JP6595808B2 - Magnesium metal fine particles and method for producing magnesium metal fine particles - Google Patents
Magnesium metal fine particles and method for producing magnesium metal fine particles Download PDFInfo
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims description 66
- 239000010419 fine particle Substances 0.000 title claims description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 26
- 239000011777 magnesium Substances 0.000 claims description 18
- 239000002480 mineral oil Substances 0.000 claims description 16
- 235000010446 mineral oil Nutrition 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 14
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 12
- 229910001111 Fine metal Inorganic materials 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 8
- 239000003595 mist Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000007769 metal material Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000002923 metal particle Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- ATTFYOXEMHAYAX-UHFFFAOYSA-N magnesium nickel Chemical compound [Mg].[Ni] ATTFYOXEMHAYAX-UHFFFAOYSA-N 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000002524 electron diffraction data Methods 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011882 ultra-fine particle Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000011084 recovery 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
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- -1 molecular weight 400 Substances 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Description
本発明は、酸化耐性に優れたマグネシウム金属微粒子及びその製造方法に関するものである。 The present invention relates to magnesium metal fine particles having excellent oxidation resistance and a method for producing the same.
マグネシウムは、比強度が高く（軽くて丈夫）、また、優れた水素吸蔵特性を有することから、微粒子（超微粒子）化することで高い貯蔵性能を発揮する水素貯蔵体の実現化が期待され、また、粉末冶金による複雑形状製品の実現も期待されている。 Magnesium has high specific strength (light and strong), and has excellent hydrogen storage properties, so it is expected to realize a hydrogen storage body that exhibits high storage performance by making fine particles (ultrafine particles). The realization of complex shaped products by powder metallurgy is also expected.
このマグネシウムを含む金属は、一般的に微粒子化することで比表面積が大きくなり、この比表面積が大きくなることで酸化速度が増大することが知られている。本発明者等は、この微粒子化により酸化しやすくなった金属微粒子の酸化を抑制し、酸化しにくい金属微粒子の実現化に向け、多くの研究・開発を行ってきており、これまでに、例えば、霧状にした有機物雰囲気中で金属細線にパルス通電してプラズマを発生させ、このプラズマを冷却することで表面に有機物被膜を形成した微粒子を生成し、この有機物被膜により酸化を抑制した金属微粒子の製造方法（特許文献１）や、有機物を塗布した金属細線にパルス通電してこの金属細線を蒸気化し、この蒸気を不活性気体中で凝結させることで表面に有機物被膜を形成した微粒子を生成し、この有機物被膜により酸化を抑制した金属微粒子の製造方法（特許文献２）、更に、前記特許文献１の方法を基に金属細線を蒸発させる際のエネルギー投入条件等の検討により、酸化速度が速いチタンにおいても、酸化しにくい金属微粒子化を実現した金属微粒子の製造方法（特許文献３）も提案している。 It is known that the metal containing magnesium generally has a specific surface area that is increased by making the particles fine, and the oxidation rate increases by increasing the specific surface area. The present inventors have conducted a lot of research and development toward the realization of metal microparticles that are difficult to oxidize by suppressing the oxidation of the metal microparticles that are easily oxidized by the micronization. , Metal fine wire in a mist-like atmosphere is pulsed to generate plasma, and this plasma is cooled to produce fine particles with an organic film formed on the surface. The method (Patent Document 1) and the fine metal wire coated with organic matter are pulsed to vaporize the fine metal wire, and the vapor is condensed in an inert gas to produce fine particles with an organic coating on the surface. In addition, a method for producing metal fine particles in which oxidation is suppressed by the organic film (Patent Document 2), and further, energy input when evaporating the metal thin wire based on the method of Patent Document 1 The study of matter such, even in the titanium faster oxidation rate, the method of manufacturing metal fine particles which realized hardly oxidized metal fine particles (Patent Document 3) is also proposed.
しかしながら、マグネシウムは、これまで本発明者等が微粒子化を実現させてきた金属に比べて酸化速度が非常に速いため、前記のいずれの方法を用いても微粒子化した際の酸化を抑制することは困難であった。 However, since magnesium has a very high oxidation rate compared to metals that have been realized by the present inventors until now, any of the above methods can be used to suppress oxidation when microparticulated. Was difficult.
