JPS6280206A - Production of nickel powder - Google Patents
Production of nickel powderInfo
- Publication number
- JPS6280206A JPS6280206A JP22104385A JP22104385A JPS6280206A JP S6280206 A JPS6280206 A JP S6280206A JP 22104385 A JP22104385 A JP 22104385A JP 22104385 A JP22104385 A JP 22104385A JP S6280206 A JPS6280206 A JP S6280206A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- nickel
- liquid
- solution
- heat treatment
- 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.)
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Links
Abstract
Description
【発明の詳細な説明】
（産業上の利用分ｅ）
この発明は、酸化性雰囲気で焼付けｏＪ′能なニッケル
ペーストに含有されるニッケル粉末の製造方法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application e) The present invention relates to a method for producing nickel powder contained in a nickel paste that can be baked in an oxidizing atmosphere.
（従来の技術）
近年、厚膜焼付は用の導電材料とし′〔、ム９゜ム９−
Ｐｉ、 Ｐ（１などの貴金属を用いる代わシに・安価な
Ｎｉ、Ｃｕ、Ｚｎなどの卑金属系の導電材料が出現しＣ
いるっ
この中で、酸化性雰囲気で焼付は可能なニッケルペース
トドし〔、ニッケル（Ｎｉ）−［１（Ｂ）系。(Prior art) In recent years, thick film baking has been used as a conductive material for
Instead of using noble metals such as Pi and P(1), inexpensive conductive materials based on base metals such as Ni, Cu, and Zn have appeared.
Nickel paste [, nickel (Ni)-[1(B) system] which can be baked in an oxidizing atmosphere in a vacuum cleaner.
ものが知られＣいる。たとえば、ニッケルと５ｉｌｌ素
との混合粉末を含むペーストは特公昭６０−１６０４１
号公報に開示されＣいる。また、（Ｈｉ＊Ｂ）ａ（Ｎｉ
、８１）ｂの粉末をビヒクルに分散させたペーストはり
、Ｂ、Ｐ ３．９４３．１６８に開示されＣ込る。Something is known. For example, a paste containing a mixed powder of nickel and 5ill element is
It is disclosed in the publication No. C. Also, (Hi*B)a(Ni
, 81) b), disclosed in P 3.943.168 and included in C.
（発明が解決しようとする問題）
上記した各ニッケルペーストのうち、前者のものは、酸
化性４囲気での焼付は時におけるニッケルの酸化防止が
硼素の粒径や混合量に大きく左右されると（＾う欠点が
見られる。また硼素粉末は硼素化合物や硼素酸化物と比
較し′〔かなシ高価であシ、シかも硬度が高く、ロール
ミルでニッケル粉末と混練すると、ロールミルの表面を
傷つけやすいという難点がある。(Problem to be Solved by the Invention) Among the above-mentioned nickel pastes, the former has the effect that the prevention of nickel oxidation during baking in an oxidizing atmosphere is greatly affected by the particle size and amount of boron mixed. Also, compared to boron compounds and boron oxides, boron powder is expensive and hard, and when kneaded with nickel powder in a roll mill, it tends to damage the surface of the roll mill. There is a drawback.
また、後者のものは、酸化に対し”Ｃ非常に安定である
が、原料であるＮ工、Ｂ、 Ｎｉ３Ｓｉを不活性雰囲気
中で溶融混合し、そののちインゴットを粉砕し′〔粉末
を得るこいう工程を経るものであるため、粉砕工程が必
要となシ、得られるニッケルー硼素系粉末のコストアッ
プの要因となるものであった。The latter is very stable against oxidation, but it is difficult to obtain powder by melting and mixing the raw materials N, B, and Ni3Si in an inert atmosphere, and then crushing the ingot. This process requires a pulverization process, which increases the cost of the resulting nickel-boron powder.
（発明の目的）
したがつＣ１この発明は液相反応によりＮｉ、 Ｂの結
晶構造を有するニッケル粉末を容易に得られる製造方法
を提供することを目的とする。(Objective of the Invention) Therefore, the object of the present invention is to provide a manufacturing method that can easily obtain a nickel powder having a crystal structure of Ni and B by a liquid phase reaction.
（発明の構成）
つまシ、この発明の要旨とするところは、ニッケル塩の
溶液を水素化硼化物の還元液にて液相還元し、該還元工
程で得られたｎｌ−Ｂ共沈粉末を熱処理することにより
、Ｎｉ、Ｂかうなるニッケル粉末を尋ることを特徴とす
るニッケル粉末の製造方法である。(Structure of the Invention) The gist of this invention is to reduce a nickel salt solution in a liquid phase using a boron hydride reducing solution, and to reduce the nl-B coprecipitated powder obtained in the reduction process. This is a method for producing nickel powder, which is characterized in that nickel powder containing Ni and B is obtained by heat treatment.
