JP5076135B2 - Manufacturing method of nickel powder with hcp structure - Google Patents
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 103
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000000843 powder Substances 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 15
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- -1 hexachloroplatinum (IV) Chemical compound 0.000 claims description 9
- 239000010419 fine particle Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 31
- 238000002441 X-ray diffraction Methods 0.000 description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 23
- 230000005415 magnetization Effects 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 12
- 230000005389 magnetism Effects 0.000 description 11
- 238000010992 reflux Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 238000004917 polyol method Methods 0.000 description 9
- 239000011164 primary particle Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 230000005291 magnetic effect Effects 0.000 description 7
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- UGNSMKDDFAUGFT-UHFFFAOYSA-N 4,4-dimethyl-2-phenyl-5h-1,3-oxazole Chemical compound CC1(C)COC(C=2C=CC=CC=2)=N1 UGNSMKDDFAUGFT-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000012798 spherical particle Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 239000000411 inducer Substances 0.000 description 3
- 229940078494 nickel acetate Drugs 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000004685 tetrahydrates Chemical class 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 2
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- NDBYXKQCPYUOMI-UHFFFAOYSA-N platinum(4+) Chemical compound [Pt+4] NDBYXKQCPYUOMI-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Description
本発明は、ｈｃｐ構造をもつニッケル粉の製法に関する。 The present invention relates to a method for producing nickel powder having an hcp structure.
ニッケル粉はその優れた耐食性および耐熱性により導電材料や触媒材料等に広く応用されているが、その結晶構造はｆｃｃ構造（面心立方構造）であった。 Nickel powder has been widely applied to conductive materials and catalyst materials due to its excellent corrosion resistance and heat resistance, but its crystal structure was an fcc structure (face-centered cubic structure).
ｆｃｃ構造のニッケルは磁性を有する。したがって、従来のニッケル粉は磁性をもつものが多く、磁性をもつことが利用される面もあるが、用途に制限を受ける場合もある。例えば積層セラミックコンデンサー用内部電極を構成するような場合には、最近の薄層化が進んだ状況下では磁性を有すると不都合が生じることがある。ニッケルの微粉を樹脂・溶剤に分散させたペーストとし、これを該内部電極構成用に使用する場合に、ニッケル微粉が磁性を有すると、ペースト内でニッケル微粉が磁気凝集を起こし、これが電極切れや電極層と誘電体層界面の平滑性悪化などの原因になることがある。 Nickel having an fcc structure is magnetic. Therefore, many of the conventional nickel powders have magnetism, and there are aspects in which the magnetism is used, but there are cases where the use is limited. For example, in the case where an internal electrode for a multilayer ceramic capacitor is formed, there may be inconvenience if it has magnetism under the recent progress of thinning. When a fine nickel powder is dispersed in a resin / solvent and used for the internal electrode structure, if the fine nickel powder has magnetism, the fine nickel powder will cause magnetic aggregation in the paste, This may cause deterioration of the smoothness of the interface between the electrode layer and the dielectric layer.
また、次世代の配線基板の回路形成方法として、顔料インクの代わりに、金属ナノ粒子を用いた導電性インクをインクジェットプリンターで基板に配線を描画する方法の開発が進められているが、このインクジェット法に用いる導電性インクの金属粒子は微粒でかつ単分散状態であることが極めて重要である。しかし、磁性を有すると磁気凝集を起こしてノズル詰まりやインクの吐出が不安定になりやすく, その結果, 微細で均一な配線が引けないなどの現象がおきるので、強磁性体であるｆｃｃ構造のニッケル粉はその使用に制限を受けることになる。 In addition, as a next-generation wiring board circuit formation method, a method of drawing wiring on a substrate with an ink jet printer using conductive ink using metal nanoparticles instead of pigment ink is being developed. It is very important that the metal particles of the conductive ink used in the method are fine and monodispersed. However, if it has magnetism, it causes magnetic agglomeration and nozzle clogging and ink ejection are likely to become unstable. As a result, phenomena such as the inability to draw fine and uniform wiring occur. Nickel powder is subject to restrictions on its use.
さらに、燃料電池などの触媒の用途では、シングルナノオーダーのＮｉ粒子が電極触媒として用いられているが、このような触媒用途ではシングルナノオーダーのＮｉ粒子を担体に均一に分散させることが重要であるところ、磁性を有すると磁気凝集を起こすので強磁性体であるｆｃｃ構造のニッケル粉の使用は制限を受ける。 Furthermore, in the application of a catalyst such as a fuel cell, single nano-order Ni particles are used as an electrode catalyst. In such a catalyst application, it is important to uniformly disperse the single nano-order Ni particles on the support. There is a limit to the use of fcc-structured nickel powder, which is a ferromagnetic material, because magnetic aggregation occurs when it has magnetism.