本発明者等は、上述のような現状の問題に鑑み、本発明者等が提案した前記特許文献１，２及び３の方法を基にして、作製条件や採用する有機物について更なる研究、実験を行ない、ようやく大気中でも酸化しにくいマグネシウム金属微粒子を得ることに成功した。 In view of the above-mentioned problems, the present inventors have conducted further research and experiments on production conditions and organic substances to be employed based on the methods of the Patent Documents 1, 2, and 3 proposed by the present inventors. Finally, we succeeded in obtaining magnesium metal fine particles that are difficult to oxidize in the atmosphere.
即ち、本発明は、前記特許文献１，２及び３の方法を応用し、これまで実現できなかった大気中で酸化しにくいマグネシウム金属微粒子及びその製造方法を提供することを目的とする。 That is, an object of the present invention is to provide magnesium metal fine particles that are difficult to oxidize in the air, which has not been realized so far, and a method for producing the same, by applying the methods of Patent Documents 1, 2, and 3.
添付図面を参照して本発明の要旨を説明する。 The gist of the present invention will be described with reference to the accompanying drawings.
マグネシウム金属材料若しくはマグネシウム合金材料から成る金属微粒子であって、この金属微粒子のマグネシウム含有量は６０〜１００モル％であり、また、この金属微粒子は酸素量が０．１ｗｔ％以下の有機物で形成された厚さが１〜１０ｎｍの被膜で表面が覆われていることを特徴とするマグネシウム金属微粒子に係るものである。 Metal fine particles made of a magnesium metal material or a magnesium alloy material, wherein the metal fine particles have a magnesium content of 60 to 100 mol%, and the metal fine particles are formed of an organic substance having an oxygen content of 0.1 wt% or less. Further, the present invention relates to magnesium metal fine particles characterized in that the surface is covered with a coating having a thickness of 1 to 10 nm .
また、請求項１記載のマグネシウム金属微粒子において、前記マグネシウム合金材料はマグネシウムとニッケルの二成分系合金であることを特徴とするマグネシウム金属微粒子に係るものである。 Further, the magnesium metal particle of claim 1 Symbol placement, the magnesium alloy material are those according to the magnesium metal particles, which is a two-component system alloy of magnesium and nickel.
また、請求項１，２いずれか１項に記載のマグネシウム金属微粒子において、前記有機物は炭化水素系鉱物油であることを特徴とするマグネシウム金属微粒子に係るものである。 The magnesium metal fine particles according to any one of claims 1 and 2 , wherein the organic substance is a hydrocarbon mineral oil.
また、不活性ガスと、蒸気状若しくは霧状にした酸素量０．１ｗｔ％以下の有機物とを混合した有機物雰囲気中で、マグネシウム金属材料若しくはマグネシウム合金材料から成る金属細線１にパルス電流を通電し該金属細線１を加熱蒸発させて金属蒸気を発生させ、前記有機物雰囲気中において前記金属蒸気を凝結させた後、回収することを特徴とするマグネシウム金属微粒子の製造方法に係るものである。 Also, by energizing the inert gas, in vapor form or atomized oxygen content 0.1 wt% or less of organic and mixed organic matter atmosphere, the pulse current to the thin metal wires 1 made of a magnesium metal material or magnesium alloy material The thin metal wire 1 is heated to evaporate to generate a metal vapor, and the metal vapor is condensed in the organic atmosphere, and then collected, and then the magnesium metal fine particles are produced.
また、請求項４記載のマグネシウム金属微粒子の製造方法において、前記金属細線１は直径０．０５ｍｍ〜１．０ｍｍのものであることを特徴とするマグネシウム金属微粒子の製造方法に係るものである。 5. The method for producing magnesium metal fine particles according to claim 4 , wherein the fine metal wire 1 has a diameter of 0.05 mm to 1.0 mm.
また、請求項４，５いずれか１項に記載のマグネシウム金属微粒子の製造方法において、前記金属細線１に該金属細線１が蒸気化するのに必要なエネルギーの１．５〜５．０倍のエネルギーを投入して前記金属細線１を加熱蒸発させることを特徴とするマグネシウム金属微粒子の製造方法に係るものである。 Moreover, in the manufacturing method of the magnesium metal fine particle of any one of Claims 4 and 5 , 1.5 to 5.0 times the energy required for the said metal fine wire 1 to vaporize to the said metal fine wire 1 The present invention relates to a method for producing magnesium metal fine particles, wherein energy is input to heat and evaporate the fine metal wires 1.
