として平板状ニッケル―鉄―亜鉛合金ナノ粒子を製造する平板状ニッケル―鉄―亜鉛合金ナノ粒子の製造方法、および、この平板状ニッケル―鉄―亜鉛合金ナノ粒子の製造方法によって製造された平板状ニッケル―鉄―亜鉛合金ナノ粒子を提供することを目的とする。 The present invention has been made in order to solve the above-described problems, and nickel-iron-zinc alloy nanoparticles having excellent plastic deformability using nickel and iron and zinc having greatly different melting points and boiling points. Of nickel-iron-zinc alloy nanoparticles, nickel-iron-zinc alloy nanoparticles produced by the method of producing nickel-iron-zinc alloy nanoparticles, and nickel-iron-zinc alloy Manufacture by manufacturing method of tabular nickel-iron-zinc alloy nanoparticles using nanoparticle as raw material, and manufacturing method of tabular nickel-iron-zinc alloy nanoparticles It is an object of the present invention to provide a formed flat nickel-iron-zinc alloy nanoparticle.
本発明者等は、上記課題を解決するために鋭意研究を行った結果、ニッケル塩と鉄塩と亜鉛塩とを含む水溶液に還元剤を添加して、混合水溶液に含まれるニッケルイオン、鉄イオンおよび亜鉛イオンを同時に還元することにより、塑性変形能に優れたニッケル―鉄―亜鉛合金ナノ粒子が得られることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have added a reducing agent to an aqueous solution containing a nickel salt, an iron salt, and a zinc salt, and nickel ions and iron ions contained in the mixed aqueous solution. It was found that nickel-iron-zinc alloy nanoparticles having excellent plastic deformability can be obtained by simultaneously reducing zinc ions and zinc ions, and the present invention has been completed.
すなわち、本発明のニッケル―鉄―亜鉛合金ナノ粒子の製造方法は、ニッケル塩と鉄塩と亜鉛塩を含む水溶液に還元剤を添加し、前記水溶液に含まれるニッケルイオン、鉄イオンおよび亜鉛イオンを同時に還元することにより、ニッケル―鉄―亜鉛合金ナノ粒子を生成することを特徴とする。 That is, in the method for producing nickel-iron-zinc alloy nanoparticles of the present invention, a reducing agent is added to an aqueous solution containing a nickel salt, an iron salt, and a zinc salt, and nickel ions, iron ions, and zinc ions contained in the aqueous solution are added. It is characterized by producing nickel-iron-zinc alloy nanoparticles by reduction at the same time.
本発明のニッケル―鉄―亜鉛合金ナノ粒子の製造方法は、前記還元剤が、アルカリおよびヒドラジンを含有してなることが好ましい。
本発明のニッケル―鉄―亜鉛合金ナノ粒子の製造方法は、前記アルカリの添加量が、前記水溶液中のニッケルイオン、鉄イオンおよび亜鉛イオンの合計モル量に対して５倍量以上かつ１０倍量以下、前記ヒドラジンの添加量は、前記水溶液中のニッケルイオン、鉄イオンおよび亜鉛イオンの合計モル量に対して２倍量以上かつ５０倍量以下であることが好ましい。
本発明のニッケル―鉄―亜鉛合金ナノ粒子の製造方法は、前記水溶液に還元剤を添加した後、この水溶液を５０℃以上かつ８０℃以下に加熱することが好ましい。
In the method for producing nickel-iron-zinc alloy nanoparticles of the present invention, the reducing agent preferably contains an alkali and hydrazine.
In the method for producing nickel-iron-zinc alloy nanoparticles of the present invention, the addition amount of the alkali is 5 times or more and 10 times the total molar amount of nickel ions, iron ions and zinc ions in the aqueous solution. Hereinafter, the addition amount of the hydrazine is preferably not less than 2 times and not more than 50 times the total molar amount of nickel ions, iron ions and zinc ions in the aqueous solution.
In the method for producing nickel-iron-zinc alloy nanoparticles of the present invention, it is preferable that after adding a reducing agent to the aqueous solution, the aqueous solution is heated to 50 ° C. or higher and 80 ° C. or lower.
本発明のニッケル―鉄―亜鉛合金ナノ粒子は、本発明のニッケル―鉄―亜鉛合金ナノ粒子の製造方法によって得られたニッケル―鉄―亜鉛合金ナノ粒子であって、飽和磁化が５０ｅｍｕ／ｇ以上かつ保磁力が１００Ｏｅ以下であることを特徴とする。 The nickel-iron-zinc alloy nanoparticles of the present invention are nickel-iron-zinc alloy nanoparticles obtained by the method for producing nickel-iron-zinc alloy nanoparticles of the present invention, and have a saturation magnetization of 50 emu / g or more. The coercive force is 100 Oe or less.
本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子の製造方法は、本発明のニッケル―鉄―亜鉛合金ナノ粒子に機械的応力を加えて塑性変形させることにより、平板状ニッケル―鉄―亜鉛合金ナノ粒子を生成することを特徴とする。 The method for producing tabular nickel-iron-zinc alloy nanoparticles according to the present invention is obtained by applying a mechanical stress to the nickel-iron-zinc alloy nanoparticles according to the present invention to cause plastic deformation. It is characterized by producing nanoparticles.
本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子は、本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子の製造方法によって得られた平板状ニッケル―鉄―亜鉛合金ナノ粒子であって、厚みが１μｍ以下かつアスペクト比が２以上であることを特徴とする。 The tabular nickel-iron-zinc alloy nanoparticles of the present invention are tabular nickel-iron-zinc alloy nanoparticles obtained by the method for producing tabular nickel-iron-zinc alloy nanoparticles of the present invention, and have a thickness of Is 1 μm or less and the aspect ratio is 2 or more.
本発明のニッケル―鉄―亜鉛合金ナノ粒子の製造方法によれば、ニッケル塩と鉄塩と亜鉛塩を含む水溶液に還元剤を添加し、前記水溶液に含まれるニッケルイオン、鉄イオンおよび亜鉛イオンを同時に還元することにより、ニッケル―鉄―亜鉛合金ナノ粒子を生成するので、従来、ニッケル、鉄および亜鉛を同時に溶融することは困難であるため、アトマイズ法では製造できなかったニッケル―鉄―亜鉛合金ナノ粒子を生成することができる。したがって、本発明のニッケル―鉄―亜鉛合金ナノ粒子の製造方法によれば、特定の結晶方向に対して塑性変形し易く、機械的応力を加えると容易に塑性変形し、飽和磁化が５０ｅｍｕ／ｇ以上かつ保磁力が１００Ｏｅ以下のニッケル―鉄―亜鉛合金ナノ粒子を、工業的規模にて低製造コストで、安全かつ効率的に製造することができる。 According to the method for producing nickel-iron-zinc alloy nanoparticles of the present invention, a reducing agent is added to an aqueous solution containing a nickel salt, an iron salt and a zinc salt, and nickel ions, iron ions and zinc ions contained in the aqueous solution are added. Since nickel-iron-zinc alloy nanoparticles are produced by reduction at the same time, it is difficult to melt nickel, iron, and zinc at the same time, so nickel-iron-zinc alloys that could not be produced by the atomization method Nanoparticles can be generated. Therefore, according to the method for producing nickel-iron-zinc alloy nanoparticles of the present invention, plastic deformation easily occurs in a specific crystal direction, and plastic deformation easily occurs when mechanical stress is applied, and the saturation magnetization is 50 emu / g. Thus, nickel-iron-zinc alloy nanoparticles having a coercive force of 100 Oe or less can be produced safely and efficiently on an industrial scale at a low production cost.