このようにニッケル粉の用途では磁性を有することが不利となることがある。非特許文献１において本願発明者の一人はポリオール法によるＮｉイオンの還元法によれば、ｆｃｃ構造（面心立方格子）とｈｃｐ構造（最密六方格子）の混合相のニッケル粉が得られることを示した。そして、ｈｃｐ構造をもつＮｉの微粒子からなるニッケル粉を特願２００４−２３１５８４号の明細書および図面に開示した。ｈｃｐ構造のニッケルは非磁性となる。
磁性をもたないニッケル粉が得られると、磁性をもつことで用途の制限を受けている分野において、用途の拡大を図ることができる。非特許文献１ではポリオール法によるとｆｃｃ構造とｈｃｐ構造の混合相が得られることを示したが、ｈｃｐ単相を安定して得られるところまでには至っていなかった。したがって、本発明はｈｃｐ単相を安定して得ることのできるニッケル粉の製法の開発を目的としたものである。 When nickel powder having no magnetism is obtained, the use can be expanded in the field where the use is restricted due to the magnetism. Non-Patent Document 1 shows that a mixed phase having an fcc structure and an hcp structure can be obtained by the polyol method, but has not yet reached a point where an hcp single phase can be stably obtained. Accordingly, the object of the present invention is to develop a nickel powder production method capable of stably obtaining an hcp single phase.
前記の課題は、ポリオール中に溶存するＮｉイオンをポリオールで還元して液中に金属Ｎｉの微粒子を析出させるさいに、ヘキサクロロ白金(IV)酸のような核誘起剤の存在下で還元するニッケル粉の製法によって解決できることがわかった。 The above-mentioned problem is that nickel that is reduced in the presence of a nucleating agent such as hexachloroplatinum (IV) acid when Ni ions dissolved in the polyol are reduced with the polyol to precipitate fine particles of metallic Ni in the liquid. It was found that this can be solved by the powder manufacturing method.
したがって本発明によると、テトラエチレングリコール中に溶存するＮｉイオンをヘキサクロロ白金（IV）酸の存在下においてテトラエチレングリコールにより２９０℃で１時間還元して液中に金属Ｎｉの微粒子を析出させることからなるｈｃｐ構造をもつニッケル粉の製法を提供する。 Therefore, according to the present invention, Ni ions dissolved in tetraethylene glycol are reduced with tetraethylene glycol at 290 ° C. for 1 hour in the presence of hexachloroplatinum (IV) acid to deposit metal Ni fine particles in the liquid. A method for producing nickel powder having an hcp structure is provided.
本発明者らは、Ｎｉイオンを溶存したポリオールを蒸発・還流条件下で処理する方法（ポリオール法）により、液中のＮｉイオンを該ポリオールでＮｉに適正に還元するとｈｃｐ構造を含むＮｉ微粒子が得られることを知見した。 When the present inventors appropriately reduced Ni ions in a liquid to Ni by a method of treating a polyol in which Ni ions are dissolved under evaporation and reflux conditions (polyol method), Ni fine particles containing an hcp structure are obtained. It was found that it was obtained.
Ｎｉ源の出発物質として酢酸ニッケルの四水塩を使用し、これを、エチレングリコール（ＥＧ）、トリメチレングリコール（ＴＭＥＧ）またはテトラエチレングリコール（ＴＥＧ）に溶解したうえ、このポリオール媒体を還流器付きの容器内で蒸発・還流させるポリオール法の実験を行った。 Nickel acetate tetrahydrate is used as a starting material for the Ni source, which is dissolved in ethylene glycol (EG), trimethylene glycol (TMEG) or tetraethylene glycol (TEG), and the polyol medium is equipped with a refluxer. The polyol method was evaporated and refluxed in the container.
ＥＧ中に存在する水酸化イオンは反応に影響を与え、ＯＨ-イオンの導入は生成するＮｉ粒子の形態に変化を与えることがわかった。図１に、Ｎｉイオンを溶存したエチレングリコール溶液に共存するＯＨ-イオン濃度（ＯＨ-／Ｎｉ比）が異なる場合に、生成するＮｉ粒子がどの様に変化するかをＳＥＭ写真で示した。 It has been found that hydroxide ions present in EG affect the reaction, and introduction of OH - ions changes the morphology of the Ni particles produced. FIG. 1 is an SEM photograph showing how the generated Ni particles change when the OH − ion concentration (OH − / Ni ratio) coexisting in the ethylene glycol solution in which Ni ions are dissolved is different.
