JP2991700B2 - Method for producing nickel fine powder - Google Patents
Method for producing nickel fine powderInfo
- Publication number
- JP2991700B2 JP2991700B2 JP10205878A JP20587898A JP2991700B2 JP 2991700 B2 JP2991700 B2 JP 2991700B2 JP 10205878 A JP10205878 A JP 10205878A JP 20587898 A JP20587898 A JP 20587898A JP 2991700 B2 JP2991700 B2 JP 2991700B2
- Authority
- JP
- Japan
- Prior art keywords
- sodium hydroxide
- nickel
- jis
- specified
- aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Description
【０００１】[0001]
【発明の属する技術分野】本発明はニッケル微粉末の製
造方法に関し、より詳しくは、主として積層セラミック
コンデンサの内部電極材料として用いるのに適してお
り、粒度分布がシャープで凝集が少なく、且つペースト
化した際の充填性に優れているニッケル微粉末の製造方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a fine nickel powder, and more particularly, it is suitable mainly for use as an internal electrode material of a multilayer ceramic capacitor, has a sharp particle size distribution, has less agglomeration, and is formed into a paste. The present invention relates to a method for producing a fine nickel powder which is excellent in the filling property at the time of making.
【０００２】[0002]
【従来の技術】積層セラミックコンデンサは、セラミッ
ク誘電体と内部電極とを交互に層状に重ねて圧着、焼
成、一体化したものである。この内部電極材料として従
来用いられていたＰｔ、Ｐｄ等の貴金属の代わりにＮｉ
等の卑金属を用いる技術が開発され、進歩してきてい
る。2. Description of the Related Art A multilayer ceramic capacitor is obtained by alternately stacking ceramic dielectrics and internal electrodes in layers, pressing, firing, and integrating them. Instead of the noble metals such as Pt and Pd conventionally used as this internal electrode material, Ni
Technologies using base metals such as have been developed and advanced.
【０００３】この開発、進歩に伴って、当該材料である
ニッケル粉末の製造方法についても様々な提案がなされ
ている。その代表的な製法としては、特開平８−２４６
００１号公報に開示されているような塩化ニッケル蒸気
の気相水素還元法の如き乾式法も挙げられるが、ニッケ
ルイオンを含む水溶液を特定条件の下、還元剤にて還元
処理してニッケルを析出させる湿式法には、エネルギー
コスト面での経済性等も含めて有利な点が多い。[0003] With the development and progress, various proposals have been made on a method for producing nickel powder as the material. A typical production method is disclosed in JP-A-8-246.
A dry method such as a gas-phase hydrogen reduction method of nickel chloride vapor as disclosed in Japanese Patent Application Laid-Open No. 001-001 is also available. However, an aqueous solution containing nickel ions is reduced with a reducing agent under specific conditions to deposit nickel. The wet method has many advantages, including economy in terms of energy costs.
【０００４】この湿式法の代表例としては、特開平７−
２０７３０７号公報、特開平７−２７８６１９号公報等
に開示されている方法が挙げられる。前者には、ヒドロ
キシルイオンとアンモニウムイオンとを含有する水溶液
に、水溶性ニッケル（II）塩水溶液を混合してアンモニ
ア・ニッケル錯体を生成させ、その後、還元剤を添加し
てアンモニア・ニッケル錯体を還元することからなる製
造方法が記載されている。又、後者には、特定の濃度の
ニッケル塩水溶液に強アルカリを加え、特定のｐＨなら
びに温度とした後、特定の温度、濃度を有する還元剤で
特定時間内に反応を終了させることからなる製造方法が
記載されている。これらの製造方法によって得られるニ
ッケル粉末については、一次粒径が前者では０．３〜
１．２μｍの範囲内、後者では０．４〜０．６μｍの範
囲内であり、また、粒度分布の幅も従来品と同等以上の
ものが得られると記載されている。A typical example of this wet method is disclosed in
207307 and JP-A-7-278619. In the former, an aqueous solution containing a hydroxyl ion and an ammonium ion is mixed with a water-soluble nickel (II) salt aqueous solution to form an ammonia-nickel complex, and then a reducing agent is added to reduce the ammonia-nickel complex. A manufacturing method is described. In the latter case, a production method comprising adding a strong alkali to a nickel salt aqueous solution having a specific concentration to obtain a specific pH and temperature, and terminating the reaction within a specific time with a reducing agent having a specific temperature and concentration. A method is described. Regarding nickel powder obtained by these production methods, the primary particle size is 0.3 to 0.3 in the former.
It is described as being within a range of 1.2 μm, the latter being within a range of 0.4 to 0.6 μm, and having a width of particle size distribution equal to or greater than that of a conventional product.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記の
製造方法で得られた粉末はある程度の粒度分布領域に収
まっているものの、特開平７−２０７３０７号公報に開
示の方法においては、その明細書第４頁表２に示されて
いるようにＤ90値は２．１３〜３．８８μｍ程度であ
り、特開平７−２７８６１９号公報に開示の方法におい
ては、その明細書第３頁表２に示されているようにＤ90
値は２．５８〜２．８７μｍ程度である。従って、上記
の製造方法は、凝集が一層少なく即ちＤ90値の小さい粉
末を得る方法としては不十分であった。本発明は、積層
セラミックコンデンサの内部電極材料として用いるのに
適した０．１〜０．９μｍ程度の１次粒子の平均粒径を
有し、低凝集で粒度分布幅が狭く、且つ高タップ密度の
ニッケル微粉末を得るための製造方法を提供することを
目的としている。However, although the powder obtained by the above-described production method falls within a certain particle size distribution range, the method disclosed in Japanese Patent Application Laid-Open No. 7-207307 discloses a method disclosed in the specification. 4 pp. table D 90 value as shown in 2 is about 2.13～3.88Myuemu, in the method disclosed in JP-a-7-278619, shown in its specification page 3 table 2 D 90 as has been
The value is about 2.58 to 2.87 μm. Thus, the method of manufacturing, aggregation was not sufficient as a method for obtaining a small powder having further reduced i.e. D 90 value. The present invention has an average primary particle diameter of about 0.1 to 0.9 μm, which is suitable for use as an internal electrode material of a multilayer ceramic capacitor, has a low aggregation, a narrow particle size distribution width, and a high tap density. It is an object of the present invention to provide a production method for obtaining a nickel fine powder.
【０００６】[0006]
【課題を解決するための手段】１次粒子の平均粒径を制
御しながら、粒度分布が狭く且つタップ密度の高いニッ
ケル粉末を製造するためには、水酸化ニッケル生成工程
や還元反応工程における溶液濃度、溶液温度、反応温
度、添加継続時間、撹拌条件等の種々の製造条件につい
て配慮する必要がある。勿論、かかる製造条件は重要な
要素であるが、これら製造条件の調整だけで目的を達成
するには限界がある。そのことは前記した先行技術に記
載のニッケル粉末の特性値を見ても明らかである。In order to produce nickel powder having a narrow particle size distribution and a high tap density while controlling the average particle size of the primary particles, it is necessary to use a solution in a nickel hydroxide production step or a reduction reaction step. It is necessary to consider various production conditions such as concentration, solution temperature, reaction temperature, duration of addition, and stirring conditions. Of course, such manufacturing conditions are important factors, but there is a limit to achieving the purpose only by adjusting these manufacturing conditions. This is apparent from the characteristic values of the nickel powder described in the above-mentioned prior art.