本発明は上述のように構成したから、大気中で保管しても酸化しにくいマグネシウム金属微粒子となり、よって、高い貯蔵性能を発揮する水素貯蔵体の実現、粉末冶金による複雑形状製品の実現が可能となる。 Since the present invention is configured as described above, it becomes magnesium metal fine particles that are difficult to oxidize even when stored in the atmosphere. Therefore, it is possible to realize a hydrogen storage body that exhibits high storage performance, and to realize complex shaped products by powder metallurgy. It becomes.
好適と考える本発明の実施形態を、図面に基づいて本発明の作用を示して簡単に説明する。 An embodiment of the present invention which is considered to be suitable will be briefly described with reference to the drawings showing the operation of the present invention.
本発明のマグネシウム金属微粒子は、蒸気状若しくは霧状にした酸素量０．１ｗｔ％以下の有機物から成る有機物雰囲気中で、マグネシウム金属材料若しくはマグネシウム合金材料から成る金属細線１にパルス電流を通電し、この金属細線１の金属蒸気を発生させ、この金属蒸気が前記有機物雰囲気により冷却され、凝結して微粒子化する際、前記有機物と反応して表面が有機物被膜で覆われたものである。 The magnesium metal fine particles of the present invention energize a pulse current to the metal thin wire 1 made of a magnesium metal material or a magnesium alloy material in an organic substance atmosphere made of an organic substance having an oxygen amount of 0.1 wt% or less in a vapor or mist form, When the metal vapor of this metal fine wire 1 is generated, and this metal vapor is cooled by the organic substance atmosphere and condensed to form fine particles, it reacts with the organic substance and the surface is covered with an organic film.
前記特許文献１，２及び３の方法では、有機物被膜を形成させるために用いる有機物として、アルコールやカルボン酸等の酸素を含む有機物を用いていた。 In the methods of Patent Documents 1, 2, and 3, organic substances containing oxygen, such as alcohol and carboxylic acid, are used as organic substances used for forming the organic film.
本発明者等は、マグネシウムは炭素よりも還元作用が大きいので、この有機物中の酸素と反応して酸化すると推測し、そこで、酸素量０．１ｗｔ％以下の有機物、例えば炭化水素系鉱物油等の酸素を含まない有機物を用いて有機物被膜を形成したところ、マグネシウムを酸化させることなく有機物被膜を形成することができ、大気中でも酸化しにくいマグネシウム及びマグネシウム合金の微粒子（超微粒子）が実現できた。 The present inventors presume that magnesium is oxidized by reacting with oxygen in the organic matter because magnesium has a reducing action larger than that of carbon, and therefore, an organic matter having an oxygen content of 0.1 wt% or less, such as a hydrocarbon mineral oil or the like. When an organic film was formed using an organic material that did not contain oxygen, it was possible to form an organic film without oxidizing magnesium, and magnesium and magnesium alloy fine particles (ultrafine particles) that were difficult to oxidize in the atmosphere could be realized. .
本発明の具体的な実施例について図面に基づいて説明する。 Specific embodiments of the present invention will be described with reference to the drawings.
本実施例は、不活性ガスと、蒸気状若しくは霧状にした酸素量０．１ｗｔ％以下の有機物とを混合した有機物雰囲気中で、マグネシウム金属材料若しくはマグネシウム合金材料から成る金属細線１にパルス電流を通電して該金属細線１を加熱蒸発させて金属蒸気を発生させ、前記有機物雰囲気中において前記金属蒸気を凝結させた後、回収することで、表面が前記有機物から成る有機物被膜で覆われた大気中で酸化しにくいマグネシウム金属微粒子を得ることができるマグネシウム金属微粒子の製造方法である。 In the present embodiment, a pulse current is applied to a thin metal wire 1 made of a magnesium metal material or a magnesium alloy material in an organic substance atmosphere in which an inert gas and an organic substance having an oxygen amount of 0.1 wt% or less in a vapor or mist form are mixed. The metal thin wire 1 is heated and evaporated to generate metal vapor, and the metal vapor is condensed in the organic substance atmosphere, and then recovered to cover the surface with the organic film composed of the organic substance. This is a method for producing a magnesium metal fine particle capable of obtaining a magnesium metal fine particle that hardly oxidizes in the atmosphere.