図１の（ａ）〜（ｄ）の写真において、（ａ）のものはＯＨ-／Ｎｉ比＝０、（ｂ）ではＯＨ-／Ｎｉ比＝１０、（ｃ）ではＯＨ-／Ｎｉ比＝５０、（ｄ）ではＯＨ-／Ｎｉ比＝１５０である。これらの図に見られるように、水素イオン濃度が増大すると、生成する粒子の粒径が減少する。図１（ａ）のものではμｍオーダの不規則な板状の粒子が認められ、Ｘ線回折ではｆｃｃ相が認められた。（ｂ）〜（ｃ）では生成する粒子の形状が球状になり、粒径が数１００ｎｍ程度に減少し、（ｄ）では数１０ｎｍに減少する。ＸＲＤから平均Ｘ線結晶粒径を求めたところ、ＯＨ-／Ｎｉ比が０から５０に増大した場合、その平均結晶粒径は５０ｎｍから１６ｎｍに減少した。室温での飽和磁化値は５５〜３８emu/g であった。飽和磁化値の低下は非磁性のｈｃｐ相の生成が寄与していると見てよい。 In photograph of FIG. 1 (a) ~ (d) , OH those of (a) - / Ni ratio = 0, in (b) OH - / Ni ratio = 10, (c) in OH - / Ni ratio = In 50, (d), the OH − / Ni ratio = 150. As seen in these figures, as the hydrogen ion concentration increases, the particle size of the generated particles decreases. In FIG. 1A, irregular plate-like particles having an order of μm were observed, and an fcc phase was observed by X-ray diffraction. In (b) to (c), the shape of the generated particles is spherical, and the particle size is reduced to about several hundred nm, and in (d), it is reduced to several tens of nm. When the average X-ray crystal grain size was determined from XRD, when the OH − / Ni ratio increased from 0 to 50, the average crystal grain size decreased from 50 nm to 16 nm. The saturation magnetization value at room temperature was 55 to 38 emu / g. It can be considered that the decrease in the saturation magnetization value is caused by the generation of a nonmagnetic hcp phase.
ＥＧに代えてＴＭＥＧを用いてＮｉ粒子を生成させたところ、反応が促進され不安定なｈｃｐ構造をもつＮｉ粒子が生成した。そのＸＲＤパターンを図２の（ｂ）に示した。このパターンに見られるように、このＮｉ粒子粉末にはｈｃｐ相が現れている。図２の（ａ）の純粋のｆｃｃ相からｆｃｃとｈｃｐの混合相に変わったと見られるが、ｈｃｐ構造のＮｉは非磁性であることから、飽和磁化値は５５emu/g から２１emu/g に低下した。 When Ni particles were produced using TMEG instead of EG, the reaction was accelerated and Ni particles having an unstable hcp structure were produced. The XRD pattern is shown in FIG. As can be seen from this pattern, an hcp phase appears in the Ni particle powder. Although it seems that the pure fcc phase in FIG. 2A has changed to a mixed phase of fcc and hcp, the saturation magnetization value is reduced from 55 emu / g to 21 emu / g because Ni in the hcp structure is non-magnetic. did.
なお、上記の実験は, エチレングリコールまたはトリメチレングリコール１００ｍＬに酢酸ニッケルの四水塩を所定量溶解し、その溶液を還流器付きの容器に入れ、この容器をオイルバス（マントルヒータ付き）にセットして、ゆるやかな機械的な攪拌を行いながら所定の昇温速度で加熱するという方法で実施したものである。 In the above experiment, a predetermined amount of nickel acetate tetrahydrate was dissolved in 100 mL of ethylene glycol or trimethylene glycol, and the resulting solution was placed in a container equipped with a reflux device, and this container was set in an oil bath (with a mantle heater). Then, it is carried out by a method of heating at a predetermined temperature increase rate while performing gentle mechanical stirring.