【０００７】本発明者らは上記課題を解決するために鋭
意研究を重ねた結果、水酸化ナトリウム水溶液と硫酸ニ
ッケル水溶液とを混合して水酸化ニッケルを生成させ、
次いで該水酸化ニッケルを還元してニッケル粉末を製造
する方法において、該水酸化ナトリウム水溶液中に微量
の不純物が存在すると、最終生成ニッケル粉末の１次粒
子の平均粒径、凝集性、粒度分布幅、及びタップ密度が
影響されること、その微量の不純物の濃度を調整するこ
とにより目的とする特定の１次粒子の平均粒径を有し、
低凝集で粒度分布幅が狭く、且つ高タップ密度のニッケ
ル微粉末を得ることができること、また、その微量の不
純物の濃度の調整法として、ＪＩＳ Ｋ１２０３で規定
する液体かせいソーダと、ＪＩＳ Ｋ ８５７６で規定
する水酸化ナトリウム及びＪＩＳ Ｋ １２０２で規定
する固形かせいソーダの一方又は両方とを混合して用い
ることが簡便であることを見出し、本発明を完成した。The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, mixed an aqueous solution of sodium hydroxide and an aqueous solution of nickel sulfate to produce nickel hydroxide.
Then, in the method for producing nickel powder by reducing the nickel hydroxide, if a small amount of impurities are present in the aqueous sodium hydroxide solution, the average particle size, aggregability, and particle size distribution of the primary particles of the final nickel powder produced , And that the tap density is affected, by adjusting the concentration of the trace amount of impurities, the average particle diameter of the specific primary particles of interest,
It is possible to obtain a nickel fine powder having a low agglomeration, a narrow particle size distribution width, and a high tap density. In addition, as a method for adjusting the concentration of a trace amount of impurities, a liquid caustic soda specified by JIS K1203 and a JIS K 8576 The present inventors have found that it is convenient to use a mixture of the specified sodium hydroxide and one or both of solid soda specified in JIS K1202, and completed the present invention.
【０００８】即ち、本発明のニッケル微粉末の製造方法
は、ＪＩＳ Ｋ １２０３で規定する液体かせいソーダ
を水酸化ナトリウム水溶液中の全水酸化ナトリウム分の
７５〜８５重量％を占める量で含有し且つＪＩＳ Ｋ
８５７６で規定する水酸化ナトリウム及びＪＩＳ Ｋ
１２０２で規定する固形かせいソーダの一方又は両方を
合計で水酸化ナトリウム水溶液中の全水酸化ナトリウム
分の２５〜１５重量％を占める量で含有する水酸化ナト
リウム水溶液と、硫酸ニッケル水溶液とを混合して水酸
化ニッケルを生成させ、次いで該水酸化ニッケルをヒド
ラジンで還元し、生成ニッケルを回収することを特徴と
する。That is, the method for producing a nickel fine powder of the present invention comprises a liquid soda specified in JIS K 1203 in an amount occupying 75 to 85% by weight of the total sodium hydroxide in an aqueous sodium hydroxide solution. JIS K
Sodium hydroxide and JIS K specified in 8576
A sodium hydroxide aqueous solution containing one or both of the solid sodium hydroxide soda specified in 1202 in an amount occupying 25 to 15% by weight of the total sodium hydroxide in the sodium hydroxide aqueous solution and a nickel sulfate aqueous solution are mixed. To produce nickel hydroxide, and then reduce the nickel hydroxide with hydrazine to recover the produced nickel.
【０００９】本発明の製造方法において、１次粒子の平
均粒径を制御しながら、低凝集で粒度分布が狭く且つタ
ップ密度の高いニッケル微粉末を製造することができる
理由、メカニズムについては現時点では明確には究明さ
れていない。しかし、本発明で用いる上記３種類の水酸
化ナトリウム原料には、それぞれ異なる濃度でＦｅ3+、
Ｃａ2+、Ａｌ3+等の陽イオンや、ＣＯ3 2- 、Ｃｌ- 等の
陰イオンが含まれており、これらの陽イオンは水酸化ニ
ッケル生成反応や還元反応時の核生成に、また、これら
の陰イオンは当該反応速度に各々大きな影響を及ぼすも
のと思われる。In the production method of the present invention, the reason why a fine nickel powder having a low agglomeration, a narrow particle size distribution and a high tap density can be produced while controlling the average particle diameter of the primary particles is described at present. Not clearly determined. However, the three kinds of sodium hydroxide raw materials used in the present invention have different concentrations of Fe 3+ ,
It contains cations such as Ca 2+ and Al 3+ and anions such as CO 3 2- and Cl − , and these cations are used for nucleation during nickel hydroxide formation reaction and reduction reaction, and These anions are thought to have a large effect on the reaction rate.
【００１０】本発明で用いるＪＩＳ Ｋ ８５７６で規
定する水酸化ナトリウムの品質（規格値）は次の通りで
ある。 純度 ９６．０％以上 塩化物（Ｃｌ） ０．００５％以下 りん酸塩（ＰＯ4 ） ０．００１％以下 けい酸塩（ＳｉＯ2 として） ０．０１％以下 硫酸塩（ＳＯ4 ） ０．００２％以下 窒素化合物（Ｎとして） ０．００１％以下 カリウム（Ｋ） ０．０５％以下 マグネシウム（Ｍｇ） ５ｐｐｍ以下 カルシウム（Ｃａ） ０．００２％以下 亜鉛（Ｚｎ） ０．００１％以下 アルミニウム（Ａｌ） ０．００２％以下 鉛（Ｐｂ） ５ｐｐｍ以下 鉄（Ｆｅ） ５ｐｐｍ以下 ニッケル（Ｎｉ） ０．００１％以下 炭酸ナトリウム（Ｎａ2 ＣＯ3 ） １．５％以下The quality (standard value) of sodium hydroxide specified in JIS K 8576 used in the present invention is as follows. Purity 96.0% or more Chloride (Cl) 0.005% or less Phosphate (PO 4 ) 0.001% or less Silicate (as SiO 2 ) 0.01% or less Sulfate (SO 4 ) 0.002 % Or less Nitrogen compound (as N) 0.001% or less Potassium (K) 0.05% or less Magnesium (Mg) 5ppm or less Calcium (Ca) 0.002% or less Zinc (Zn) 0.001% or less Aluminum (Al) 0.002% or less Lead (Pb) 5ppm or less Iron (Fe) 5ppm or less Nickel (Ni) 0.001% or less Sodium carbonate (Na 2 CO 3 ) 1.5% or less
【００１１】本発明で用いるＪＩＳ Ｋ １２０２で規
定する固形かせいソーダの品質は次表に示す通りであ
る。 The quality of the solid soda specified in JIS K 1202 used in the present invention is as shown in the following table.
