JP4505633B2 - Manufacturing method of nickel powder with hcp structure - Google Patents
Manufacturing method of nickel powder with hcp structure Download PDFInfo
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- JP4505633B2 JP4505633B2 JP2004231584A JP2004231584A JP4505633B2 JP 4505633 B2 JP4505633 B2 JP 4505633B2 JP 2004231584 A JP2004231584 A JP 2004231584A JP 2004231584 A JP2004231584 A JP 2004231584A JP 4505633 B2 JP4505633 B2 JP 4505633B2
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Description
本発明は、ｈｃｐ構造をもつニッケル粉およびその製法に関する。 The present invention relates to nickel powder having an hcp structure and a method for producing the same.
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 configuration, if the nickel fine powder has magnetism, the nickel fine powder causes 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。
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, the use of fcc-structured nickel powder, which is a ferromagnetic material, is limited because it causes magnetic aggregation if it has magnetism.
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。しかし、
磁性をもたないニッケル粉は知られておらず、製造もされていない。
Thus, it may be disadvantageous to have magnetism in the use of nickel powder. But,
Nickel powder without magnetism is not known or manufactured.
本発明は、磁性を有しないか、有しても僅かであるニッケル粉を得ること、さらには粒
径および結晶構造の制御可能な製法を確立することを課題としてなされたものである。
An object of the present invention is to obtain a nickel powder that has no or little magnetism, and further to establish a production method capable of controlling the grain size and crystal structure.
前記の磁性に関する課題は、ｈｃｐ構造（六方最密構造）をもつＮｉの微粒子からなるニッケル粉によって解決できることがわかった。また、粒径および結晶構造の制御に関す
る課題は、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ことからなるｈｃｐ構造をもつニッケル粉の製法によって解決できる
ことがわかった。
It has been found that the above-mentioned problems relating to magnetism can be solved by nickel powder comprising Ni fine particles having an hcp structure (hexagonal close-packed structure). In addition, the problems related to the control of the particle size and crystal structure can be solved by a method for producing nickel powder having an hcp structure, in which Ni ions dissolved in the polyol are reduced with the polyol and metal Ni fine particles are precipitated in the liquid. I understood.
したがって本発明によると、ｈｃｐ構造（またはｈｃｐ構造とｆｃｃ構造）をもつＮｉの微粒子からなる、飽和磁化値４０emu/g 以下（０emu/g を含む）のニッケル粉を提供す
る。このニッケル粉はＴＥＭ観察による平均粒径が好ましくは５μｍ以下である。
Therefore, according to the present invention, there is provided nickel powder having a saturation magnetization value of 40 emu / g or less (including 0 emu / g) made of Ni fine particles having an hcp structure (or hcp structure and fcc structure). The nickel powder preferably has an average particle size of 5 μm or less as observed by TEM.
本発明者は、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 reduce Ni ions in a liquid to Ni by the polyol (polyol method) by treating a polyol in which Ni ions are dissolved under evaporation / reflux conditions, hcp
It has been found that Ni fine particles including a structure can be 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（ＴＥ
Ｇ）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 can be ethylene glycol (EG), trimethylene glycol (TMEG) or tetraethylene glycol (TE
An experiment of a polyol method in which the polyol medium was evaporated and refluxed in a container equipped with a refluxer after being dissolved in G) was conducted.
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. 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. Saturation magnetization at room temperature is 55-38emu /
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 result is shown in the XRD pattern of FIG.
It was shown in the SEM image of b). FIG. 3B shows a peak only for hcp, and it can be seen that this Ni particle powder has a pure hcp structure. This Ni particle powder is the SEM of FIG.
As can be seen in the image, the average particle size of the primary particles was about 150 nm, and the saturation magnetization value did not have a value as measured.
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. Adopting 0.94 as K in Scherrer's equation, D = K · λ / β COSθ
The X-ray tube was calculated from D = 0.94 × 1.5405 / β COSθ 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.
〔比較例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。
[ Comparative 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 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 192 ° C. for 1 hour. 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１０
０ｍＬ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、ＴＥ
Ｍ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. The residue (particle powder) after removing the supernatant was again methanol 10
0 mL was added 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. TE
M and SEM observations were also made.
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.
〔比較例２〕
水酸化イオン（ＯＨ-）の導入のために、ＯＨ-／Ｎｉのモル比が５０となる量のＮａＯＨを原料溶解時に添加した以外は比較例１を繰り返した。
[ Comparative Example 2 ]
Comparative 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 50.
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. X-ray diffraction revealed an fcc phase, but from the saturation magnetization value, the nickel powder of this example was fcc phase + hcp.
It can be seen that it is a double phase of phases.
〔比較例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。
[ Comparative 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 results are shown in FIG.
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.
〔比較例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、比較例３を繰り返した。
[ Comparative Example 4 ]
Comparative Example 3 was repeated except that nickel (II) acetate 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１２
ｎｍ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. X-ray crystal grain size (Dx) is 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.
〔実施例１〕
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 1 ]
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.
In addition, the X-ray diffraction pattern is shown in FIG. 3B, and it can be seen that it is an hcp single phase.
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| US20090032799A1 (en) | 2007-06-12 | 2009-02-05 | Siphoton, Inc | Light emitting device |
| US7956370B2 (en) | 2007-06-12 | 2011-06-07 | Siphoton, Inc. | Silicon based solid state lighting |
| US8283676B2 (en) | 2010-01-21 | 2012-10-09 | Siphoton Inc. | Manufacturing process for solid state lighting device on a conductive substrate |
| US8722441B2 (en) | 2010-01-21 | 2014-05-13 | Siphoton Inc. | Manufacturing process for solid state lighting device on a conductive substrate |
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| CN113725452B (en) * | 2021-08-25 | 2023-04-04 | 武汉大学苏州研究院 | Hexagonal close-packed nickel and polycrystalline phase nickel heterojunction electrocatalyst, preparation method and application |
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| JPS59173206A (en) * | 1982-12-21 | 1984-10-01 | ユニヴア−シテ・パリ・セテイエ−ム | Method of reducing metal compound with polyol and powdery metal manufactured thereby |
| JP2004308014A (en) * | 2003-04-09 | 2004-11-04 | Samsung Electronics Co Ltd | Nonmagnetic nickel powder, and its production method |
| JP2004353089A (en) * | 2003-05-27 | 2004-12-16 | Samsung Electronics Co Ltd | Method for producing non-magnetic nickel powder |
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| JPS59173206A (en) * | 1982-12-21 | 1984-10-01 | ユニヴア−シテ・パリ・セテイエ−ム | Method of reducing metal compound with polyol and powdery metal manufactured thereby |
| JP2004308014A (en) * | 2003-04-09 | 2004-11-04 | Samsung Electronics Co Ltd | Nonmagnetic nickel powder, and its production method |
| JP2004353089A (en) * | 2003-05-27 | 2004-12-16 | Samsung Electronics Co Ltd | Method for producing non-magnetic nickel powder |
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