さらに、実験を重ねた結果、ＴＥＧを用いて反応温度２９０℃でＮｉ粒子を生成させたところ、ｈｃｐ単相のＮｉナノ粒子を合成することができた。その詳細は後記の実施例に示すが、例えばＴＭＥＧでＮｉイオン濃度が０.０２Ｍでは、図３（ａ）のＸＲＤパターンおよび図４（ａ）のＳＥＭ像に見られるように、ｆｃc 単相が現れた。ＴＥＧで反応温度２９０℃、同じＮｉイオン濃度０.０２Ｍでもｆｃｃ単相であった。しかし、ＴＥＧでＮｉイオン濃度を低下させた場合にはｆｃｃ相とｈｃｐ相の混合したものが現れるようになり、さらにＮｉイオン濃度を０.００２５Ｍまで低下させた場合には、純粋なｈｃｐ構造のＮｉ粒子を得ることができた。その結果を図３（ｂ）のＸＲＤパターンおよび図４（ｂ）のＳＥＭ像に示した。図３（ｂ）はｈｃｐだけのピークが現れており、このＮｉ粒子粉末は純粋なｈｃｐ構造を有することがわかる。このＮｉ粒子粉末は図４（ｂ）のＳＥＭ像に見られるように、１次粒子の平均粒径が約１５０ｎｍであり、飽和磁化値は実測されるような値を有しなかった。 Furthermore, as a result of repeated experiments, when Ni particles were generated at a reaction temperature of 290 ° C. using TEG, hcp single-phase Ni nanoparticles could be synthesized. The details will be shown in the examples described later. For example, at TMEG with a Ni ion concentration of 0.02 M, as shown in the XRD pattern of FIG. 3A and the SEM image of FIG. Appeared. Even when the reaction temperature was 290 ° C. with TEG and the same Ni ion concentration was 0.02 M, it was an fcc single phase. However, when the Ni ion concentration is decreased by TEG, a mixture of the fcc phase and the hcp phase appears, and when the Ni ion concentration is further decreased to 0.0025M, a pure hcp structure is obtained. Ni particles could be obtained. The results are shown in the XRD pattern of FIG. 3B and the SEM image of FIG. 4B. FIG. 3B shows a peak only for hcp, and it can be seen that this Ni particle powder has a pure hcp structure. As seen in the SEM image of FIG. 4B, this Ni particle powder had an average primary particle diameter of about 150 nm, and the saturation magnetization value did not have a value as measured.
ここまでは、先述の特願２００４−２３１５８４号に記載したとおりであるが、さらに研究を続けた結果、Ｎｉ核の生成を促進する適切な物質（核誘起剤と呼ぶ）、代表的にはヘキサクロロ白金（IV）酸、の存在下で前記のＮｉ粒子の生成反応を進行させると一層ｈｃｐ構造が発現しやすいことがわかった。この関係を図６に示す。図６は、溶媒且つ還元剤のテトラエチレングリコールに、酢酸ニッケル（II）四水和物を０.０１mol ／Ｌの量で添加して昇温しＮｉ粒子の析出反応を行なわせた場合に、ヘキサクロロ白金（IV）酸を０.０１２５ｇ添加した場合（●印）と、無添加の場合（◆印）とについて（いずれも反応時間は１時間で同条件の攪拌を実施）、横軸に反応温度を、縦軸に得られたＮｉ粒子の飽和磁化量をとってｈｃｐ構造の生成挙動を対比したものである。図６から明らかなように、ヘキサクロロ白金（IV）酸無添加の場合（◆印）では、反応温度の上昇に伴う飽和磁化の低下は僅かであるのに対し、ヘキサクロロ白金（IV）酸を添加した場合（●印））では、反応温度が５２３Ｋ（２５０℃）近くになると飽和磁化が極端に落ちている（磁性をもたないｈｃｐ構造が支配的になる）ことがわかる。事実、反応温度５６３Ｋ（２９０℃）で得られたＮｉ粒子粉末（ヘキサクロロ白金（IV）酸を添加したもの）のＸ線回折測定ではｈｃｐ―Ｎｉに由来するピークしか観察されなかった。他方、核誘発剤無添加で反応温度５６３Ｋ（２９０℃）で得られたもののＸ線回折測定ではｆｃｃ＋ｈｃｐの混合相でであり、適切な核誘発剤の添加はｈｃｐ相の発現促進に効果があることが確められた。 Up to this point, as described in the above-mentioned Japanese Patent Application No. 2004-231484, as a result of further research, an appropriate substance that promotes the formation of Ni nuclei (called a nuclear inducer), typically hexachloro It was found that the hcp structure is more easily expressed when the formation reaction of the Ni particles proceeds in the presence of platinum (IV) acid. This relationship is shown in FIG. FIG. 6 shows a case where nickel acetate (II) tetrahydrate is added in an amount of 0.01 mol / L to tetraethylene glycol as a solvent and a reducing agent, and the temperature is raised to cause precipitation of Ni particles. When 0.0125 g of hexachloroplatinic (IV) acid is added (marked with ●) and when it is not added (marked with ◆), the reaction time is 1 hour and stirring is performed under the same conditions. The temperature is taken as the saturation magnetization of the Ni particles obtained on the vertical axis, and the generation behavior of the hcp structure is compared. As is clear from FIG. 6, in the case of no hexachloroplatinum (IV) acid added (♦ mark), the decrease in saturation magnetization with the increase in the reaction temperature is slight, while hexachloroplatinum (IV) acid is added. When the reaction temperature is close to 523 K (250 ° C.), the saturation magnetization is extremely lowered (the hcp structure having no magnetism is dominant). In fact, only a peak derived from hcp-Ni was observed in the X-ray diffraction measurement of Ni particle powder (added with hexachloroplatinum (IV) acid) obtained at a reaction temperature of 563 K (290 ° C.). On the other hand, what was obtained at a reaction temperature of 563 K (290 ° C.) without addition of a nuclear inducer was a mixed phase of fcc + hcp in the X-ray diffraction measurement, and the addition of an appropriate nuclear inducer is effective in promoting the expression of the hcp phase. It was confirmed.