【００１２】本発明で用いるＪＩＳ Ｋ １２０３で規
定する液体かせいソーダの品質は次の通りである。水酸
化ナトリウム（ＮａＯＨ）含有量４５％の液体かせいソ
ーダについては次表に示す通りである。 水酸化ナトリウム（ＮａＯＨ）含有量４５％以外の液体
かせいソーダについての各成分は、上表の数値を基に水
酸化ナトリウム（ＮａＯＨ）含有量に比例した数値以下
である。The quality of the liquid skein soda specified in JIS K 1203 used in the present invention is as follows. The liquid soda having a sodium hydroxide (NaOH) content of 45% is as shown in the following table. Each component of the liquid soda except for the sodium hydroxide (NaOH) content of 45% is not more than the value proportional to the sodium hydroxide (NaOH) content based on the values in the above table.
【００１３】従って、これらの不純物とも呼ぶべきイオ
ンの濃度を調整すれば、製造されるニッケル粉末の特性
も自ずと制御できると考えられる。例えば、水酸化ナト
リウム源として、経済面を重視してＪＩＳ Ｋ １２０
３で規定する液体かせいソーダのみを用いた場合には、
含まれる不純物イオン濃度が高く且つ濃度がばらつくた
め、各反応の度に大きめの核が増え、発生量がばらつく
と同時に、反応速度が大きく振れ、仕上がったニッケル
粉末の１次粒子の平均粒径は大きめで粒度が不揃いにな
りやすい。Therefore, it is considered that the characteristics of the produced nickel powder can be controlled by adjusting the concentration of the ions, which are also called impurities. For example, as a sodium hydroxide source, JIS K 120
When only the liquid skein soda specified in 3 is used,
Since the concentration of impurity ions contained is high and the concentration varies, larger nuclei increase in each reaction, the amount of generation varies, and at the same time, the reaction speed fluctuates greatly. The average particle size of the primary particles of the finished nickel powder is Large and easy to have irregular particle size.
【００１４】一方、ニッケル粉末の特性、殊に粒度分布
を向上させるために、水酸化ナトリウム源としてＪＩＳ
Ｋ ８５７６で規定する水酸化ナトリウム又はＪＩＳ
Ｋ１２０２で規定する固形かせいソーダを用いた場合
には、含まれる不純物イオン濃度が低いので、細かめの
核が発生し、反応速度は安定するため、仕上がったニッ
ケル粉末の１次粒子の平均粒径は小さく、粒度分布の狭
いものが得られる。しかし、経済面で実用的ではない
上、１次粒子の平均粒径の大き目のニッケル粉末を得る
ことができない。On the other hand, in order to improve the characteristics of the nickel powder, especially the particle size distribution, JIS is used as a sodium hydroxide source.
Sodium hydroxide or JIS specified in K 8576
When the solid caustic soda specified in K1202 is used, the concentration of impurity ions contained therein is low, so fine nuclei are generated, and the reaction rate is stabilized. Therefore, the average particle size of the primary particles of the finished nickel powder Is small and a narrow particle size distribution can be obtained. However, it is not economically practical and it is not possible to obtain a nickel powder having a large average primary particle size.
【００１５】本発明者らはこうした傾向を把握し、水酸
化ナトリウム源としてＪＩＳ Ｋ１２０３で規定する液
体かせいソーダと、ＪＩＳ Ｋ ８５７６で規定する水
酸化ナトリウム及びＪＩＳ Ｋ １２０２で規定する固
形かせいソーダの一方又は両方とを併用した水溶液を用
いることにより、不純物イオンの影響を小さくしなが
ら、経済面を配慮しつつ目的のニッケル粉末が得られる
ことを見出したのである。The present inventors have grasped such a tendency, and as a sodium hydroxide source, one of liquid sodium hydroxide soda specified by JIS K1203 and sodium hydroxide soda specified by JIS K8576 and solid sodium hydroxide soda specified by JIS K1202. Alternatively, they have found that by using an aqueous solution in which both are used, it is possible to obtain the desired nickel powder while reducing the influence of impurity ions and considering the economic aspect.
【００１６】[0016]
【発明の実施の形態】本発明の第一の実施態様として、
ＪＩＳ Ｋ １２０３で規定する液体かせいソーダを水
酸化ナトリウム水溶液中の全水酸化ナトリウム分の７５
〜８５重量％を占める量で含有し且つＪＩＳ Ｋ ８５
７６で規定する水酸化ナトリウムを水酸化ナトリウム水
溶液中の全水酸化ナトリウム分の２５〜１５重量％を占
める量で含有する水酸化ナトリウム水溶液を用いる。こ
の場合には、得られるニッケル粉末の１次粒子の平均粒
径は０．１〜０．３μｍ程度になる。DESCRIPTION OF THE PREFERRED EMBODIMENTS As a first embodiment of the present invention,
The liquid sodium hydroxide specified in JIS K 1203 is converted to 75% of the total sodium hydroxide in the aqueous sodium hydroxide solution.
８５85% by weight and JIS K85
An aqueous sodium hydroxide solution containing sodium hydroxide specified in 76 in an amount occupying 25 to 15% by weight of the total sodium hydroxide in the aqueous sodium hydroxide solution is used. In this case, the average particle size of the primary particles of the obtained nickel powder is about 0.1 to 0.3 μm.
【００１７】このような実施態様において、ＪＩＳ Ｋ
１２０３で規定する液体かせいソーダが水酸化ナトリ
ウム水溶液中の全水酸化ナトリウム分の７５重量％未
満、即ちＪＩＳ Ｋ ８５７６で規定する水酸化ナトリ
ウムが水酸化ナトリウム水溶液中の全水酸化ナトリウム
分の２５重量％を超える場合には、不純物イオン濃度が
低過ぎるので、１次粒子の平均粒径が０．１μｍよりも
小さくて凝集が大きいニッケル粉末となる上、コスト面
でも不経済である。又、逆に、ＪＩＳ Ｋ １２０３で
規定する液体かせいソーダが水酸化ナトリウム水溶液中
の全水酸化ナトリウム分の８５重量％を超える、即ちＪ
ＩＳ Ｋ ８５７６で規定する水酸化ナトリウムが水酸
化ナトリウム水溶液中の全水酸化ナトリウム分の１５重
量％未満の場合には、不純物イオン濃度が高過ぎ、反応
速度が不安定になり、その結果ニッケル粉末の粒度分布
の幅が広くなったり、タップ密度が小さくなるなどの弊
害が生じる。In such an embodiment, JIS K
The liquid sodium hydroxide specified in 1203 is less than 75% by weight of the total sodium hydroxide in the aqueous sodium hydroxide solution, that is, the sodium hydroxide specified in JIS K 8576 is 25% by weight of the total sodium hydroxide in the aqueous sodium hydroxide solution. %, The impurity ion concentration is too low, resulting in nickel powder having an average primary particle size of less than 0.1 μm and large aggregation, and is uneconomical in terms of cost. Conversely, the liquid soda specified in JIS K 1203 exceeds 85% by weight of the total sodium hydroxide in the aqueous sodium hydroxide solution,
If the sodium hydroxide specified in IS K 8576 is less than 15% by weight of the total sodium hydroxide in the aqueous sodium hydroxide solution, the impurity ion concentration is too high, and the reaction rate becomes unstable. The width of the particle size distribution becomes wide, and the tap density becomes small.