本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子の製造方法によれば、本発明のニッケル―鉄―亜鉛合金ナノ粒子に機械的応力を加えて塑性変形させることにより、平板状ニッケル―鉄―亜鉛合金ナノ粒子を生成するので、厚みが１μｍ以下かつアスペクト比が２以上の平板状ニッケル―鉄―亜鉛合金ナノ粒子を、工業的規模にて低製造コストで、効率的に製造することができる。 According to the method for producing tabular nickel-iron-zinc alloy nanoparticles of the present invention, a mechanical stress is applied to the nickel-iron-zinc alloy nanoparticles of the present invention to cause plastic deformation, thereby producing tabular nickel-iron- Since zinc alloy nanoparticles are generated, plate-like nickel-iron-zinc alloy nanoparticles having a thickness of 1 μm or less and an aspect ratio of 2 or more can be efficiently produced on an industrial scale at a low production cost. .
本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子は、本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子の製造方法によって得られた平板状ニッケル―鉄―亜鉛合金ナノ粒子であって、厚みが１μｍ以下かつアスペクト比が２以上であるので、従来の球状のニッケル―鉄合金ナノ粒子よりも、渦電流による損失を低減することができる。また、本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子は、塗膜や軟磁性金属／樹脂複合体に適用することにより、これら塗膜や複合体の表面平滑性を向上させることができる。 The tabular nickel-iron-zinc alloy nanoparticles of the present invention are tabular nickel-iron-zinc alloy nanoparticles obtained by the method for producing tabular nickel-iron-zinc alloy nanoparticles of the present invention, and have a thickness of Is 1 μm or less and the aspect ratio is 2 or more, the loss due to eddy current can be reduced as compared with the conventional spherical nickel-iron alloy nanoparticles. Further, the flat nickel-iron-zinc alloy nanoparticles of the present invention can be applied to a coating film or a soft magnetic metal / resin composite to improve the surface smoothness of the coating film or the composite.
本発明のニッケル―鉄―亜鉛合金ナノ粒子の製造方法およびニッケル―鉄―亜鉛合金ナノ粒子、平板状ニッケル―鉄―亜鉛合金ナノ粒子の製造方法および平板状ニッケル―鉄―亜鉛合金ナノ粒子の最良の形態について説明する。
なお、この形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。
The best method for producing nickel-iron-zinc alloy nanoparticles, nickel-iron-zinc alloy nanoparticles, plate-like nickel-iron-zinc alloy nanoparticles, and plate-like nickel-iron-zinc alloy nanoparticles Will be described.
This embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.
本発明のニッケル―鉄―亜鉛合金ナノ粒子の製造方法は、ニッケル塩と鉄塩と亜鉛塩とを含む水溶液に還元剤を添加し、この水溶液に含まれるニッケルイオン、鉄イオンおよび亜鉛イオンを同時に還元することにより、ニッケル―鉄―亜鉛合金ナノ粒子を生成する方法である。 In the method for producing nickel-iron-zinc alloy nanoparticles of the present invention, a reducing agent is added to an aqueous solution containing a nickel salt, an iron salt and a zinc salt, and nickel ions, iron ions and zinc ions contained in the aqueous solution are simultaneously added. This is a method for producing nickel-iron-zinc alloy nanoparticles by reduction.
本発明のニッケル―鉄―亜鉛合金ナノ粒子の製造方法に用いられるニッケル塩としては、水溶性のものであれば特に限定されないが、例えば、塩化ニッケル（ＮｉＣｌ２）、硝酸ニッケル（Ｎｉ（ＮＯ３）２）、酢酸ニッケル（Ｎｉ（ＣＨ３ＣＯＯ）２）、硫酸ニッケル（ＮｉＳＯ４）などが挙げられる。 The nickel salt used in the method for producing nickel-iron-zinc alloy nanoparticles of the present invention is not particularly limited as long as it is water-soluble. For example, nickel chloride (NiCl 2 ), nickel nitrate (Ni (NO 3) 2 ), nickel acetate (Ni (CH 3 COO) 2 ), nickel sulfate (NiSO 4 ) and the like.
本発明のニッケル―鉄―亜鉛合金ナノ粒子の製造方法に用いられる鉄塩としては、水溶性のものであれば鉄の価数は２価でも３価でもよく、例えば、塩化第一鉄（ＦｅＣｌ２）、塩化第二鉄（ＦｅＣｌ３）、硝酸第一鉄（Ｆｅ（ＮＯ３）２）、硝酸第二鉄（Ｆｅ（ＮＯ３）３）、酢酸第一鉄（Ｆｅ（ＣＨ３ＣＯ２）２）、酢酸第二鉄（Ｆｅ（ＣＨ３ＣＯ２）３）、硫酸第一鉄（ＦｅＳＯ４）、硫酸第二鉄（Ｆｅ２（ＳＯ４）３）などが挙げられる。 As the iron salt used in the method for producing nickel-iron-zinc alloy nanoparticles of the present invention, the valence of iron may be divalent or trivalent as long as it is water-soluble. For example, ferrous chloride (FeCl 2 ), ferric chloride (FeCl 3 ), ferrous nitrate (Fe (NO 3 ) 2 ), ferric nitrate (Fe (NO 3 ) 3 ), ferrous acetate (Fe (CH 3 CO 2 ) 2 ), ferric acetate (Fe (CH 3 CO 2 ) 3 ), ferrous sulfate (FeSO 4 ), ferric sulfate (Fe 2 (SO 4 ) 3 ) and the like.
本発明のニッケル―鉄―亜鉛合金ナノ粒子の製造方法に用いられる亜鉛塩としては、水溶性のものであれば特に限定されないが、例えば、塩化亜鉛（ＺｎＣｌ２）、硝酸亜鉛（Ｚｎ（ＮＯ３）２）、酢酸亜鉛（Ｚｎ（ＣＨ３ＣＯＯ）２）、硫酸亜鉛（ＺｎＳＯ４）などが挙げられる。 The zinc salt used in the method for producing nickel-iron-zinc alloy nanoparticles of the present invention is not particularly limited as long as it is water-soluble. For example, zinc chloride (ZnCl 2 ), zinc nitrate (Zn (NO 3) 2 ), zinc acetate (Zn (CH 3 COO) 2 ), zinc sulfate (ZnSO 4 ) and the like.