具体的には、本実施例は、金属細線１は直径０．０５ｍｍ〜１．０ｍｍのものを採用し、また、この金属細線１を加熱蒸発させる際は、この金属細線１が蒸気化するのに必要なエネルギー（細線蒸発エネルギー）の１．５〜５．０倍のエネルギーを投入している。 Specifically, in this embodiment, the fine metal wire 1 has a diameter of 0.05 mm to 1.0 mm, and when the fine metal wire 1 is heated and evaporated, the fine metal wire 1 is vaporized. Energy of 1.5 to 5.0 times as much as that required for energy (thin wire evaporation energy).
また、本実施例では、図１に示すようなパルス細線放電装置２を用いており、このパルス細線放電装置２は、高圧充電電源４、コンデンサー５、スイッチ６を主構成部品とする放電回路部と、金属細線１にパルス電流を通電し加熱蒸発させて微粒子を形成するチャンバー３とで構成している。 Further, in this embodiment, a pulse thin wire discharge device 2 as shown in FIG. 1 is used, and this pulse thin wire discharge device 2 is a discharge circuit section having a high voltage charging power source 4, a capacitor 5 and a switch 6 as main components. And a chamber 3 for forming fine particles by applying a pulse current to the fine metal wire 1 and heating and evaporating it.
また、このチャンバー３は、雰囲気ガスを導入するガス導入口７と、真空排気口８とが設けられており、この真空排気口８に回収フィルター９を設けてチャンバー３内で形成したマグネシウム金属微粒子を回収する構成としている。 The chamber 3 is provided with a gas introduction port 7 for introducing atmospheric gas and a vacuum exhaust port 8, and a magnesium metal fine particle formed in the chamber 3 by providing a recovery filter 9 at the vacuum exhaust port 8. It is set as the structure which collects.
以下、本実施例のより具体的なマグネシウム金属微粒子の製造方法、及びこの製造方法により製造されたマグネシウム金属微粒子について詳述する。 Hereinafter, a more specific method for producing magnesium metal fine particles of this example and the magnesium metal fine particles produced by this production method will be described in detail.
[具体例１]
直径０．３ｍｍ、長さ３２ｍｍのマグネシウム金属細線１を、チャンバー３内に配置した放電回路の電極10間にセットした後、チャンバー３内に酸素量０．１ｗｔ％以下の鉱物油（本実施例では、村松石油社製 ネオバック ＭＲ−２００：炭化水素系鉱物油、分子量４００、硫黄０．１７〜０．１８％含有の酸素を含まない鉱物油を使用）を入れ、チャンバー３内を真空排気することにより、このチャンバー３内に酸素量０．１ｗｔ％以下の鉱物油の蒸気若しくは霧を発生させ、更に、ガス導入口７よりアルゴンガスを導入し、チャンバー内３の圧力を１００ｋＰａにして、このチャンバー３内を酸素量０．１ｗｔ％以下の鉱物油蒸気／霧とアルゴンガスとが均一に混合した有機物雰囲気にした。
[Specific Example 1]
A magnesium metal fine wire 1 having a diameter of 0.3 mm and a length of 32 mm is set between the electrodes 10 of the discharge circuit arranged in the chamber 3, and then the mineral oil having an oxygen content of 0.1 wt% or less (in this embodiment) Then, Muramatsu Petroleum Neoback MR-200: Hydrocarbon mineral oil, molecular weight 400, sulfur containing 0.17 to 0.18% oxygen-free mineral oil is used) and the chamber 3 is evacuated. As a result, vapor or mist of mineral oil having an oxygen amount of 0.1 wt% or less is generated in the chamber 3, and further, argon gas is introduced from the gas inlet 7, and the pressure in the chamber 3 is set to 100 kPa. The inside of the chamber 3 was made an organic atmosphere in which mineral oil vapor / mist having an oxygen amount of 0.1 wt% or less and argon gas were uniformly mixed.
尚、通常、鉱物油は０．１ｗｔ％以上の水分を含むと白濁して機能を失うことが知られており、水分子中の酸素量は１６／１８（０．８９）であるため、白濁が無いことが確認されている本実施例の鉱物油は、酸素量が０．１ｗｔ％以下の鉱物油であると言える。 Normally, mineral oil is known to become cloudy and lose its function when it contains water of 0.1 wt% or more, and the amount of oxygen in the water molecule is 16/18 (0.89). It can be said that the mineral oil of this example, which has been confirmed to be free of oxygen, is a mineral oil having an oxygen content of 0.1 wt% or less.