【００１８】本発明の第二の実施態様として、ＪＩＳ
Ｋ １２０３で規定する液体かせいソーダを水酸化ナト
リウム水溶液中の全水酸化ナトリウム分の７５〜８５重
量％を占める量で含有し且つＪＩＳ Ｋ １２０２で規
定する固形かせいソーダを水酸化ナトリウム水溶液中の
全水酸化ナトリウム分の２５〜１５重量％を占める量で
含有する水酸化ナトリウム水溶液を用いる。この場合に
は、得られるニッケル粉末の１次粒子の平均粒径は０．
７〜０．９μｍ程度になる。As a second embodiment of the present invention, JIS
Liquid sodium hydroxide specified in K1203 is contained in an amount occupying 75 to 85% by weight of the total sodium hydroxide in the aqueous sodium hydroxide solution, and solid sodium hydroxide specified in JIS K1202 is contained in the aqueous sodium hydroxide solution. An aqueous sodium hydroxide solution containing 25 to 15% by weight of sodium hydroxide is used. In this case, the average particle size of the primary particles of the obtained nickel powder is 0.1.
It is about 7 to 0.9 μm.
【００１９】このような実施態様において、ＪＩＳ Ｋ
１２０３で規定する液体かせいソーダが水酸化ナトリ
ウム水溶液中の全水酸化ナトリウム分の７５重量％未
満、即ちＪＩＳ Ｋ １２０２で規定する固形かせいソ
ーダが水酸化ナトリウム水溶液中の全水酸化ナトリウム
分の２５重量％を超える場合には、不純物イオン濃度が
低過ぎるので、１次粒子の平均粒径が小さくて凝集が大
きいニッケル粉末となる上、コスト面でも不経済であ
る。又、逆に、ＪＩＳ Ｋ １２０３で規定する液体か
せいソーダが水酸化ナトリウム水溶液中の全水酸化ナト
リウム分の８５重量％を超える、即ちＪＩＳ Ｋ １２
０２で規定する固形かせいソーダが水酸化ナトリウム水
溶液中の全水酸化ナトリウム分の１５重量％未満の場合
には、不純物イオン濃度が高過ぎ、１次粒子の平均粒径
が０．９μｍより大きくなる上、反応速度が不安定にな
り、その結果ニッケル粉末の粒度分布の幅が広くなった
り、タップ密度が小さくなるなどの弊害が生じる。In such an embodiment, JIS K
The liquid sodium hydroxide specified in 1203 is less than 75% by weight of the total sodium hydroxide in the aqueous sodium hydroxide solution, that is, the solid sodium hydroxide specified in JIS K 1202 is 25% by weight of the total sodium hydroxide in the aqueous sodium hydroxide solution. %, The impurity ion concentration is too low, resulting in a nickel powder having a small average particle size of primary particles and large aggregation, and is uneconomical in terms of cost. Conversely, the liquid soda specified in JIS K 1203 exceeds 85% by weight of the total sodium hydroxide in the aqueous sodium hydroxide solution, that is, JIS K 123.
When the amount of the solid sodium hydroxide specified in 02 is less than 15% by weight of the total sodium hydroxide in the aqueous sodium hydroxide solution, the impurity ion concentration is too high, and the average primary particle size is larger than 0.9 μm. In addition, the reaction rate becomes unstable, and as a result, adverse effects such as an increase in the width of the particle size distribution of the nickel powder and a decrease in the tap density are caused.
【００２０】本発明の第三の実施態様として、ＪＩＳ
Ｋ １２０３で規定する液体かせいソーダを水酸化ナト
リウム水溶液中の全水酸化ナトリウム分の７５〜８５重
量％を占める量で含有し且つＪＩＳ Ｋ ８５７６で規
定する水酸化ナトリウム及びＪＩＳ Ｋ １２０２で規
定する固形かせいソーダの両方を合計で水酸化ナトリウ
ム水溶液中の全水酸化ナトリウム分の２５〜１５重量％
を占める量で含有する水酸化ナトリウム水溶液を用い
る。この場合には、得られるニッケル粉末の１次粒子の
平均粒径は０．１〜０．９μｍ程度になる。As a third embodiment of the present invention, JIS
Liquid sodium hydroxide specified in K1203 is contained in an amount occupying 75 to 85% by weight of the total sodium hydroxide in the aqueous sodium hydroxide solution, and sodium hydroxide specified in JIS K8576 and solid specified in JIS K1202 25-15% by weight of total sodium hydroxide in sodium hydroxide aqueous solution
Aqueous solution containing sodium hydroxide in an amount occupying the same. In this case, the average particle size of the primary particles of the obtained nickel powder is about 0.1 to 0.9 μm.
【００２１】このような実施態様において、ＪＩＳ Ｋ
１２０３で規定する液体かせいソーダが水酸化ナトリ
ウム水溶液中の全水酸化ナトリウム分の７５重量％未
満、即ちＪＩＳ Ｋ ８５７６で規定する水酸化ナトリ
ウムとＪＩＳ Ｋ １２０２で規定する固形かせいソー
ダの合計が水酸化ナトリウム水溶液中の全水酸化ナトリ
ウム分の２５重量％を超える場合には、不純物イオン濃
度が低過ぎるので、１次粒子の平均粒径が０．１μｍよ
りも小さくて凝集が大きいニッケル粉末となる上、コス
ト面でも不経済である。又、逆に、ＪＩＳ Ｋ １２０
３で規定する液体かせいソーダが水酸化ナトリウム水溶
液中の全水酸化ナトリウム分の８５重量％を超える、即
ちＪＩＳ Ｋ ８５７６で規定する水酸化ナトリウムと
ＪＩＳ Ｋ１２０２で規定する固形かせいソーダの合計
が水酸化ナトリウム水溶液中の全水酸化ナトリウム分の
１５重量％未満の場合には、不純物イオン濃度が高過
ぎ、１次粒子の平均粒径が０．９μｍより大きくなる
上、反応速度が不安定になり、その結果ニッケル粉末の
粒度分布の幅が広くなったり、タップ密度が小さくなる
などの弊害が生じる。In such an embodiment, JIS K
The liquid caustic soda specified in 1203 is less than 75% by weight of the total sodium hydroxide in the aqueous sodium hydroxide solution. If the total sodium hydroxide content in the sodium aqueous solution exceeds 25% by weight, the concentration of impurity ions is too low, so that the average particle size of the primary particles is smaller than 0.1 μm and the agglomeration becomes large. It is uneconomical in terms of cost. Conversely, JIS K 120
The liquid soda specified in No. 3 exceeds 85% by weight of the total sodium hydroxide in the aqueous sodium hydroxide solution, that is, the sum of sodium hydroxide specified in JIS K 8576 and the solid determined soda specified in JIS K1202 is hydroxylated. If the total sodium hydroxide content in the sodium aqueous solution is less than 15% by weight, the impurity ion concentration is too high, the average particle size of the primary particles becomes larger than 0.9 μm, and the reaction rate becomes unstable, As a result, adverse effects such as an increase in the width of the particle size distribution of the nickel powder and a decrease in the tap density are caused.