このようなニッケル塩、鉄塩および亜鉛塩の水溶液を調製する際、ニッケル塩、鉄塩および亜鉛塩を溶解する純水の量は、金属イオン（ニッケルイオン（Ｎｉ２＋）、鉄イオン（Ｆｅ２＋、Ｆｅ３＋）および亜鉛イオン（Ｚｎ２＋））０．１ｍｏｌに対して、０．１Ｌ以上かつ２Ｌ以下が好ましい。
ニッケル塩、鉄塩および亜鉛イオンを溶解する純水の量を、金属イオン（ニッケルイオン（Ｎｉ２＋）、鉄イオン（Ｆｅ２＋、Ｆｅ３＋）および亜鉛イオン（Ｚｎ２＋））０．１ｍｏｌに対して、０．１Ｌ以上かつ２Ｌ以下とするのが好ましい理由は、純水の量が０．１Ｌ未満では、ニッケル―鉄―亜鉛合金の結晶核の量が多くなり過ぎて、ニッケル―鉄―亜鉛合金ナノ粒子同士が近付き過ぎる状態で成長するため、凝集が起こり易くなるからであり、一方、純水の量が２Ｌを超えると、還元剤によりこのニッケル塩―鉄塩―亜鉛塩水溶液に含まれるニッケルイオン、鉄イオンおよび亜鉛イオンを還元した際、ニッケル―鉄―亜鉛合金ナノ粒子の結晶核の生成する量が少なく、粗大粒子化し易くなるからである。
When preparing such an aqueous solution of nickel salt, iron salt and zinc salt, the amount of pure water in which the nickel salt, iron salt and zinc salt are dissolved is selected from metal ions (nickel ions (Ni 2+ ), iron ions (Fe 2+ )). , Fe 3+ ) and zinc ions (Zn 2+ )) of 0.1 mol are preferably 0.1 L or more and 2 L or less.
The amount of pure water that dissolves nickel salt, iron salt and zinc ion is 0.1 mol of metal ion (nickel ion (Ni 2+ ), iron ion (Fe 2+ , Fe 3+ ) and zinc ion (Zn 2+ )). The reason why it is preferable that the amount be 0.1 L or more and 2 L or less is that if the amount of pure water is less than 0.1 L, the amount of crystal nuclei of the nickel-iron-zinc alloy becomes too large, and the nickel-iron-zinc alloy This is because the nanoparticles grow too close to each other, so that aggregation easily occurs. On the other hand, when the amount of pure water exceeds 2 L, nickel contained in the nickel salt-iron salt-zinc salt aqueous solution by the reducing agent. This is because when ions, iron ions and zinc ions are reduced, the amount of crystal nuclei of the nickel-iron-zinc alloy nanoparticles generated is small, and it becomes easy to make coarse particles.
ニッケル塩、鉄塩および亜鉛塩の混合比率のうち、鉄塩の添加量は、目的とするニッケル―鉄―亜鉛合金ナノ粒子の磁気特性に応じて適宜調節されるが、ニッケル―鉄―亜鉛合金ナノ粒子は、鉄の添加量が少ないと保持力がより小さくなり、鉄の添加量が多くなると飽和磁化がより大きくなる傾向にあるが、２０重量％以上かつ６０重量％以下の範囲であることが好ましい。 Among the mixing ratios of nickel salt, iron salt and zinc salt, the amount of iron salt added is appropriately adjusted according to the magnetic properties of the target nickel-iron-zinc alloy nanoparticles, but the nickel-iron-zinc alloy Nanoparticles tend to have lower coercive force when the amount of iron added is small, and the saturation magnetization tends to increase when the amount of iron added is large, but it should be in the range of 20 wt% or more and 60 wt% or less. Is preferred.
ニッケル塩、鉄塩および亜鉛塩の混合比率のうち、亜鉛塩の添加量は、２重量％以上かつ１０重量％以下の範囲にあることが好ましい。
亜鉛塩の添加量が２重量％以上かつ１０重量％以下の範囲であることが好ましい理由は、亜鉛塩の添加量が２重量％未満では、ニッケル―鉄―亜鉛合金ナノ粒子が十分な塑性変形能を得られないためであり、一方、亜鉛塩の添加量が１０重量％を超えると、亜鉛原子自体の磁気モーメントが小さいので飽和磁化が小さくなるからである。
Of the mixing ratio of nickel salt, iron salt and zinc salt, the amount of zinc salt added is preferably in the range of 2 wt% or more and 10 wt% or less.
The reason why the amount of zinc salt added is preferably in the range of 2 wt% or more and 10 wt% or less is that when the amount of zinc salt added is less than 2 wt%, the nickel-iron-zinc alloy nanoparticles are sufficiently plastically deformed. On the other hand, if the addition amount of the zinc salt exceeds 10% by weight, the magnetic moment of the zinc atom itself is small, so that the saturation magnetization becomes small.
さらに、本発明のニッケル―鉄―亜鉛合金ナノ粒子の製造方法では、ニッケル塩、鉄塩および亜鉛塩を溶解する純水中に、メタノールやエタノールなどの水溶性のアルコールを１０〜４０体積％程度添加することが好ましい。このようにニッケル塩、鉄塩および亜鉛塩を溶解する純水中に水溶性のアルコールを所定量添加すると、ニッケルイオン、鉄イオンおよび亜鉛イオンの還元反応の際、ニッケル―鉄―亜鉛合金の結晶核が生成し易くなるので好ましい。 Furthermore, in the method for producing nickel-iron-zinc alloy nanoparticles of the present invention, about 10 to 40% by volume of a water-soluble alcohol such as methanol or ethanol in pure water in which nickel salt, iron salt and zinc salt are dissolved. It is preferable to add. When a predetermined amount of water-soluble alcohol is added to pure water in which nickel salt, iron salt and zinc salt are dissolved in this way, during the reduction reaction of nickel ion, iron ion and zinc ion, crystals of nickel-iron-zinc alloy It is preferable because nuclei are easily generated.
本発明のニッケル―鉄―亜鉛合金ナノ粒子の製造方法に用いられる還元剤としては、ニッケル塩―鉄塩―亜鉛塩水溶液中で還元力を発揮するものが用いられるが、例えば、ヒドラジン（Ｎ２Ｈ４）と水酸化アルカリ、ホルムアルデヒドスルホキシル酸ナトリウム、水素化ホウ素金属塩などが挙げられる。
本発明のニッケル―鉄―亜鉛合金ナノ粒子の製造方法では、比較的強い還元力を得られることから、還元剤として、水酸化アルカリとヒドラジンを併用してなるものが好ましい。
As the reducing agent used in the method for producing nickel-iron-zinc alloy nanoparticles of the present invention, a reducing agent that exhibits reducing power in an aqueous solution of nickel salt-iron salt-zinc salt is used. For example, hydrazine (N 2 H 4 ), alkali hydroxide, sodium formaldehyde sulfoxylate, metal borohydride and the like.
In the method for producing nickel-iron-zinc alloy nanoparticles of the present invention, a relatively strong reducing power can be obtained, so that a combination of alkali hydroxide and hydrazine as a reducing agent is preferable.