このように本発明によると、ｆｃc 相とｈｃｐ相の複相構造の微粒子からなるニッケル粉, さらには、ｈｃｐ単相の微粒子からなるニッケル粉が得られる。前者ではｈｃｐ相の割合が増えるに従って飽和磁化値が下がり、後者では飽和磁化値は０emu/g に近くなる。したがって、本発明のニッケル粉は磁性をもたないか、有しても僅かであるという特徴を有しており、このために、これまでの強磁性ニッケル粉のものでは適用できなかった分野への利用ができるようになり、ニッケル粉の用途の拡大ができる。そして、本発明に従うニッケル粉は極めて微粒子であるから、ナノテクノロジー分野での新規材料として有用である。 As described above, according to the present invention, nickel powder composed of fine particles having a multi-phase structure of fcc phase and hcp phase, and further nickel powder composed of fine particles of hcp single phase can be obtained. In the former, the saturation magnetization value decreases as the ratio of the hcp phase increases, and in the latter, the saturation magnetization value approaches 0 emu / g. Therefore, the nickel powder of the present invention has a feature that it has no or little magnetism, and for this reason, to the field that could not be applied with conventional ferromagnetic nickel powders. The use of nickel powder can be expanded. And since the nickel powder according to the present invention is extremely fine, it is useful as a new material in the nanotechnology field.
以下に実施例を挙げるが、各例のＸ線結晶粒径（Ｄｘ）は Scherrer の式を用いて求めたものである。 Scherrer の式、Ｄ＝Ｋ・λ／β COSθにおけるＫとして0.94を採用し、Ｘ線の管球はＣｕを用いて、Ｄ＝0.94×1.5405／β COSθより算出した。回折ピークに関しては、ｈｃｐ相、ｆｃｃ相ともに４５度付近にメインピークが観察されるのでこのメインピークを採用した。 Examples are given below, and the X-ray crystal grain size (Dx) in each example is determined using the Scherrer equation. The Scherrer's equation, D = K · λ / β COSθ was 0.94 as K, and the X-ray tube was calculated from D = 0.94 × 1.5405 / βCOSθ using Cu. Regarding the diffraction peak, since the main peak is observed at around 45 degrees in both the hcp phase and the fcc phase, this main peak was adopted.
〔例１〕
エチレングリコール（沸点：１９７℃）１００ｍＬに、酢酸ニッケル（II）四水和物を０.０１mol ／Ｌになるよう添加し、固形分が存在しなくなるまで溶解した。この溶液を還流器のついた容器に移してオイルバスに載せ、容器内に不活性ガスとして窒素ガスを４００ｍＬ／ｍｉｎの流量で吹込みながら、該溶液をマグネットスターラーを用いて（以下の例も同じ）１６０ｒｐｍの回転速度で撹拌しつつ加熱し、１９２℃の温度で１時間の還流を行って、反応を終了した。そのさい、昇温速度は１０℃／min とした。
[Example 1]
Nickel (II) acetate tetrahydrate was added to 100 mL of ethylene glycol (boiling point: 197 ° C.) to a concentration of 0.01 mol / L and dissolved until no solid content existed. This solution is transferred to a container equipped with a refluxer and placed in an oil bath. While blowing nitrogen gas as an inert gas at a flow rate of 400 mL / min into the container, the solution is removed using a magnetic stirrer (the following examples are also used). The same) was heated with stirring at a rotation speed of 160 rpm, and refluxed at a temperature of 192 ° C. for 1 hour to complete the reaction. At that time, the heating rate was set to 10 ° C./min.