【００２２】本発明の製造方法においては、水酸化ニッ
ケル生成工程や還元反応工程での諸条件も重要である。
まず、水酸化ニッケル生成工程については、水酸化ナト
リウム水溶液と硫酸ニッケル水溶液とを混合する際の両
者の混合比は化学当量で水酸化ナトリウム：硫酸ニッケ
ル＝１．６６〜１．８４：１であることが好ましく、
１．７０〜１．８０：１であることが更に好ましい。そ
の混合比が１．６６：１よりも小さい（水酸化ナトリウ
ムの相対量が少ない）場合には、水酸化ニッケルの生成
に長時間を要したり、目標とする１次粒子の平均粒径の
ニッケル粉末が得られ難かったり、１次粒子の粒度分布
の幅が広くなったりする傾向がある。逆にその混合比が
１．８４：１を超える場合には、増加するコストに見合
った効果が得られない。In the production method of the present invention, various conditions in the nickel hydroxide production step and the reduction reaction step are also important.
First, in the nickel hydroxide producing step, the mixing ratio of the aqueous sodium hydroxide solution and the aqueous nickel sulfate solution is a chemical equivalent of sodium hydroxide: nickel sulfate = 1.66 to 1.84: 1. Preferably,
More preferably, the ratio is 1.70 to 1.80: 1. When the mixing ratio is smaller than 1.66: 1 (the relative amount of sodium hydroxide is small), it takes a long time to produce nickel hydroxide, or the average primary particle There is a tendency that it is difficult to obtain a nickel powder and the width of the particle size distribution of the primary particles is wide. On the other hand, if the mixing ratio exceeds 1.84: 1, the effect corresponding to the increased cost cannot be obtained.
【００２３】また、水酸化ナトリウム水溶液と硫酸ニッ
ケル水溶液とを混合する際には、水酸化ナトリウム水溶
液と硫酸ニッケル水溶液とを一気に混合することも可能
であるが、この場合にはゼリー状となる傾向があって後
処理が面倒である。従って、水酸化ナトリウム水溶液に
硫酸ニッケル水溶液を徐々に添加するか、又は硫酸ニッ
ケル水溶液に水酸化ナトリウム水溶液を徐々に添加する
ことが好ましい。When the aqueous sodium hydroxide solution and the aqueous nickel sulfate solution are mixed, it is possible to mix the aqueous sodium hydroxide solution and the aqueous nickel sulfate solution at once, but in this case, the aqueous solution tends to be jelly-like. And post-processing is troublesome. Therefore, it is preferable to gradually add an aqueous solution of nickel sulfate to an aqueous solution of sodium hydroxide, or to add an aqueous solution of sodium hydroxide to an aqueous solution of nickel sulfate.
【００２４】次に、還元反応工程については、水酸化ニ
ッケルをヒドラジンで還元する際の両者の混合比は化学
当量で水酸化ニッケル：ヒドラジン＝１：９．５〜１
０．５であることが好ましく、１：９．７〜１０．３で
あることが更に好ましい。その混合比が１：９．５０よ
りも大きい（ヒドラジンの相対量が少ない）場合には、
還元反応に支障をきたし、１次粒子の粒度分布の幅が広
くなったりする傾向がある。逆にその混合比が１：１
０．５０より小さい場合には、反応が早く進み、１次粒
子の平均粒径が小さくなる上、増加するコストに見合っ
た効果が得られない傾向がある。Next, in the reduction reaction step, when the nickel hydroxide is reduced with hydrazine, the mixing ratio of the two is a chemical equivalent of nickel hydroxide: hydrazine = 1: 9.5-1.
It is preferably 0.5, more preferably 1: 9.7 to 10.3. When the mixing ratio is larger than 1: 9.50 (the relative amount of hydrazine is small),
The reduction reaction is hindered, and the size distribution of the primary particles tends to be wide. Conversely, the mixing ratio is 1: 1
When it is smaller than 0.50, the reaction proceeds rapidly, the average particle size of the primary particles becomes small, and the effect corresponding to the increased cost tends to be not obtained.
【００２５】又、水酸化ニッケル生成工程及び還元反応
工程での温度条件については、５５〜７０℃で実施する
ことが好ましく、５５〜６５℃で実施することが更に好
ましい。該温度が５５℃未満の場合には、各々の反応の
進行に支障をきたすため、目標とする１次粒子の平均粒
径が得られ難かったり、１次粒子の粒度分布の幅が広く
なったりする傾向がある。逆に、該温度が７０℃を超え
る場合には、増加するコストに見合った効果が得られな
い。The temperature conditions in the nickel hydroxide production step and the reduction reaction step are preferably carried out at 55 to 70 ° C., more preferably at 55 to 65 ° C. When the temperature is lower than 55 ° C., the progress of each reaction is hindered, so that it is difficult to obtain the target average particle size of the primary particles, or the width of the particle size distribution of the primary particles becomes wide. Tend to. Conversely, if the temperature exceeds 70 ° C., an effect corresponding to the increased cost cannot be obtained.
【００２６】以上に説明した本発明の製造方法によれ
ば、目的とする１次粒子の平均粒径が０．１〜０．９μ
ｍであり、この範囲内であれば１次粒子の平均粒径によ
らずＤ90値が２．１μｍ以下であり、且つタップ密度が
３．５ｇ／ｃｃ以上であるニッケル微粉末を得ることが
できる。このようなニッケル微粉末は積層セラミックコ
ンデンサの内部電極材料として用いるのに極めて好適で
ある。According to the production method of the present invention described above, the target primary particles have an average particle size of 0.1 to 0.9 μm.
a m, D 90 value regardless of the average particle size of the primary particles This range is less than or equal to 2.1 .mu.m, and the tap density is possible to obtain a nickel powder is 3.5 g / cc or more it can. Such nickel fine powder is extremely suitable for use as an internal electrode material of a multilayer ceramic capacitor.
【００２７】[0027]
【実施例】以下、実施例によって本発明を具体的に説明
するが、本発明はかかる事例に限定されるものではな
い。 実施例１ ＪＩＳ Ｋ １２０３で規定する液体かせいソーダ（Ｎ
ａＯＨ濃度４５重量％品）を純水で濃度２５重量％に希
釈した水溶液１７２８ｇに、ＪＩＳ Ｋ ８５７６で規
定する水酸化ナトリウム（ＮａＯＨ品位９７％）１０８
ｇを溶解して、１３．５ｍｏｌ／ｌの水溶液を調製し
た。The present invention will be described below in detail with reference to examples, but the present invention is not limited to such examples. Example 1 A liquid caustic soda (N) specified in JIS K 1203
sodium hydroxide (NaOH grade 97%) specified by JIS K 8576 was added to 1,728 g of an aqueous solution obtained by diluting an aOH concentration of 45% by weight) with pure water to a concentration of 25% by weight.
g was dissolved to prepare a 13.5 mol / l aqueous solution.
【００２８】硫酸ニッケル（ＮｉＳＯ4 ・６Ｈ2 Ｏ品位
２２．２重量％品）を純水に溶解して調製した１．７ｍ
ｏｌ／ｌの水溶液２．２７リットルを上記の水酸化ナト
リウム水溶液１リットルに、液温を６０℃に保持しなが
ら、５０分間にわたって連続的に添加して水酸化ニッケ
ルのスラリーを得た。該水酸化ニッケルスラリーに、液
温を６０℃に保持しながら、濃度２０ｍｏｌ／ｌの抱水
ヒドラジン０．９６リットルを一括添加し、撹拌してニ
ッケル微粒子を生成させた。得られたニッケル微粒子を
純水で充分に洗浄し、濾過した後、常法に従って乾燥・
篩分処理を行ってニッケル微粉末を得た。1.7 m prepared by dissolving nickel sulfate (NiSO 4 .6H 2 O grade 22.2% by weight) in pure water.