水酸化アルカリとヒドラジンを還元剤として使用した場合、水酸化アルカリの添加量が、ニッケル塩―鉄塩―亜鉛塩水溶液中のニッケルイオンおよび鉄イオンのモル量に対して５倍量以上かつ１０倍量以下が好ましく、５．５倍量以上かつ７倍量以下がより好ましい。
水酸化アルカリの添加量を、ニッケル塩―鉄塩―亜鉛塩水溶液中のニッケルイオン、鉄イオンおよび亜鉛イオンのモル量に対して５倍量以上かつ１０倍量以下とした理由は、水酸化アルカリの添加量が５倍量未満では、ヒドラジンが十分に還元性を発揮するｐＨ１２以上の強アルカリ性に達しないからであり、一方、水酸化アルカリの添加量が１０倍量を超えても、ｐＨがあまり変わらないからである。
When alkali hydroxide and hydrazine are used as the reducing agent, the amount of alkali hydroxide added is at least 5 times and 10 times the molar amount of nickel ions and iron ions in the nickel salt-iron salt-zinc salt aqueous solution. The amount is preferably not more than the amount, more preferably not less than 5.5 times and not more than 7 times.
The reason why the amount of alkali hydroxide added was 5 to 10 times the molar amount of nickel ions, iron ions and zinc ions in the nickel salt-iron salt-zinc salt aqueous solution was If the added amount is less than 5 times, the hydrazine does not reach a strong alkalinity of pH 12 or more, which exhibits sufficient reducing properties. On the other hand, even if the added amount of alkali hydroxide exceeds 10 times the pH, Because it doesn't change much.
また、水酸化アルカリとヒドラジンを還元剤として使用した場合、ヒドラジンの添加量が、ニッケル塩―鉄塩―亜鉛塩水溶液中のニッケルイオン、鉄イオンおよび亜鉛イオンのモル量に対して２倍量以上かつ５０倍量以下が好ましく、５倍量以上かつ３０倍量以下がより好ましい。
ヒドラジンの添加量を、ニッケル塩―鉄塩―亜鉛塩水溶液中のニッケルイオン、鉄イオンおよび亜鉛イオンのモル量に対して２倍量以上かつ５０倍量以下とした理由は、ヒドラジンの添加量が２倍量未満では、ニッケルイオン、鉄イオンおよび亜鉛イオンの還元反応が十分に進行しないからであり、一方、ヒドラジンの添加量が５０倍量を超えても、未反応のヒドラジンが残るだけで生成するニッケル―鉄―亜鉛合金ナノ粒子に変化がないからである。
In addition, when alkali hydroxide and hydrazine are used as the reducing agent, the amount of hydrazine added is more than twice the molar amount of nickel ion, iron ion and zinc ion in the nickel salt-iron salt-zinc salt aqueous solution. And 50 times or less is preferable and 5 times or more and 30 times or less is more preferable.
The reason why the amount of hydrazine added is more than twice and less than 50 times the molar amount of nickel ion, iron ion and zinc ion in the nickel salt-iron salt-zinc salt aqueous solution is that the amount of hydrazine added is If the amount is less than 2 times, the reduction reaction of nickel ion, iron ion and zinc ion does not proceed sufficiently. On the other hand, even if the amount of hydrazine exceeds 50 times, it is produced only by leaving unreacted hydrazine. This is because there is no change in the nickel-iron-zinc alloy nanoparticles.
また、本発明のニッケル―鉄―亜鉛合金ナノ粒子の製造方法では、ニッケル塩―鉄塩―亜鉛塩水溶液において、還元剤によるニッケルイオン、鉄イオンおよび亜鉛イオンの還元反応の反応速度を高め、ニッケル―鉄―亜鉛合金ナノ粒子を効率よく生成するためには、ニッケル塩―鉄塩―亜鉛塩水溶液に所定量の還元剤を添加した後、このニッケル塩―鉄塩―亜鉛塩水溶液を５０℃以上かつ８０℃以下に加熱することが好ましく、５５℃以上かつ６５℃以下に加熱することがより好ましい。
還元剤を添加した後のニッケル塩―鉄塩―亜鉛塩水溶液を加熱する温度が５０℃未満では、ニッケルイオン、鉄イオンおよび亜鉛イオンの還元反応の進行が緩慢となるため、ニッケル―鉄―亜鉛合金ナノ粒子の生成効率が悪くなる。一方、還元剤を添加した後のニッケル塩―鉄塩―亜鉛塩水溶液を加熱する温度が８０℃を超えると、生成したニッケル―鉄―亜鉛合金ナノ粒子が酸化するおそれがある。
In the method for producing nickel-iron-zinc alloy nanoparticles of the present invention, in the nickel salt-iron salt-zinc salt aqueous solution, the reaction rate of the reduction reaction of nickel ions, iron ions and zinc ions by the reducing agent is increased, -In order to efficiently produce iron-zinc alloy nanoparticles, after adding a predetermined amount of reducing agent to the nickel salt-iron salt-zinc salt aqueous solution, the nickel salt-iron salt-zinc salt aqueous solution is kept at 50 ° C or higher. And it is preferable to heat to 80 ° C. or lower, more preferably to 55 ° C. or higher and 65 ° C. or lower.
If the temperature at which the nickel salt-iron salt-zinc salt aqueous solution is heated after the addition of the reducing agent is less than 50 ° C., the progress of the reduction reaction of nickel ions, iron ions, and zinc ions becomes slow, so nickel-iron-zinc The generation efficiency of alloy nanoparticles is deteriorated. On the other hand, when the temperature of heating the nickel salt-iron salt-zinc salt aqueous solution after adding the reducing agent exceeds 80 ° C., the produced nickel-iron-zinc alloy nanoparticles may be oxidized.
また、ニッケル塩―鉄塩―亜鉛塩水溶液に所定量の還元剤を添加した後、このニッケル塩―鉄塩―亜鉛塩水溶液を５０℃以上かつ８０℃以下に加熱する時間を、１時間以上かつ３時間以下とすることが好ましく、１時間以上かつ２時間以下とすることがより好ましい。 Further, after adding a predetermined amount of reducing agent to the nickel salt-iron salt-zinc salt aqueous solution, the time for heating the nickel salt-iron salt-zinc salt aqueous solution to 50 ° C. or more and 80 ° C. or less is 1 hour or more and It is preferably 3 hours or less, and more preferably 1 hour or more and 2 hours or less.
このように、ニッケル塩―鉄塩―亜鉛塩水溶液に所定量の還元剤を添加した後、このニッケル塩―鉄塩―亜鉛塩水溶液を５０℃以上かつ８０℃以下の温度範囲にて、１時間以上かつ３時間以下、加熱することにより、ニッケルイオン、鉄イオンおよび亜鉛イオンの還元反応が開始すると、黒色の粒子が生成する。
また、ニッケルイオン、鉄イオンおよび亜鉛イオンの還元反応が均一に進行するようにするために、還元剤を添加した後のニッケル塩―鉄塩―亜鉛塩水溶液を、攪拌しながら加熱することが好ましい。
Thus, after adding a predetermined amount of reducing agent to the nickel salt-iron salt-zinc salt aqueous solution, the nickel salt-iron salt-zinc salt aqueous solution is heated at a temperature range of 50 ° C. to 80 ° C. for 1 hour. When the reduction reaction of nickel ions, iron ions, and zinc ions starts by heating for 3 hours or less, black particles are generated.