その後、電極10を５ｋＶに充電した容量１０μＦのコンデンサーに接続し、パルス大電流放電によって４μｓｅｃ加熱し、マグネシウム金属細線１を蒸発させた。この際、マグネシウム金属細線１を蒸発（蒸気化）させるのに必要な細線蒸発エネルギーと、投入エネルギーとの比である投入エネルギー比（Ｋ）の値が１以下の場合、加熱が不均一となって蒸発しきれない粗大液滴が形成され、形成される微粒子形状が大径となってしまうことから、投入エネルギー比（Ｋ）が１．５〜５．０（本実施例では、Ｋ＝４．４）となるエネルギーを投入した。 Thereafter, the electrode 10 was connected to a capacitor having a capacity of 10 μF charged to 5 kV, and heated for 4 μsec by pulsed high current discharge to evaporate the magnesium metal fine wire 1. At this time, when the value of the input energy ratio (K), which is the ratio of the fine wire evaporation energy required for evaporating (vaporizing) the magnesium metal fine wire 1 to the input energy, is 1 or less, the heating becomes non-uniform. Thus, coarse droplets that cannot be evaporated are formed, and the shape of the formed fine particles becomes large, so that the input energy ratio (K) is 1.5 to 5.0 (in this embodiment, K = 4). 4) was applied.
蒸発したマグネシウム金属細線１は、金属蒸気となり、チャンバー３内で有機物雰囲気により冷却され、凝結して微粒子化する。本実施例では、チャンバー３内の有機物雰囲気を、真空排気口８を通じて排気し、この排気の際に真空排気口８の途中に配設した回収フィルター９を介して脱気することで微粒子を回収した。 The evaporated magnesium metal fine wire 1 becomes a metal vapor, is cooled in the chamber 3 by the organic substance atmosphere, and is condensed and formed into fine particles. In the present embodiment, the organic substance atmosphere in the chamber 3 is exhausted through the vacuum exhaust port 8 and fine particles are recovered by deaeration through a recovery filter 9 disposed in the middle of the vacuum exhaust port 8 at the time of this exhaust. did.
図２は、上記の製造方法により得られた本実施例のマグネシウム金属微粒子のＳＥＭ写真と電子回析図形（左上）である。この図２のＳＥＭ写真から、マグネシウム金属微粒子の直径は２０〜２００ｎｍであり、このマグネシウム金属微粒子が超微粒子であることが確認でき、また、微粒子表面が１〜１０ｎｍの有機物被膜で覆われていることも確認できた。 FIG. 2 is an SEM photograph and an electron diffraction pattern (upper left) of the magnesium metal fine particles of this example obtained by the above-described production method. From the SEM photograph of FIG. 2, the diameter of the magnesium metal fine particles is 20 to 200 nm, and it can be confirmed that the magnesium metal fine particles are ultrafine particles, and the surface of the fine particles is covered with an organic film of 1 to 10 nm. I was able to confirm that.
また、図３は、本実施例のマグネシウム金属微粒子の粉末Ｘ線回析図形である。この粉末Ｘ線回析図形と図２の電子回析図形には、マグネシウム（Mg）以外のピークは見られず、形成されたマグネシウム金属微粒子が酸化されていないことを示している。本発明者等は、本実施例のマグネシウム金属微粒子を大気中（室温）に１か月間放置保管したが、同様にマグネシウム以外のピークは見られず、酸化物は検出されなかった。 FIG. 3 is a powder X-ray diffraction pattern of the magnesium metal fine particles of this example. In the powder X-ray diffraction pattern and the electron diffraction pattern of FIG. 2, no peaks other than magnesium (Mg) are observed, indicating that the formed magnesium metal fine particles are not oxidized. The inventors of the present invention stored the magnesium metal fine particles of this example in the atmosphere (room temperature) for one month, but similarly no peaks other than magnesium were observed, and no oxide was detected.
以上より、本実施例のマグネシウム金属微粒子は、酸素量０．１ｗｔ％以下の有機物により表面を覆われることで酸化が抑制され、酸化物とならずマグネシウム金属状態を保持することが確認できた。 From the above, it was confirmed that the magnesium metal fine particles of this example were prevented from being oxidized by covering the surface with an organic substance having an oxygen amount of 0.1 wt% or less, and maintained the magnesium metal state without becoming an oxide.