反応終了後の液に３倍量のメタノールを添加したうえで遠心分離器にかけ、その後、上澄み液を取り除いた。上澄み液を除いたあとの残留分（粒子粉末）に再びメタノール１００ｍＬを添加して超音波洗浄槽に装填し、この超音波洗浄槽で該粒子粉末を分散させた。得られた分散液を遠心分離器にかけたあと上澄み液を取り除いた。得られた残留分（粒子粉末）に対し、前記同様のメタノールを加えて超音波洗浄槽および遠心分離器で処理する洗浄操作を、さらに２回繰り返した。最後に上澄み液を分別して得られたニッケル粉含有物を、Ｘ線回折（ＸＲＤ）、磁気測定（ＶＳＭ）に供し、下記の結果を得た。なお、ＴＥＭおよびＳＥＭ観察も行った。 Three times the amount of methanol was added to the liquid after completion of the reaction, followed by centrifugation, and then the supernatant was removed. 100 mL of methanol was again added to the residue (particle powder) after removing the supernatant, and the mixture was loaded into an ultrasonic cleaning tank, and the particle powder was dispersed in this ultrasonic cleaning tank. After the obtained dispersion was centrifuged, the supernatant was removed. The washing operation of adding the same methanol as described above to the obtained residue (particle powder) and treating the residue with an ultrasonic washing tank and a centrifuge was further repeated twice. Finally, the nickel powder-containing material obtained by separating the supernatant was subjected to X-ray diffraction (XRD) and magnetic measurement (VSM), and the following results were obtained. TEM and SEM observations were also performed.
透過電子顕微鏡（ＴＥＭ）から観測された１次粒子の平均粒径は数μｍであった。ＳＥＭ観察から不規則な板状粒子であることが観察された。Ｘ線回折ではｆｃｃ構造に由来する回折ピークしか観察されなかった。ＶＳＭによる飽和磁化の測定結果は、５５emu/g であった。Ｘ線結晶粒径（Ｄｘ）は５０ｎｍであった。ＳＥＭ観察結果を図１の（ａ）に示した。Ｘ線回折結果および飽和磁化値から本例のニッケル粉はｆｃｃ構造であると見てよい。 The average particle diameter of primary particles observed from a transmission electron microscope (TEM) was several μm. From SEM observation, it was observed that the particles were irregular plate-like particles. In X-ray diffraction, only diffraction peaks derived from the fcc structure were observed. The measurement result of saturation magnetization by VSM was 55 emu / g. The X-ray crystal grain size (Dx) was 50 nm. The result of SEM observation is shown in FIG. From the X-ray diffraction result and the saturation magnetization value, it can be seen that the nickel powder of this example has an fcc structure.
〔例２〕
水酸化イオン（ＯＨ-）の導入のために、ＯＨ-／Ｎｉのモル比が１５０となる量のＮａＯＨを原料溶解時に添加した以外は例１を繰り返した。
[Example 2]
Example 1 was repeated except that NaOH was added at the time of melting the raw material in order to introduce hydroxide ions (OH − ) so that the molar ratio of OH − / Ni was 150.
得られたニッケル粉含有物を例１と同様の測定に供した。透過電子顕微鏡（ＴＥＭ）から観測された１次粒子の平均粒径は数１００ｎｍであった。ＳＥＭ観察からは球状粒子が観察された。Ｘ線回折ではｆｃｃ構造に由来する回折ピークしか観察されなかった。しかし、ＶＳＭによる飽和磁化の測定結果は３８emu/g であり、例１のものより低下した。Ｘ線結晶粒径（Ｄｘ）は１６ｎｍであった。ＳＥＭ観察結果を図１（ｃ）に示した。Ｘ線回折ではｆｃｃ相が現れたが、飽和磁化値から本例のニッケル粉はｆｃｃ相＋ｈｃｐ相の複相であると見てよい。 The obtained nickel powder-containing material was subjected to the same measurement as in Example 1. The average particle diameter of primary particles observed from a transmission electron microscope (TEM) was several hundred nm. Spherical particles were observed from SEM observation. In X-ray diffraction, only diffraction peaks derived from the fcc structure were observed. However, the measurement result of saturation magnetization by VSM was 38 emu / g, which was lower than that of Example 1. The X-ray crystal grain size (Dx) was 16 nm. The SEM observation result is shown in FIG. Although the fcc phase appeared in the X-ray diffraction, it can be seen from the saturation magnetization value that the nickel powder of this example is a double phase of the fcc phase + hcp phase.
〔例３〕
トリメチレングリコール（沸点：２２９.２℃）１００ｍＬに、酢酸ニッケル（II）四水和物を０.０２mol ／Ｌになるよう添加し、固形分が存在しなくなるまで溶解した。この溶液を還流器のついた容器に移してオイルバスに載せ、容器内に不活性ガスとして窒素ガスを４００ｍＬ／ｍｉｎの流量で吹込みながら、該溶液を１６０ｒｐｍの回転速度で撹拌しつつ加熱し、２００℃の温度で１時間の還流を行って、反応を終了した。そのさい、昇温速度は１０℃／min とした。
[Example 3]
To 100 mL of trimethylene glycol (boiling point: 229.2 ° C.), nickel (II) acetate tetrahydrate was added to 0.02 mol / L and dissolved until no solid content existed. This solution is transferred to a container equipped with a reflux device and placed in an oil bath. While blowing nitrogen gas as an inert gas at a flow rate of 400 mL / min into the container, the solution is heated while being stirred at a rotation speed of 160 rpm. The reaction was terminated by refluxing at a temperature of 200 ° C. for 1 hour. At that time, the heating rate was set to 10 ° C./min.