Further, in order to allow the reduction reaction of nickel ions, iron ions and zinc ions to proceed uniformly, it is preferable to heat the nickel salt-iron salt-zinc salt aqueous solution after adding the reducing agent while stirring. .
このようにして生成した黒色の粒子から、必要に応じて、不純物イオンを除去した後、乾燥してニッケル―鉄―亜鉛合金ナノ粒子が得られる。
ニッケル―鉄―亜鉛合金ナノ粒子から不純物イオンを除去する方法としては、例えば、ニッケル―鉄―亜鉛合金ナノ粒子を純水中に分散させた後、ろ過する工程を繰り返す方法が挙げられる。
Impurity ions are removed from the black particles thus produced, if necessary, followed by drying to obtain nickel-iron-zinc alloy nanoparticles.
Examples of the method for removing impurity ions from the nickel-iron-zinc alloy nanoparticles include a method in which nickel-iron-zinc alloy nanoparticles are dispersed in pure water and then filtered.
本発明のニッケル―鉄―亜鉛合金ナノ粒子の製造方法によれば、成分の金属元素を溶融する必要がないので、高融点のニッケルおよび鉄と、沸点の低い亜鉛の合金ナノ粒子を、工業的規模にて低製造コストで、安全かつ効率的に製造することができる。
そして、本発明のニッケル―鉄―亜鉛合金ナノ粒子の製造方法によって得られた、本発明のニッケル―鉄―亜鉛合金ナノ粒子は、飽和磁化が５０ｅｍｕ／ｇ以上かつ保磁力が１００Ｏｅ以下であり、高い飽和磁化と低い保磁力をもつ軟磁性を示すと共に、特定の結晶方向に対して塑性変形し易く、小さな機械的応力で塑性変形可能な高い塑性変形能を有している。
このように、本発明のニッケル―鉄―亜鉛合金ナノ粒子は、小さな機械的応力で塑性変形可能なことから、塗料やペーストを作製する際の混合や混練によっても平板化することができるので、工程を簡略化することができる。
According to the method for producing nickel-iron-zinc alloy nanoparticles of the present invention, since it is not necessary to melt the metal element as a component, high melting point nickel and iron and zinc alloy nanoparticles having a low boiling point are industrially produced. It can be manufactured safely and efficiently at a low manufacturing cost on a scale.
And the nickel-iron-zinc alloy nanoparticles of the present invention obtained by the method for producing nickel-iron-zinc alloy nanoparticles of the present invention have a saturation magnetization of 50 emu / g or more and a coercive force of 100 Oe or less, It exhibits soft magnetism with high saturation magnetization and low coercive force, is easily plastically deformed in a specific crystal direction, and has high plastic deformability that can be plastically deformed with a small mechanical stress.
Thus, since the nickel-iron-zinc alloy nanoparticles of the present invention can be plastically deformed with a small mechanical stress, they can be flattened by mixing and kneading when preparing paints and pastes. The process can be simplified.
次に、本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子の製造方法について説明する。
本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子の製造方法は、本発明のニッケル―鉄―亜鉛合金ナノ粒子に機械的応力を加えて塑性変形させることにより、平板状ニッケル―鉄―亜鉛合金ナノ粒子を生成する方法である。
Next, a method for producing tabular nickel-iron-zinc alloy nanoparticles of the present invention will be described.
The method for producing tabular nickel-iron-zinc alloy nanoparticles according to the present invention is obtained by applying a mechanical stress to the nickel-iron-zinc alloy nanoparticles according to the present invention to cause plastic deformation. A method for producing nanoparticles.
ニッケル―鉄―亜鉛合金ナノ粒子に機械的応力を加える手段としては、ボールミル、アトライタ、振動ミル、遊星ミルなどの湿式混合機の他、圧延機、粉末鍛造機などが用いられるが、ニッケル―鉄―亜鉛合金ナノ粒子に強い衝撃を加えず、有効なエネルギーを効果的に加えることができる点、取り扱いの容易さ、工程のスケールアップの容易さなどを考慮すると、湿式混合機が好ましく、この湿式混合機の中でもボールミルが特に好ましい。
なお、本発明のニッケル―鉄―亜鉛合金ナノ粒子は、亜鉛が添加されているため、塑性変形能が極めて高く、したがって、過剰に高いエネルギーを加えることなく、平板状に変形することができる。
As means for applying mechanical stress to nickel-iron-zinc alloy nanoparticles, wet mills such as ball mills, attritors, vibration mills and planetary mills, as well as rolling mills and powder forging machines are used. -Considering the fact that effective energy can be effectively applied without applying a strong impact to the zinc alloy nanoparticles, the wet mixer is preferred, considering the ease of handling and the ease of scale-up of the process. Among the mixers, a ball mill is particularly preferable.
The nickel-iron-zinc alloy nanoparticles of the present invention have extremely high plastic deformability because zinc is added, and therefore can be deformed into a flat plate shape without applying excessively high energy.
ボールミルを用いる場合、充填するボールの量は、ボールミルの容積の２０〜５０体積％が好ましい。
また、ボールの材質は、ニッケル―鉄―亜鉛合金ナノ粒子を汚染するおそれがなく、このナノ粒子に機械的応力を効果的に加えることができるものであり、比重の大きなものであればよく、特に、耐食性などの点からジルコニアが好ましい。
When a ball mill is used, the amount of balls to be filled is preferably 20 to 50% by volume of the ball mill volume.
Also, the material of the ball can be used to effectively apply mechanical stress to the nanoparticles without any risk of contaminating the nickel-iron-zinc alloy nanoparticles. In particular, zirconia is preferable from the viewpoint of corrosion resistance.
また、ボールミルに充填するニッケル―鉄―亜鉛合金ナノ粒子の重量は、ボールの重量に対して、１／１００の以上かつ１／１０の以下とすることが好ましい。
ボールミルに充填するニッケル―鉄―亜鉛合金ナノ粒子の量が、ボールの重量に対して、１／１００未満では、ボールに対するニッケル―鉄―亜鉛合金ナノ粒子の量が少な過ぎて、このナノ粒子は過剰に機械的応力が加えられて粉砕され、所定の平板状ニッケル―鉄―亜鉛合金ナノ粒子を生成できない。一方、ボールミルに充填するニッケル―鉄―亜鉛合金ナノ粒子の量が、ボールの重量に対して、１／１０を超えると、ボールに対するニッケル―鉄―亜鉛合金ナノ粒子の量が多過ぎて、このナノ粒子に機械的応力が効果的に加えられないため、平板状ニッケル―鉄―亜鉛合金ナノ粒子の生成効率が悪くなる。
The weight of the nickel-iron-zinc alloy nanoparticles filled in the ball mill is preferably 1/100 or more and 1/10 or less of the weight of the ball.