上記した工程に訃い°（ニッケル塩の溶液とし°Ｃは、
たとえば硫酸ニッケル、硝酸ニッケル、塩化ニッケルを
純水に溶解したものなど（以後、第１液という）がある
。実際には、たとえばピロリン酸ナトリウムとアンモニ
ア水を純水に溶解したものなど（以後、第２液という）
と第１液と混合し、ニッケルの錯塩としたものを用いる
。Due to the above process (as a solution of nickel salt, °C is
For example, there are solutions in which nickel sulfate, nickel nitrate, and nickel chloride are dissolved in pure water (hereinafter referred to as the first solution). In reality, for example, sodium pyrophosphate and aqueous ammonia are dissolved in pure water (hereinafter referred to as the second solution).
and the first liquid to form a nickel complex salt.
また、水素化硼化物からなる還元液とし′Ｃは、たとえ
ば水素化硼素ナトリウム、水気化１１ｆｉカリウム、水
素化硼素リチウムなどを水酸化ナトリウム、水酸化カリ
ウムなどを純水に溶解した溶液に溶かしたもの（以後、
第３液という）がある。In addition, the reducing liquid consisting of boron hydride 'C' is obtained by dissolving, for example, sodium borohydride, vaporized potassium 11fi, lithium borohydride, etc. in a solution of sodium hydroxide, potassium hydroxide, etc. dissolved in pure water. things (hereafter,
There is a third liquid).
（作用）
まず、第１液と第２液を混合し−Ｃニッケルの錯塩を準
備する。このニッケルの錯塩を加温しＣおき１．＄３液
を分岐ロートやマイクロチューブボングを用い′Ｃ徐々
に滴下する。このとき第３液が還元剤の役割を果たし、
Ｎｉ−Ｂの共沈粉末の沈＃！物が得られることになる。(Operation) First, the first liquid and the second liquid are mixed to prepare a -C nickel complex salt. This nickel complex salt was heated to a temperature of 1. Gradually drip the $3 solution using a branched funnel or microtube bong. At this time, the third liquid plays the role of a reducing agent,
Precipitation # of Ni-B co-precipitated powder! You will get something.
この沈Ｒ物は洗浄、濾過され（Ｍｉ−Ｂの共沈粉末とし
゛〔得られる。This precipitate is washed and filtered to obtain a coprecipitated powder of Mi-B.
得られたＮｉ−Ｂ共沈粉末は酸化性雰囲気または不活性
雰囲気で熱処理される。この熱処理によシＮｉ−Ｂ共沈
粉末はＮｉ３Ｂの結晶構造からなる粉末が得られること
になる。ここで、前者、つまシネ活性雰囲気での熱処理
による場合、５５０〜９００℃、望ましくは５８０〜７
００Ｃの温度で熱処理する。これは５５０ｃ未満での熱
処理では十分な熱処理が行われず、Ｎｉ、Ｂの結晶構造
で有する粉末が得られなくなるからであり、一方％９０
０Ｃを越えるとｊＪ ｉ Ｏが生じることになり、比抵
抗の高ｈニッケル粉末が得られるからである。また、後
者つまシネ活性雰囲気での熱処理による場合、３００〜
１０００ｃ、望ましくは３００〜８００Ｃの温度で熱処
理する。不活性雰囲気での熱処理は酸化性雰囲気での熱
処理と異なり％ ３０ｏｒからＮｉ、Ｂの結晶構造か：
らなＬ粉末が得られる。一方熱処理温度の上昇に伴Ｌｒ
ｈ比抵抗が上昇するため、比抵抗の上昇を抑制するため
の温度は１０００ｃが限度である。The obtained Ni-B co-precipitated powder is heat treated in an oxidizing atmosphere or an inert atmosphere. Through this heat treatment, a Ni--B co-precipitated powder having a crystal structure of Ni3B is obtained. Here, in the case of the former, when heat treatment is performed in an active atmosphere, the temperature is 550 to 900°C, preferably 580 to 7°C.
Heat treatment at a temperature of 00C. This is because heat treatment at less than 550c does not provide sufficient heat treatment and powder having a crystal structure of Ni and B cannot be obtained.
This is because if the temperature exceeds 0C, jJ i O will be generated, and a high-h nickel powder with specific resistance will be obtained. In addition, when the latter is heat treated in an active atmosphere, 300~
Heat treatment is carried out at a temperature of 1000C, preferably 300-800C. Heat treatment in an inert atmosphere differs from heat treatment in an oxidizing atmosphere because the crystal structure of Ni and B changes from 30or:
A fine L powder is obtained. On the other hand, as the heat treatment temperature increases, Lr
h Since the specific resistance increases, the temperature for suppressing the increase in specific resistance is limited to 1000C.