その結果、透過電子顕微鏡（ＴＥＭ）から観測された１次粒子の平均粒径は１００〜６００ｎｍであった。また、ＳＥＭ観察から球状粒子が観察された。Ｘ線回折ではｆｃｃ構造に由来する回折ピークしか観察されなかった。ＶＳＭによる飽和磁化の測定結果は、５５emu/g であった。Ｘ線結晶粒径（Ｄｘ）は２９ｎｍであった。ＳＥＭ観察結果を図４（ａ）に、またＸ線回折パターンを図３（ａ）に示した。Ｘ線回折結果および飽和磁化値から本例のニッケル粉はｆｃｃ構造であると見てよい。 As a result, the average particle diameter of primary particles observed from a transmission electron microscope (TEM) was 100 to 600 nm. In addition, spherical particles were observed from SEM observation. In X-ray diffraction, only diffraction peaks derived from the fcc structure were observed. The measurement result of saturation magnetization by VSM was 55 emu / g. The X-ray crystal grain size (Dx) was 29 nm. The SEM observation result is shown in FIG. 4A, and the X-ray diffraction pattern is shown in FIG. From the X-ray diffraction result and the saturation magnetization value, it can be seen that the nickel powder of this example has an fcc structure.
〔例４〕
酢酸ニッケル（II）四水和物を０.００２５mol ／Ｌになるように添加した以外は、例３を繰り返した。
[Example 4]
Example 3 was repeated except that nickel acetate (II) tetrahydrate was added to 0.0025 mol / L.
得られたニッケル粉含有物を例３と同様の測定に供した。透過電子顕微鏡（ＴＥＭ）から観測された１次粒子の平均粒径は６０〜７０ｎｍであった。ＳＥＭ観察からは球状粒子が観察された。Ｘ線回折ではｆｃｃ構造とｈｃｐ構造に由来する回折ピークが観察された。ＶＳＭによる飽和磁化の測定結果は２１emu/g であった。Ｘ線結晶粒径（Ｄｘ）は１２ｎｍであった。ＳＥＭ観察結果を図５に示した。またＸ線回折パターンを図２（ｂ）に示しが、ｆｃｃ相＋ｈｃｐ相が共存しているのがわかる。 The obtained nickel powder-containing material was subjected to the same measurement as in Example 3. The average particle diameter of primary particles observed from a transmission electron microscope (TEM) was 60 to 70 nm. Spherical particles were observed from SEM observation. In X-ray diffraction, diffraction peaks derived from the fcc structure and the hcp structure were observed. The measurement result of saturation magnetization by VSM was 21 emu / g. The X-ray crystal grain size (Dx) was 12 nm. The SEM observation results are shown in FIG. Further, the X-ray diffraction pattern is shown in FIG. 2B, and it can be seen that the fcc phase + hcp phase coexist.
〔例５〕
テトラエチングリコール（沸点：３２７.３℃）１００ｍＬに、酢酸ニッケル（II）四水和物を０.００２５mol ／Ｌになるよう添加し、固形分が存在しなくなるまで溶解した。この溶液を還流器のついた容器に移してオイルバスに載せ、容器内に不活性ガスとして窒素ガスを４００ｍＬ／ｍｉｎの流量で吹込みながら、該溶液を１６０ｒｐｍの回転速度で撹拌しつつ加熱し、２９０℃の温度で１時間の還流を行って、反応を終了した。そのさい、昇温速度は１０℃／min とした。
[Example 5]
To 100 mL of tetraethine glycol (boiling point: 327.3 ° C.), nickel (II) acetate tetrahydrate was added to a concentration of 0.0025 mol / L and dissolved until no solid content existed. This solution is transferred to a container equipped with a reflux device and placed in an oil bath. While blowing nitrogen gas as an inert gas at a flow rate of 400 mL / min into the container, the solution is heated while being stirred at a rotation speed of 160 rpm. The reaction was terminated by refluxing at a temperature of 290 ° C. for 1 hour. At that time, the heating rate was set to 10 ° C./min.