尚、有機物は、本実施例に挙げたものに限らず、酸素量０．１ｗｔ％以下で窒素やアルゴン等の不活性ガス中で炭化せず蒸気状若しくは霧状になり得るものであれば適宜採用し得るものとする。 The organic substance is not limited to those described in the present embodiment, and may be appropriately selected as long as it can be vaporized or atomized without being carbonized in an inert gas such as nitrogen or argon with an oxygen amount of 0.1 wt% or less. It can be adopted.
[具体例２]
直径０．３ｍｍ、長さ３２ｍｍのマグネシウム細線と、直径０．３ｍｍ、長さ３２ｍｍのニッケル細線とをよじって形成したマグネシウム−ニッケル金属細線１をチャンバー３内に配置した放電回路の電極10間にセットした後、チャンバー３内に酸素量０．１ｗｔ％以下の鉱物油（本実施例では、村松石油社製 ネオバック ＭＲ−２００：炭化水素系鉱物油、分子量４００、硫黄０．１７〜０．１８％含有の酸素を含まない鉱物油を使用）を入れ、チャンバー３内を真空排気することにより、このチャンバー３内に酸素量０．１ｗｔ％以下の鉱物油の蒸気若しくは霧を発生させ、更に、ガス導入口７よりアルゴンガスを導入し、チャンバー内３の圧力を１００ｋＰａにして、このチャンバー３内を酸素量０．１ｗｔ％以下の鉱物油蒸気／霧とアルゴンガスとが均一に混合した有機物雰囲気にした。
[Specific Example 2]
A magnesium-nickel metal wire 1 formed by joining a magnesium wire having a diameter of 0.3 mm and a length of 32 mm and a nickel wire having a diameter of 0.3 mm and a length of 32 mm is disposed between the electrodes 10 of the discharge circuit disposed in the chamber 3. After setting, mineral oil having an oxygen amount of 0.1 wt% or less in the chamber 3 (in this example, Neoback MR-200 manufactured by Muramatsu Oil Co., Ltd., hydrocarbon mineral oil, molecular weight 400, sulfur 0.17 to 0.18 % Containing mineral oil containing no oxygen) and evacuating the chamber 3 to generate vapor or mist of mineral oil having an oxygen amount of 0.1 wt% or less in the chamber 3, Argon gas is introduced from the gas introduction port 7, the pressure in the chamber 3 is set to 100 kPa, and the inside of the chamber 3 is treated with mineral oil vapor / mist and oxygen with an oxygen content of 0.1 wt% or less. An organic substance atmosphere in which Lugon gas was uniformly mixed was used.
その後、電極10を５ｋＶに充電した容量１０μＦのコンデンサーに接続し、パルス大電流放電によって６μｓｅｃ加熱し、マグネシウム−ニッケル金属細線１を蒸発させた。 Thereafter, the electrode 10 was connected to a capacitor having a capacity of 10 μF charged to 5 kV and heated for 6 μsec by pulsed high-current discharge to evaporate the magnesium-nickel metal fine wire 1.
蒸発したマグネシウム−ニッケル金属細線１は、金属蒸気となり、チャンバー３内で有機物雰囲気により冷却され、凝結して微粒子化する。尚、回収方法は具体例１と同様である。 The evaporated magnesium-nickel metal fine wire 1 becomes a metal vapor, is cooled in the chamber 3 by an organic substance atmosphere, and is condensed and formed into fine particles. The recovery method is the same as that in Example 1.
図４は、上記の製造方法により得られた本実施例のマグネシウム−ニッケル合金微粒子のＳＥＭ写真であり、図５は、電子回析図形である。この図４のＳＥＭ写真から、マグネシウム−ニッケル合金微粒子の直径は２０〜９０ｎｍであり、このマグネシウム−ニッケル合金微粒子が具体例１同様、超微粒子であることが確認でき、また、微粒子表面が１〜１０ｎｍの有機物被膜で覆われていることも確認できた。 FIG. 4 is an SEM photograph of the magnesium-nickel alloy fine particles of this example obtained by the above production method, and FIG. 5 is an electron diffraction pattern. From the SEM photograph of FIG. 4, the diameter of the magnesium-nickel alloy fine particles is 20 to 90 nm, and it can be confirmed that the magnesium-nickel alloy fine particles are ultrafine particles as in Example 1, and the surface of the fine particles is 1 to It was also confirmed that the film was covered with a 10 nm organic film.