2.27 liters of an aqueous solution of ol / l were continuously added to 1 liter of the above-mentioned sodium hydroxide aqueous solution over a period of 50 minutes while maintaining the liquid temperature at 60 ° C. to obtain a nickel hydroxide slurry. While maintaining the liquid temperature at 60 ° C., 0.96 liter of hydrazine hydrate having a concentration of 20 mol / l was added to the nickel hydroxide slurry at a time, followed by stirring to produce nickel fine particles. The obtained nickel fine particles are sufficiently washed with pure water, filtered, dried and dried according to a conventional method.
A sieving treatment was performed to obtain a fine nickel powder.
【００２９】実施例２ ＪＩＳ Ｋ １２０３で規定する液体かせいソーダ（Ｎ
ａＯＨ濃度４５重量％品）を純水で濃度２５重量％に希
釈した水溶液１７２８ｇに、ＪＩＳ Ｋ ８５７６で規
定する水酸化ナトリウム（ＮａＯＨ品位９７％）７６ｇ
及びＪＩＳ Ｋ１２０２で規定する固形かせいソーダ
（ＮａＯＨ品位９６％）３２ｇを溶解して１３．５ｍｏ
ｌ／ｌの水溶液を調製し、その水酸化ナトリウム水溶液
１リットルを用いた以外は、実施例１と同様の条件でニ
ッケル微粉末を得た。Example 2 Liquid soda (N) specified in JIS K1203
(aOH concentration: 45% by weight) diluted with pure water to a concentration of 25% by weight to 1728 g of an aqueous solution, and 76 g of sodium hydroxide (NaOH grade: 97%) specified by JIS K 8576
And 32 g of solid caustic soda (NaOH grade 96%) specified in JIS K1202 and dissolved in 13.5 mo
A 1 / l aqueous solution was prepared and nickel fine powder was obtained under the same conditions as in Example 1 except that 1 liter of the aqueous sodium hydroxide solution was used.
【００３０】実施例３ ＪＩＳ Ｋ １２０３で規定する液体かせいソーダ（Ｎ
ａＯＨ濃度４５重量％品）を純水で濃度２５重量％に希
釈した水溶液１７２８ｇに、ＪＩＳ Ｋ １２０２で規
定する固形かせいソーダ（ＮａＯＨ品位９６％）１０８
ｇを溶解して１３．５ｍｏｌ／ｌの水溶液を調製し、そ
の水酸化ナトリウム水溶液１リットルを用いた以外は、
実施例１と同様の条件でニッケル微粉末を得た。Example 3 A liquid caustic soda (N) specified in JIS K1203
Aqueous solid soda (NaOH grade 96%) 108 specified in JIS K 1202 was added to 1,728 g of an aqueous solution obtained by diluting an aOH concentration of 45% by weight with pure water to a concentration of 25% by weight.
g was dissolved to prepare a 13.5 mol / l aqueous solution, and 1 liter of the aqueous sodium hydroxide solution was used.
Under the same conditions as in Example 1, nickel fine powder was obtained.
【００３１】比較例１ ＪＩＳ Ｋ １２０３で規定する液体かせいソーダ（Ｎ
ａＯＨ濃度４５重量％品）を純水で希釈して得た１３．
５ｍｏｌ／ｌの水溶液１リットルを用いた以外は、実施
例１と同様の条件でニッケル微粉末を得た。Comparative Example 1 Liquid soda (N) specified in JIS K 1203
(aOH concentration of 45% by weight) was diluted with pure water.
A nickel fine powder was obtained under the same conditions as in Example 1 except that 1 liter of a 5 mol / l aqueous solution was used.
【００３２】比較例２ ＪＩＳ Ｋ ８５７６で規定する水酸化ナトリウム（Ｎ
ａＯＨ品位９７％）を純水で希釈して得た１３．５ｍｏ
ｌ／ｌの水溶液１リットルを用いた以外は、実施例１と
同様の条件でニッケル微粉末を得た。Comparative Example 2 Sodium hydroxide (N) specified in JIS K 8576
aOH grade 97%) diluted with pure water to obtain 13.5mo
A nickel fine powder was obtained under the same conditions as in Example 1 except that 1 liter of a 1 / l aqueous solution was used.
【００３３】比較例３ ＪＩＳ Ｋ １２０２で規定する固形かせいソーダ（Ｎ
ａＯＨ品位９６％）を純水で希釈して得た１３．５ｍｏ
ｌ／ｌの水溶液１リットルを用いた以外は、実施例１と
同様の条件でニッケル微粉末を得た。Comparative Example 3 Solid soda (N) specified in JIS K1202
aOH grade 96%) diluted with pure water to obtain 13.5 mo
A nickel fine powder was obtained under the same conditions as in Example 1 except that 1 liter of a 1 / l aqueous solution was used.
【００３４】比較例４ ＪＩＳ Ｋ １２０３で規定する液体かせいソーダ（Ｎ
ａＯＨ濃度４５重量％品）を純水で濃度２５重量％に希
釈した水溶液１５１２ｇに、ＪＩＳ Ｋ ８５７６で規
定する水酸化ナトリウム（ＮａＯＨ品位９７％）１６２
ｇを溶解して、１３．５ｍｏｌ／ｌの水溶液を調製し、
その水酸化ナトリウム水溶液１リットルを用いた以外
は、実施例１と同様の条件でニッケル微粉末を得た。Comparative Example 4 Liquid soda (N) specified in JIS K 1203
sodium hydroxide (NaOH grade 97%) 162 specified in JIS K 8576 to 1512 g of an aqueous solution obtained by diluting an aOH concentration of 45% by weight) with pure water to a concentration of 25% by weight.
g to prepare a 13.5 mol / l aqueous solution,
A nickel fine powder was obtained under the same conditions as in Example 1 except that 1 liter of the aqueous sodium hydroxide solution was used.
【００３５】比較例５ ＪＩＳ Ｋ １２０３で規定する液体かせいソーダ（Ｎ
ａＯＨ濃度４５重量％品）を純水で濃度２５重量％に希
釈した水溶液１５１２ｇに、ＪＩＳ Ｋ １２０２で規
定する固形かせいソーダ（ＮａＯＨ品位９６％）１６２
ｇを溶解して１３．５ｍｏｌ／ｌの水溶液を調製し、そ
の水酸化ナトリウム水溶液１リットルを用いた以外は、
実施例１と同様の条件でニッケル微粉末を得た。Comparative Example 5 Liquid soda (N) specified in JIS K1203
Aqueous soda (NaOH grade 96%) 162 specified in JIS K 1202 was added to 1512 g of an aqueous solution obtained by diluting an aOH concentration of 45% by weight with pure water to a concentration of 25% by weight.
g was dissolved to prepare a 13.5 mol / l aqueous solution, and 1 liter of the aqueous sodium hydroxide solution was used.
Under the same conditions as in Example 1, nickel fine powder was obtained.