その結果、透過電子顕微鏡（ＴＥＭ）から観測された１次粒子の平均粒径は約１５０ｎｍであった。また、ＳＥＭ観察から球状粒子が観察された。Ｘ線回折ではｈｃｐ構造に由来する回折ピークしか観察されなかった。ＶＳＭによる飽和磁化の測定結果は、ほぼ０emu/g であった。Ｘ線結晶粒径（Ｄｘ）は４３ｎｍであった。ＳＥＭ観察結果を図４（ｂ）に、またＸ線回折パターンを図３（ｂ）に示したが、ｈｃｐ単相であることがわかる。 As a result, the average particle diameter of primary particles observed from a transmission electron microscope (TEM) was about 150 nm. In addition, spherical particles were observed from SEM observation. In X-ray diffraction, only diffraction peaks derived from the hcp structure were observed. The measurement result of saturation magnetization by VSM was almost 0 emu / g. The X-ray crystal grain size (Dx) was 43 nm. The SEM observation result is shown in FIG. 4 (b) and the X-ray diffraction pattern is shown in FIG. 3 (b). It can be seen that it is an hcp single phase.
〔例６〕
テトラエチレングリコール１００ｍＬに、酢酸ニッケル（II）四水和物を０.０１mol
／Ｌになるよう添加し、さらにヘキサクロロ白金（IV）酸（和光純薬株式会社製）を０.１２５ｇ添加し、固形分が存在しなくなるまで溶解した。この溶液を還流器のついた容器に移してオイルバスに載せ、容器内に不活性ガスとして窒素ガスを４００ｍＬ／ｍｉｎの流量で吹込みながら、該溶液を１６０ｒｐｍの回転速度で撹拌しつつ加熱し、反応温度を２９０℃の温度で１時間の還流を行って、反応を終了した。そのさい、昇温速度は１０℃／min とした。得られたＮｉ粉のＸ線回折パターンを図７に示した。図７に見られるようにｈｃｐ―Ｎｉに由来するピークしか観察されなかった。また、このＮｉ粉のＳＥＭ写真を図８に示したが、数１００ｎｍの一次粒子が凝集した状態のものが観察される。
[Example 6]
To 100 mL of tetraethylene glycol, 0.01 mol of nickel (II) acetate tetrahydrate
Then, 0.125 g of hexachloroplatinic (IV) acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added and dissolved until no solid content existed. This solution is transferred to a container equipped with a reflux device and placed in an oil bath. While blowing nitrogen gas as an inert gas at a flow rate of 400 mL / min into the container, the solution is heated while being stirred at a rotation speed of 160 rpm. The reaction was terminated by refluxing for 1 hour at a reaction temperature of 290 ° C. At that time, the heating rate was set to 10 ° C./min. The X-ray diffraction pattern of the obtained Ni powder is shown in FIG. As can be seen in FIG. 7, only peaks derived from hcp-Ni were observed. Moreover, although the SEM photograph of this Ni powder was shown in FIG. 8, the thing of the state which the primary particle of several 100 nm aggregated is observed.
〔例７〕
テトラエチレングリコール１００ｍＬに、酢酸ニッケル（II）四水和物を０.００５mol ／Ｌになるよう添加し、さらにヘキサクロロ白金（IV）酸（和光純薬株式会社製）を０.１２５ｇ添加し、固形分が存在しなくなるまで溶解した。この溶液を還流器のついた容器に移してオイルバスに載せ、容器内に不活性ガスとして窒素ガスを４００ｍＬ／ｍｉｎの流量で吹込みながら、該溶液を１６０ｒｐｍの回転速度で撹拌しつつ加熱し、反応温度を２９０℃の温度で１時間の還流を行って、反応を終了した。そのさい、昇温速度は１０℃／min とした。得られたＮｉ粉のＸ線回折パターンを図９に示した。図９に見られるようにｈｃｐ―Ｎｉに由来するピークしか観察されなかった。また、このＮｉ粉のＳＥＭ写真を図１０に示したが、１００ｎｍ程度以下の一次粒子が凝集した状態のものが観察され、例６のもの（図７）と比較すると、Ｎｉ塩の仕込み濃度を下げた本例では一次粒子がより微粒子化していることがわかる。
[Example 7]
To 100 mL of tetraethylene glycol, nickel acetate (II) tetrahydrate was added to 0.005 mol / L, and further 0.125 g of hexachloroplatinic acid (IV) (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Dissolved until no more minutes were present. This solution is transferred to a container equipped with a reflux device and placed in an oil bath. While blowing nitrogen gas as an inert gas at a flow rate of 400 mL / min into the container, the solution is heated while being stirred at a rotation speed of 160 rpm. The reaction was terminated by refluxing for 1 hour at a reaction temperature of 290 ° C. At that time, the heating rate was set to 10 ° C./min. The X-ray diffraction pattern of the obtained Ni powder is shown in FIG. As can be seen in FIG. 9, only peaks derived from hcp-Ni were observed. Moreover, although the SEM photograph of this Ni powder was shown in FIG. 10, the thing of the state which the primary particle about 100 nm or less aggregated was observed, and compared with the thing of FIG. In this lowered example, it can be seen that the primary particles are made finer.
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