また、図５に示す電子回析図形は、マグネシウム（Mg）とマグネシウム−ニッケル合金（Mg2Ni）以外のピークは見られず、形成されたマグネシウム−ニッケル合金微粒子が酸化されていないことを示している。本発明者等は、このマグネシウム−ニッケル合金微粒子を大気中（室温）に１か月間放置保管したが、具体例１同様にマグネシウム及びマグネシウム−ニッケル合金以外のピークは見られず、酸化物は検出されなかった。 Further, the electron diffraction pattern shown in FIG. 5 shows that no peaks other than magnesium (Mg) and magnesium-nickel alloy (Mg 2 Ni) are observed, and the formed magnesium-nickel alloy fine particles are not oxidized. ing. The inventors of the present invention stored the magnesium-nickel alloy fine particles in the atmosphere (room temperature) for one month, but no peaks other than magnesium and magnesium-nickel alloy were observed as in Example 1, and the oxide was detected. Was not.
以上より、本実施例のマグネシウム−ニッケル合金微粒子は、酸素量０．１ｗｔ％以下の有機物により表面を覆われることで酸化が抑制され、酸化物とならずマグネシウム−ニッケル合金状態を保持することが確認できた。 As described above, the magnesium-nickel alloy fine particles of this example are prevented from being oxidized by covering the surface with an organic substance having an oxygen content of 0.1 wt% or less, and can maintain a magnesium-nickel alloy state without becoming an oxide. It could be confirmed.
尚、マグネシウム合金に関しては、本実施例のマグネシウム−ニッケル合金に限らず、例えば安価で大量に生産されている鉄などの第三周期遷移金属を含むものとしても良い。 Note that the magnesium alloy is not limited to the magnesium-nickel alloy of the present embodiment, and may include a third-period transition metal such as iron that is inexpensively produced in large quantities.
[比較例１]
直径０．３ｍｍ、長さ２０ｍｍのマグネシウム金属細線を、酸素を含む有機物としてオレイン酸液中の電極にセットし、その後、電極を４ｋＶに充電した容量１０μＦのコンデンサーに接続し、パルス大電流放電によって加熱し、マグネシウム金属細線を蒸発させた。プラズマの冷却により凝結して微粒子化したものをフィルターごと回収した。
[Comparative Example 1]
A magnesium metal wire having a diameter of 0.3 mm and a length of 20 mm is set on an electrode in an oleic acid solution as an organic substance containing oxygen, and then the electrode is connected to a capacitor having a capacity of 10 μF charged to 4 kV, and pulsed high current discharge is performed. Heated to evaporate the magnesium metal wires. What was condensed and formed into fine particles by cooling the plasma was collected together with the filter.
図６は、この回収した粒子の粉末Ｘ線回析図形である。この粉末Ｘ線回析図形では、マグネシウムのピークの他に、４３（deg.）と６２（deg.）等で酸化マグネシウム（MgO）の幅広いピークがかなりの高さで現れており、形成された粒子のほとんどが酸化されていることを示している。 FIG. 6 is a powder X-ray diffraction pattern of the collected particles. In this powder X-ray diffraction pattern, in addition to the magnesium peak, a wide peak of magnesium oxide (MgO) appeared at a considerable height at 43 (deg.), 62 (deg.), Etc., and was formed. It shows that most of the particles are oxidized.
オレイン酸分子（C18H34O2）の酸素量は１１ｗｔ％あり、このような酸素量の多い有機物では酸化を抑制することができず、マグネシウム金属微粒子を得ることができないことが確認できた。 Oleic acid molecules (C 18 H 34 O 2 ) have an oxygen content of 11 wt%, and it was confirmed that organic substances having such a large amount of oxygen cannot suppress oxidation and magnesium metal fine particles cannot be obtained. .
尚、本発明は、本実施例に限られるものではなく、各構成要件の具体的構成は適宜設計し得るものである。 Note that the present invention is not limited to this embodiment, and the specific configuration of each component can be designed as appropriate.
１ 金属細線 1 Metal thin wire
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