If the amount of nickel-iron-zinc alloy nanoparticles filled in the ball mill is less than 1/100 of the weight of the ball, the amount of nickel-iron-zinc alloy nanoparticles relative to the ball is too small. Excessive mechanical stress is applied and pulverized, and the predetermined flat plate-like nickel-iron-zinc alloy nanoparticles cannot be produced. On the other hand, if the amount of nickel-iron-zinc alloy nanoparticles filling the ball mill exceeds 1/10 of the weight of the ball, the amount of nickel-iron-zinc alloy nanoparticles relative to the ball is too large. Since mechanical stress is not effectively applied to the nanoparticles, the generation efficiency of the tabular nickel-iron-zinc alloy nanoparticles is deteriorated.
ニッケル―鉄―亜鉛合金ナノ粒子を塑性変形させるために、このナノ粒子に機械的応力を加える時間は、ニッケル―鉄合金ナノ粒子を塑性変形するためには、１０時間以上機械的応力を加える必要があるのに比べて極めて短く、１０分〜１２０分程度とする。 In order to plastically deform nickel-iron-zinc alloy nanoparticles, the mechanical stress must be applied to the nanoparticles for 10 hours or more in order to plastically deform nickel-iron alloy nanoparticles. It is extremely short compared to the case where there is a difference between 10 minutes and 120 minutes.
また、ボールミルにニッケル―鉄―亜鉛合金ナノ粒子を充填する際、アルコールを添加することにより、ニッケル―鉄―亜鉛合金ナノ粒子が粉砕されて、その微細粒子が生成するのを抑制し、ニッケル―鉄―亜鉛合金ナノ粒子の塑性変形により、平板状ニッケル―鉄―亜鉛合金ナノ粒子が生成するのを促進することができる。さらに、アルコールを添加することにより、ニッケル―鉄―亜鉛合金ナノ粒子の凝集を防いで不均一性を緩和するだけでなく、このナノ粒子の表面の酸化被膜を還元反応により除去して、粒子同士の凝着を容易にすることができる。 In addition, when the ball mill is filled with nickel-iron-zinc alloy nanoparticles, the addition of alcohol suppresses the formation of fine particles by pulverizing the nickel-iron-zinc alloy nanoparticles. The plastic deformation of iron-zinc alloy nanoparticles can promote the formation of tabular nickel-iron-zinc alloy nanoparticles. Furthermore, by adding alcohol, the nickel-iron-zinc alloy nanoparticles are not only prevented from agglomerating and the non-uniformity is mitigated. Can be easily adhered.
本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子の製造方法に用いられるアルコールとしては、特に限定されないが、反応後に回収し易い点を考慮すると、低沸点のメタノールやエタノールが好ましい。
また、アルコールの添加量は、ニッケル―鉄―亜鉛合金ナノ粒子の重量の２倍以上かつ５倍以下とすることが好ましい。
アルコールの添加量が、ニッケル―鉄―亜鉛合金ナノ粒子の重量の２倍未満では、ニッケル―鉄―亜鉛合金ナノ粒子の微細粒子化の抑制、ニッケル―鉄―亜鉛合金ナノ粒子の凝集の防止、ニッケル―鉄―亜鉛合金ナノ粒子の表面の酸化被膜の除去などの効果が十分に得られない。一方、アルコールの添加量が、ニッケル―鉄―亜鉛合金ナノ粒子の重量の５倍を超えても、処理時間が長くなるだけで、得られる平板状ニッケル―鉄―亜鉛合金ナノ粒子に変化がない。
The alcohol used in the method for producing tabular nickel-iron-zinc alloy nanoparticles of the present invention is not particularly limited, but in view of easy recovery after the reaction, low boiling point methanol or ethanol is preferable.
Moreover, it is preferable that the addition amount of the alcohol is not less than 2 times and not more than 5 times the weight of the nickel-iron-zinc alloy nanoparticles.
If the amount of alcohol added is less than twice the weight of the nickel-iron-zinc alloy nanoparticles, suppression of micronization of nickel-iron-zinc alloy nanoparticles, prevention of aggregation of nickel-iron-zinc alloy nanoparticles, Effects such as removal of the oxide film on the surface of nickel-iron-zinc alloy nanoparticles cannot be obtained sufficiently. On the other hand, even if the amount of alcohol added exceeds 5 times the weight of the nickel-iron-zinc alloy nanoparticles, the treatment time is increased and the resulting flat nickel-iron-zinc alloy nanoparticles remain unchanged. .
本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子の製造方法によれば、本発明のニッケル―鉄―亜鉛合金ナノ粒子に機械的応力を加えて塑性変形させることにより、平板状ニッケル―鉄―亜鉛合金ナノ粒子を生成するので、極めて短時間にニッケル―鉄―亜鉛合金ナノ粒子を塑性変形させることができ、ニッケル―鉄―亜鉛合金ナノ粒子に大きな機械的応力を加えることがないので、平板状ニッケル―鉄―亜鉛合金ナノ粒子を、工業的規模にて低製造コストで、安全かつ効率的に製造することができる。 According to the method for producing tabular nickel-iron-zinc alloy nanoparticles of the present invention, a mechanical stress is applied to the nickel-iron-zinc alloy nanoparticles of the present invention to cause plastic deformation, thereby producing tabular nickel-iron- Since zinc alloy nanoparticles are generated, nickel-iron-zinc alloy nanoparticles can be plastically deformed in a very short time, and no large mechanical stress is applied to the nickel-iron-zinc alloy nanoparticles. The nickel-iron-zinc alloy nanoparticles can be produced safely and efficiently at a low production cost on an industrial scale.
そして、本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子の製造方法によって得られた、本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子は、厚みが１μｍ以下かつアスペクト比が２以上であることが好ましい。
本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子の厚みが１μｍ以下であることが好ましい理由は、厚みが１μｍを超えると、渦電流による損失を低減できないからである。
本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子のアスペクト比が２以上であることが好ましい理由は、アスペクト比が２を超えると、十分に配向方向の透磁率を高めることができないからである。
The tabular nickel-iron-zinc alloy nanoparticles of the present invention obtained by the method for producing tabular nickel-iron-zinc alloy nanoparticles of the present invention have a thickness of 1 μm or less and an aspect ratio of 2 or more. It is preferable.
The reason why the thickness of the tabular nickel-iron-zinc alloy nanoparticles of the present invention is preferably 1 μm or less is that when the thickness exceeds 1 μm, loss due to eddy current cannot be reduced.
The reason why the aspect ratio of the tabular nickel-iron-zinc alloy nanoparticles of the present invention is preferably 2 or more is that when the aspect ratio exceeds 2, the permeability in the orientation direction cannot be sufficiently increased. .