【００３６】比較例６ ＪＩＳ Ｋ １２０３で規定する液体かせいソーダ（Ｎ
ａＯＨ濃度４５重量％品）を純水で濃度２５重量％に希
釈した水溶液１９４４ｇに、ＪＩＳ Ｋ ８５７６で規
定する水酸化ナトリウム（ＮａＯＨ品位９７％）３８ｇ
及びＪＩＳ Ｋ１２０２で規定する固形かせいソーダ
（ＮａＯＨ品位９６％）１６ｇを溶解して１３．５ｍｏ
ｌ／ｌの水溶液を調製し、その水酸化ナトリウム水溶液
１リットルを用いた以外は、実施例１と同様の条件でニ
ッケル微粉末を得た。Comparative Example 6 Liquid caustic soda (N) specified in JIS K 1203
38 g of sodium hydroxide (NaOH grade 97%) specified by JIS K 8576 was added to 1944 g of an aqueous solution obtained by diluting an aOH concentration of 45% by weight) with pure water to a concentration of 25% by weight.
And 16 g of solid caustic soda (NaOH grade 96%) specified in JIS K1202 and dissolved in 13.5 mo
A 1 / l aqueous solution was prepared and nickel fine powder was obtained under the same conditions as in Example 1 except that 1 liter of the aqueous sodium hydroxide solution was used.
【００３７】ニッケル微粉末の特性値測定及びＳＥＭ写
真 上記の実施例１〜３及び比較例１〜６で得た各々のニッ
ケル微粉末について、電子顕微鏡写真によりフェレ径
（１次粒子の平均粒径）を求め、マイクロトラックによ
りＤ90値を求め、タップデンサーによるタップ密度を測
定した。その測定値は下記の表に示す通りであった。ま
た、実施例２で得たニッケル微粉末のＳＥＭ写真（倍率
８０００倍）は図１に示す通りであり、比較例５で得た
ニッケル微粉末のＳＥＭ写真（倍率８０００倍）は図２
に示す通りであった。Measurement of characteristic value of nickel fine powder and SEM photograph For each of the nickel fine powders obtained in Examples 1 to 3 and Comparative Examples 1 to 6, the Feret diameter (average particle diameter of primary particles) was determined by an electron micrograph. ) is obtained, obtains a D 90 value by Microtrac, was measured tap density by tap Denser. The measured values were as shown in the table below. The SEM photograph (8000 times magnification) of the nickel fine powder obtained in Example 2 is as shown in FIG. 1, and the SEM photograph (8000 times magnification) of the nickel fine powder obtained in Comparative Example 5 is shown in FIG.
As shown in FIG.
【００３８】 [0038]
【００３９】上記の表に示すデータからも明らかなよう
に、実施例１〜３で得た本発明のニッケル微粉末は、１
次粒子の平均粒径が０．２〜０．８μｍであり、Ｄ90値
が２．１μｍ以下であり、且つタップ密度が３．５ｇ／
ｃｃ以上であり、また、図１〜２のＳＥＭ写真からも明
らかなように、本発明のニッケル微粉末は低凝集で粒度
分布幅が狭い。一方、比較例１〜６で得たニッケル微粉
末は、Ｄ90値が２．１μｍを超えており、且つタップ密
度が３．５ｇ／ｃｃ未満である。As is clear from the data shown in the above table, the nickel fine powder of the present invention obtained in Examples 1 to 3 was 1
An average particle size of the next particle is 0.2 to 0.8 [mu] m, and a D 90 value of 2.1μm or less, and a tap density of 3.5 g /
cc or more, and as is clear from the SEM photographs of FIGS. 1 and 2, the nickel fine powder of the present invention has low aggregation and a narrow particle size distribution width. On the other hand, the nickel powder obtained in Comparative Examples 1 to 6, exceeds the D 90 value is 2.1 .mu.m, and a tap density of less than 3.5 g / cc.
【００４０】[0040]
【発明の効果】本発明の製造方法によって得られるニッ
ケル微粉末は、１次粒子の平均粒径が０．１〜０．９μ
ｍであり、Ｄ90値が２．１μｍ以下であり、且つタップ
密度が３．５ｇ／ｃｃ以上であり、即ち、低凝集で粒度
分布幅が狭く、且つ高タップ密度のニッケル微粉末であ
り、積層セラミックコンデンサの内部電極材料として用
いるのに極めて好適である。The nickel fine powder obtained by the production method of the present invention has an average primary particle diameter of 0.1 to 0.9 μm.
m, and not more than D 90 value is 2.1 .mu.m, and have a tap density of 3.5 g / cc or more, i.e., narrow particle size distribution width at a low aggregation, a and nickel fine powder of high tap density, It is extremely suitable for use as an internal electrode material of a multilayer ceramic capacitor.
【図１】 実施例２で得たニッケル微粉末のＳＥＭ写真
である。FIG. 1 is an SEM photograph of the nickel fine powder obtained in Example 2.
【図２】 比較例５で得たニッケル微粉末のＳＥＭ写真
である。FIG. 2 is an SEM photograph of the nickel fine powder obtained in Comparative Example 5.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ２２Ｃ 19/00 Ｃ２２Ｃ 1/04 Ｂ Ｈ０１Ｇ 4/12 ３６１ Ｑ // Ｂ２２Ｆ 5/00 Ｃ２２Ｂ 3/00 Ｔ Ｃ２２Ｃ 1/04 23/04 Ｂ２２Ｆ 5/00 Ｈ (56)参考文献 特開 平６−290985（ＪＰ，Ａ) 特開 平６−336601（ＪＰ，Ａ) 特公 昭41−4567（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.6，ＤＢ名) B22F 9/24 B22F 1/00 C22B 3/44 C22B 5/00 C22B 23/00 C22C 19/00 H01G 4/12 361 B22F 5/00 C22C 1/04 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification symbol FI C22C 19/00 C22C 1/04 B H01G 4/12 361 Q // B22F 5/00 C22B 3/00 T C22C 1/04 23 / 04 B22F 5/00 H (56) References JP-A-6-290985 (JP, A) JP-A-6-336601 (JP, A) JP-B-41-4567 (JP, B1) (58) Fields investigated (Int.Cl. 6 , DB name) B22F 9/24 B22F 1/00 C22B 3/44 C22B 5/00 C22B 23/00 C22C 19/00 H01G 4/12 361 B22F 5/00 C22C 1/04
Claims (8)
いソーダを水酸化ナトリウム水溶液中の全水酸化ナトリ
ウム分の７５〜８５重量％を占める量で含有し且つＪＩ
ＳＫ ８５７６で規定する水酸化ナトリウム及びＪＩＳ
Ｋ １２０２で規定する固形かせいソーダの一方又は
両方を合計で水酸化ナトリウム水溶液中の全水酸化ナト
リウム分の２５〜１５重量％を占める量で含有する水酸
化ナトリウム水溶液と、硫酸ニッケル水溶液とを混合し
て水酸化ニッケルを生成させ、次いで該水酸化ニッケル
をヒドラジンで還元し、生成ニッケルを回収することを
特徴とするニッケル微粉末の製造方法。1. A liquid caustic soda as defined by JIS K 1203 is contained in an amount occupying 75 to 85% by weight of the total sodium hydroxide in an aqueous sodium hydroxide solution.
Sodium hydroxide and JIS specified in SK 8576
A mixture of a sodium hydroxide aqueous solution containing one or both of solid soda specified in K1202 in an amount occupying 25 to 15% by weight of the total sodium hydroxide in the sodium hydroxide aqueous solution, and a nickel sulfate aqueous solution Producing nickel hydroxide, and then reducing the nickel hydroxide with hydrazine to recover the produced nickel.
いソーダを水酸化ナトリウム水溶液中の全水酸化ナトリ
ウム分の７５〜８５重量％を占める量で含有し且つＪＩ
ＳＫ ８５７６で規定する水酸化ナトリウムを水酸化ナ
トリウム水溶液中の全水酸化ナトリウム分の２５〜１５
重量％を占める量で含有する水酸化ナトリウム水溶液を
用いることを特徴とする請求項１記載の製造方法。2. A liquid caustic soda specified by JIS K 1203 in an amount occupying 75 to 85% by weight of the total sodium hydroxide in an aqueous sodium hydroxide solution and JIS
The sodium hydroxide specified in SK 8576 is converted to 25 to 15 of the total sodium hydroxide in the aqueous sodium hydroxide solution.
2. The method according to claim 1, wherein an aqueous sodium hydroxide solution is used in an amount occupying the weight%.
いソーダを水酸化ナトリウム水溶液中の全水酸化ナトリ
ウム分の７５〜８５重量％を占める量で含有し且つＪＩ
ＳＫ １２０２で規定する固形かせいソーダを水酸化ナ
トリウム水溶液中の全水酸化ナトリウム分の２５〜１５
重量％を占める量で含有する水酸化ナトリウム水溶液を
用いることを特徴とする請求項１記載の製造方法。3. A liquid caustic soda specified in JIS K 1203 in an amount occupying 75 to 85% by weight of the total sodium hydroxide in an aqueous sodium hydroxide solution, and JIS
The solid caustic soda specified in SK 1202 is converted to 25 to 15 of the total sodium hydroxide in the aqueous sodium hydroxide solution.
2. The method according to claim 1, wherein an aqueous sodium hydroxide solution is used in an amount occupying the weight%.
いソーダを水酸化ナトリウム水溶液中の全水酸化ナトリ
ウム分の７５〜８５重量％を占める量で含有し且つＪＩ
ＳＫ ８５７６で規定する水酸化ナトリウム及びＪＩＳ
Ｋ １２０２で規定する固形かせいソーダの両方を合
計で水酸化ナトリウム水溶液中の全水酸化ナトリウム分
の２５〜１５重量％を占める量で含有する水酸化ナトリ
ウム水溶液を用いることを特徴とする請求項１記載の製
造方法。4. A liquid caustic soda as defined by JIS K 1203 in an amount occupying 75 to 85% by weight of the total sodium hydroxide in an aqueous sodium hydroxide solution and JIS
Sodium hydroxide and JIS specified in SK 8576
An aqueous sodium hydroxide solution containing both the solid sodium hydroxide specified by K1202 in a total amount of 25 to 15% by weight of the total sodium hydroxide in the aqueous sodium hydroxide solution is used. The manufacturing method as described.
溶液とを混合する際の両者の混合比は化学当量で水酸化
ナトリウム：硫酸ニッケル＝１．６６〜１．８４：１で
あることを特徴とする請求項１〜４の何れかに記載の製
造方法。5. The mixing ratio of the aqueous sodium hydroxide solution and the aqueous nickel sulfate solution is a chemical equivalent of sodium hydroxide: nickel sulfate = 1.66 to 1.84: 1. The method according to claim 1.
溶液とを混合する際に、水酸化ナトリウム水溶液及び硫
酸ニッケル水溶液の一方を他方に徐々に添加することを
特徴とする請求項１〜５の何れかに記載の製造方法。6. The method according to claim 1, wherein when mixing the aqueous sodium hydroxide solution and the aqueous nickel sulfate solution, one of the aqueous sodium hydroxide solution and the aqueous nickel sulfate solution is gradually added to the other. The production method described in 1.
の両者の混合比は化学当量で水酸化ニッケル：ヒドラジ
ン＝１：９．５〜１０．５であることを特徴とする請求
項１〜６の何れかに記載の製造方法。7. The method according to claim 1, wherein the mixing ratio of nickel hydroxide and hydrazine in the reduction of hydrazine is a chemical equivalent of nickel hydroxide: hydrazine = 1: 9.5 to 10.5. The production method according to any one of the above.
であり、Ｄ90値が２．１μｍ以下であり且つタップ密度
が３．５ｇ／ｃｃ以上であるニッケル微粉末を製造する
ことを特徴とする請求項１〜７の何れかに記載の製造方
法。8. The primary particles have an average particle size of 0.1 to 0.9 μm.
, And the production method according to any one of claims 1 to 7, characterized in that and tap density D 90 value is not more than 2.1μm to produce a nickel powder is 3.5 g / cc or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10205878A JP2991700B2 (en) | 1997-09-11 | 1998-07-06 | Method for producing nickel fine powder |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9-247125 | 1997-09-11 | ||
| JP24712597 | 1997-09-11 | ||
| JP10205878A JP2991700B2 (en) | 1997-09-11 | 1998-07-06 | Method for producing nickel fine powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11152507A JPH11152507A (en) | 1999-06-08 |
| JP2991700B2 true JP2991700B2 (en) | 1999-12-20 |
Family
ID=26515309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10205878A Expired - Fee Related JP2991700B2 (en) | 1997-09-11 | 1998-07-06 | Method for producing nickel fine powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2991700B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1248814C (en) * | 1999-08-31 | 2006-04-05 | 东邦钛株式会社 | Nickel powder for monolithic ceramic capacitor |
| TW467780B (en) | 1999-11-10 | 2001-12-11 | Mitsui Mining & Smelting Co | Nickel powder, a production thereof and conductive paste |
| WO2001036131A1 (en) * | 1999-11-12 | 2001-05-25 | Mitsui Mining And Smelting Co., Ltd. | Nickel powder and conductive paste |
| JP3957444B2 (en) * | 1999-11-22 | 2007-08-15 | 三井金属鉱業株式会社 | Nickel powder, manufacturing method thereof, and paste for forming electronic component electrodes |
| CN1265921C (en) * | 2004-12-28 | 2006-07-26 | 成都开飞高能化学工业有限公司 | Wet manufacturing method for high vibrancy solid ultra micro sphere metal nickel powder |
| CN100391663C (en) * | 2006-04-10 | 2008-06-04 | 李小毛 | Process for preparing nano nickel powder |
| JP2007197836A (en) * | 2007-03-06 | 2007-08-09 | Mitsui Mining & Smelting Co Ltd | Nickel powder |
| KR101044726B1 (en) * | 2009-01-06 | 2011-06-28 | 충남대학교산학협력단 | A method for producing ultrafine nickel powder by chemical reduction |
| JP5063624B2 (en) * | 2009-02-12 | 2012-10-31 | 株式会社ノリタケカンパニーリミテド | Method for producing nickel fine particles |
-
1998
- 1998-07-06 JP JP10205878A patent/JP2991700B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11152507A (en) | 1999-06-08 |
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