本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子は、外部磁場を加えることにより、同じ方向を向くように配向させることが可能であり、その平板状の面内の一方向に沿って、同体積の球状のニッケル―鉄―亜鉛合金ナノ粒子よりも強く磁化する。よって、本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子は、その面内の一方向の透磁率が、同体積の球状のニッケル―鉄―亜鉛合金ナノ粒子に比べて格段に大きくなる。なお、本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子は、このナノ粒子が配向した平面上からＸ線回折（ＸＲＤ）を測定すると、配向していないものに比べて結晶面のピークが強く検出されることから、特定の結晶面で塑性変形が起こり、それにより配向していることが分かる。
したがって、本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子によれば、特定方向の磁場に対して強く磁性を示す高透磁率材料が容易に得られる。
The plate-like nickel-iron-zinc alloy nanoparticles of the present invention can be oriented so as to face in the same direction by applying an external magnetic field. Magnetizes stronger than spherical spherical nickel-iron-zinc alloy nanoparticles. Accordingly, the planar nickel-iron-zinc alloy nanoparticles of the present invention have a remarkably larger magnetic permeability in one plane than the spherical nickel-iron-zinc alloy nanoparticles having the same volume. The flat nickel-iron-zinc alloy nanoparticles of the present invention have a crystal face peak stronger than that of non-oriented particles when X-ray diffraction (XRD) is measured from the plane on which the nanoparticles are oriented. From the detection, it can be seen that plastic deformation occurs in a specific crystal plane and is thereby oriented.
Therefore, according to the tabular nickel-iron-zinc alloy nanoparticles of the present invention, a high permeability material that exhibits strong magnetism against a magnetic field in a specific direction can be easily obtained.
また、本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子は高透磁率材料であることから、このナノ粒子を、樹脂などの非磁性材料中にフィラーとして配向分散させることにより、高透磁率の軟磁性金属／樹脂複合体が得られる。
さらに、本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子を、非極性の溶媒中に分散させることにより、塗料やペーストが得られる。このような塗料やペーストは、電気機器やＩＣタグ（ＲＦＩＤシステム）などに塗布して磁気シールド膜を形成することにより、これら電気機器やＩＣタグ（ＲＦＩＤシステム）などに磁気シールド性を付与することができる。
Further, since the plate-like nickel-iron-zinc alloy nanoparticles of the present invention are high magnetic permeability materials, by aligning and dispersing these nanoparticles as fillers in nonmagnetic materials such as resins, high magnetic permeability can be obtained. A soft magnetic metal / resin composite is obtained.
Furthermore, a coating material or a paste can be obtained by dispersing the tabular nickel-iron-zinc alloy nanoparticles of the present invention in a nonpolar solvent. Such paints and pastes are applied to electrical devices and IC tags (RFID systems) to form a magnetic shield film, thereby providing magnetic shielding properties to these electrical devices and IC tags (RFID systems). Can do.
また、本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子は、金属であるから、導電性も有するので、回路基板における電極材料、燃料電池や二次電池における電極材料としても好適である。
さらに、本発明の平板状ニッケル―鉄―亜鉛合金ナノ粒子は、平板状であるから、隠蔽性にも優れているので、各種装飾品、あるいは表面処理などにも適用可能である。
Further, since the plate-like nickel-iron-zinc alloy nanoparticles of the present invention are metal, they also have conductivity, and are therefore suitable as electrode materials for circuit boards, fuel cells and secondary batteries.
Furthermore, since the tabular nickel-iron-zinc alloy nanoparticles of the present invention are tabular, they are excellent in concealment, and therefore can be applied to various ornamental products or surface treatments.
以下、実施例により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限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.
「実施例」
塩化ニッケル六水和物（ＮｉＣｌ２・６Ｈ２Ｏ、特級試薬、関東化学社製）３５．５ｇと、塩化第一鉄四水和物（ＦｅＣｌ２・４Ｈ２Ｏ、特級試薬、関東化学社製）７．９ｇと、硝酸亜鉛六水和物（Ｚｎ（ＮＯ３）２・６Ｈ２Ｏ）３．２ｇとを、純水３００ｍＬとメタノール２００ｍＬの混合溶液に溶解し、塩化ニッケル、塩化第一鉄および硝酸亜鉛の水溶液を調製した。
次いで、この水溶液に、濃度が６ｍｏｌ／Ｌの水酸化ナトリウム水溶液２００ｍＬを攪拌しながら添加した。
次いで、この水溶液を攪拌しながら６０℃に加熱し、さらに、ヒドラジン一水和物（Ｎ２Ｈ４・Ｈ２Ｏ、特級試薬、関東化学社製）３００ｇを添加して、これらの水溶液を攪拌しながら６０℃にて３時間、加熱して、黒色の粒子を得た。
次いで、この黒色の粒子を純水とエタノールで洗浄した後、真空中で乾燥して微粒子を得た。
"Example"
35.5 g of nickel chloride hexahydrate (NiCl 2 · 6H 2 O, special grade reagent, manufactured by Kanto Chemical Co.) and ferrous chloride tetrahydrate (FeCl 2 · 4H 2 O, special grade reagent, manufactured by Kanto Chemical Co., Inc.) ) 7.9 g and zinc nitrate hexahydrate (Zn (NO 3 ) 2 · 6H 2 O) 3.2 g are dissolved in a mixed solution of 300 mL of pure water and 200 mL of methanol, and nickel chloride, ferrous chloride And an aqueous solution of zinc nitrate was prepared.
Next, 200 mL of a sodium hydroxide aqueous solution having a concentration of 6 mol / L was added to this aqueous solution while stirring.
Next, this aqueous solution was heated to 60 ° C. while stirring, and 300 g of hydrazine monohydrate (N 2 H 4 .H 2 O, special grade reagent, manufactured by Kanto Chemical Co., Inc.) was further added, and these aqueous solutions were stirred. While heating at 60 ° C. for 3 hours, black particles were obtained.
Next, the black particles were washed with pure water and ethanol and then dried in vacuum to obtain fine particles.
得られた微粒子をＸ線回折（ＸＲＤ）により分析した結果、ニッケル、鉄および亜鉛の合金粒子であることが分かった。この微粒子は、結晶構造が面心立方をなすことも確認された。また、（１１１）面のピーク角度より格子定数を算出したところ、０．３５５１ｎｍであった。
さらに、振動試料型磁力計（ＶＳＭ）により、このニッケル、鉄および亜鉛の合金粒子の飽和磁化および保磁力を測定したところ、飽和磁化は８１ｅｍｕ／ｇ、保磁力は３３Ｏｅであった。
次いで、このニッケル―鉄―亜鉛合金ナノ粒子１ｇと、直径が０．４ｍｍのジルコニア製のボール１２ｇと、エタノール１０ｇとを、容積が７５ｍＬの樹脂製容器内に充填し、この樹脂製容器をボールミルにて３０分回転させて、このニッケル―鉄―亜鉛合金ナノ粒子に機械的応力を加えた。
そして、走査型電子顕微鏡（ＳＥＭ）により、処理後のニッケル―鉄―亜鉛合金ナノ粒子の電子顕微鏡（図１参照）を得た。
As a result of analyzing the obtained fine particles by X-ray diffraction (XRD), it was found to be alloy particles of nickel, iron and zinc. The fine particles were also confirmed to have a face-centered cubic crystal structure. The lattice constant calculated from the peak angle of (111) plane was 0.3551 nm.
Further, when the saturation magnetization and coercivity of the alloy particles of nickel, iron and zinc were measured with a vibrating sample magnetometer (VSM), the saturation magnetization was 81 emu / g and the coercivity was 33 Oe.
Next, 1 g of the nickel-iron-zinc alloy nanoparticles, 12 g of a zirconia ball having a diameter of 0.4 mm, and 10 g of ethanol are filled in a 75 mL resin container, and the resin container is placed in a ball mill. Then, mechanical stress was applied to the nickel-iron-zinc alloy nanoparticles.
And the electron microscope (refer FIG. 1) of the nickel-iron-zinc alloy nanoparticle after a process was obtained with the scanning electron microscope (SEM).
「比較例」
塩化ニッケル六水和物（ＮｉＣｌ２・６Ｈ２Ｏ、特級試薬、関東化学社製）３５．５ｇと、塩化第一鉄四水和物（ＦｅＣｌ２・４Ｈ２Ｏ、特級試薬、関東化学社製）７．９ｇとを、純水３００ｍＬとメタノール２００ｍＬの混合溶液に溶解し、塩化ニッケルと塩化第一鉄の水溶液を調製した。
次いで、この水溶液に、濃度が６ｍｏｌ／Ｌの水酸化ナトリウム水溶液２００ｍＬを攪拌しながら添加した。
次いで、この水溶液を攪拌しながら６０℃に加熱し、さらに、ヒドラジン一水和物（Ｎ２Ｈ４・Ｈ２Ｏ、特級試薬、関東化学社製）３００ｇを添加して、これらの水溶液を攪拌しながら６０℃にて３時間、加熱して、黒色の粒子を得た。
次いで、この黒色の粒子を純水とエタノールで洗浄した後、真空中で乾燥して微粒子を得た。
"Comparative example"
35.5 g of nickel chloride hexahydrate (NiCl 2 · 6H 2 O, special grade reagent, manufactured by Kanto Chemical Co.) and ferrous chloride tetrahydrate (FeCl 2 · 4H 2 O, special grade reagent, manufactured by Kanto Chemical Co., Inc.) ) 7.9 g was dissolved in a mixed solution of 300 mL of pure water and 200 mL of methanol to prepare an aqueous solution of nickel chloride and ferrous chloride.
Next, 200 mL of a sodium hydroxide aqueous solution having a concentration of 6 mol / L was added to this aqueous solution while stirring.
Next, this aqueous solution was heated to 60 ° C. while stirring, and 300 g of hydrazine monohydrate (N 2 H 4 .H 2 O, special grade reagent, manufactured by Kanto Chemical Co., Inc.) was further added, and these aqueous solutions were stirred. While heating at 60 ° C. for 3 hours, black particles were obtained.
Next, the black particles were washed with pure water and ethanol and then dried in vacuum to obtain fine particles.
得られた微粒子をＸ線回折（ＸＲＤ）により分析した結果、ニッケルと鉄の合金粒子であることが分かった。この微粒子は、結晶構造が面心立方をなすことも確認された。また、（１１１）面のピーク角度より格子定数を算出したところ、０．３５５１ｎｍであった。
さらに、振動試料型磁力計（ＶＳＭ）により、このニッケルと鉄の合金粒子の飽和磁化および保磁力を測定したところ、飽和磁化は９２ｅｍｕ／ｇ、保磁力は５９Ｏｅであった。
次いで、このニッケル―鉄合金ナノ粒子１ｇと、直径が０．４ｍｍのジルコニア製のボール１２ｇと、エタノール１０ｇとを、容積が７５ｍＬの樹脂製容器内に充填し、この樹脂製容器をボールミルにて３０分回転させて、このニッケル―鉄合金ナノ粒子に機械的応力を加えた。
そして、走査型電子顕微鏡（ＳＥＭ）により、処理後のニッケル―鉄合金ナノ粒子の電子顕微鏡（図２参照）を得た。
As a result of analyzing the obtained fine particles by X-ray diffraction (XRD), it was found to be alloy particles of nickel and iron. The fine particles were also confirmed to have a face-centered cubic crystal structure. The lattice constant calculated from the peak angle of (111) plane was 0.3551 nm.
Furthermore, when the saturation magnetization and coercivity of the alloy particles of nickel and iron were measured with a vibrating sample magnetometer (VSM), the saturation magnetization was 92 emu / g and the coercivity was 59 Oe.
Next, 1 g of the nickel-iron alloy nanoparticles, 12 g of a zirconia ball having a diameter of 0.4 mm, and 10 g of ethanol are filled into a 75 mL resin container, and the resin container is filled with a ball mill. Rotating for 30 minutes, mechanical stress was applied to the nickel-iron alloy nanoparticles.
And the electron microscope (refer FIG. 2) of the nickel-iron alloy nanoparticle after a process was obtained with the scanning electron microscope (SEM).
図１と図２を比較すると、同じ条件で、それぞれの合金ナノ粒子に機械的応力を加えたにもかかわらず、亜鉛を添加した実施例のニッケル―鉄―亜鉛合金ナノ粒子は、明らかに平板状粒子になっているのに対して、亜鉛を添加していない比較例のニッケル―鉄合金ナノ粒子は、球状の粒子が多く残留していることが確認された。 Comparing FIG. 1 and FIG. 2, the nickel-iron-zinc alloy nanoparticles of the example in which zinc was added despite the mechanical stress being applied to the respective alloy nanoparticles under the same conditions are clearly flat. In contrast to the nickel-iron alloy nanoparticles of the comparative example to which zinc was not added, it was confirmed that many spherical particles remained, whereas the particles were shaped like particles.
Claims (7)
厚みが１μｍ以下かつアスペクト比が２以上であることを特徴とする平板状ニッケル―鉄―亜鉛合金ナノ粒子。
Plate-like nickel-iron-zinc alloy nanoparticles obtained by the method for producing tabular nickel-iron-zinc alloy nanoparticles according to claim 6,
A flat nickel-iron-zinc alloy nanoparticle having a thickness of 1 μm or less and an aspect ratio of 2 or more.
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| CN103586481A (en) * | 2013-10-19 | 2014-02-19 | 南昌大学 | A kind of preparation method of Fe100-xNix nanometer powder |
| WO2014080600A1 (en) * | 2012-11-20 | 2014-05-30 | Ｊｆｅミネラル株式会社 | Nickel powder, conductive paste, and laminated ceramic electronic component |
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| JP6000983B2 (en) * | 2012-11-20 | 2016-10-05 | Ｊｆｅミネラル株式会社 | Nickel powder, conductive paste, and multilayer ceramic electronic components |
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