このようにし′Ｃ得られたＮｉ、Ｂの粉末は粒径が０．
２μ〜１．５μｍの範囲のものである。Ｎｉ、Ｂ粉末は
ガラス７リツト、有機質ビヒクルとともに混練され゛Ｃ
ペースト状とされ、アルミナ、シルコニ乙コージェライ
トのセラミック基板あるｂは板物コンデンサ、積層コン
デンサに塗布、印刷などの手段で付与され、酸化性雰囲
気で焼付けられることにより、導電体とし〔の役割分乗
たす。使用されるガラス７リツトとしＣはホウケイ酸系
のものが用いられる。また有機質ビヒクルとしＣは、た
とエバエチルセルロースをテルヒネオール、エステル類
、アルコール類、アセトラなどで希釈したものが用いら
れる。The Ni and B powders obtained in this way have a particle size of 0.
It is in the range of 2 μm to 1.5 μm. Ni and B powders were kneaded with 7 liters of glass and an organic vehicle.
It is made into a paste and is applied to plate capacitors and multilayer capacitors by means such as coating or printing, and is baked in an oxidizing atmosphere to transform it into a conductor. Tasu. The glass used is 7 liters, and C is a borosilicate type glass. Further, as the organic vehicle C, a diluted ethyl cellulose with tercineol, esters, alcohols, acetra, etc. is used.
この発明にかかるニッケルθ末の製造方法の好ましい実
施、態様とし′〔は次のようなものがある。Preferred implementations and embodiments of the method for producing nickel θ powder according to the present invention are as follows.
■ ニッケル塩の溶液を水素化硼化物の還元液にて液相
還元するに際し、水素化硼化物の還元液のアルカリ濃度
を１別却することにより、還元工程か得られるＮｉ−Ｂ
共沈粉末の粒径を制御するニッケル粉末の製造方法。■ When a solution of nickel salt is subjected to liquid-phase reduction with a reducing solution of boron hydride, the alkaline concentration of the reducing solution of boron hydride is reduced by 1 to reduce the Ni-B obtained from the reduction process.
A method for producing nickel powder that controls the particle size of coprecipitated powder.
■ ニッケル塩の溶液を水素化硼化物の還元液にて液相
還元するに際し、反応時における温度を制御することに
より、還元工程が得られるＮｉ−Ｂ共沈粉末の粒径を制
御するニッケル粉末の製造方法。■ Nickel powder that controls the particle size of the Ni-B co-precipitated powder obtained in the reduction process by controlling the temperature during the reaction when a nickel salt solution is reduced in a liquid phase using a boron hydride reducing solution. manufacturing method.
（りニッケル塩の溶液を水素化硼化物の還元液にて液相
還元するに際し、ニッケル塩の溶液に水素化硼化物の還
元液を／ＪＱえる速度を制御することにより、還元１穆
で得られるＮｉ−Ｂ共沈粉末の粒径を制御するニッケル
粉末の製造方法。(When performing liquid phase reduction of a nickel salt solution with a boron hydride reducing solution, by controlling the rate at which the boron hydride reducing solution is added to the nickel salt solution, it is possible to obtain A method for producing nickel powder that controls the particle size of Ni-B co-precipitated powder.
（効 果）
この発明によれば、ニッケル塩の溶液を水素化硼化物の
還元液にて液相還元し、得られた旧−Ｂ共沈粉末を熱処
理することにより、Ｎｉ、Ｂからなるニッケル粉末を得
るというものであシ、比較的容易な方法でＮｉ５Ｂの結
晶構造を有するニッケル粉末が得られるものである。(Effects) According to the present invention, a solution of nickel salt is reduced in a liquid phase with a reducing solution of boron hydride, and the obtained prior-B coprecipitated powder is heat-treated to reduce the amount of nickel made of Ni and B. It is a method to obtain a powder, and a nickel powder having a crystal structure of Ni5B can be obtained by a relatively easy method.
また、得られたＭＬ、Ｂ粉末は酸化に対しＣ安定であｆ
ｉ、７００を以下での酸化性雰囲気で熱処理を繰シ返し
′Ｃも酸化されない。通線Ｎｉは３５０Ｃから酸化され
るが、特に酸化の著し一４２０〜５５０Ｃでも、このＮ
ｉＪＢｆ！＆末は酸化されずに安定な状態にある。In addition, the obtained ML and B powders are stable against oxidation and f
The heat treatment was repeated in an oxidizing atmosphere at a temperature of 700° C. C was not oxidized. Conductive Ni is oxidized from 350C, but even at 420 to 550C, where the oxidation is particularly severe, this N
iJBf! The & end is not oxidized and is in a stable state.
さらに、０．２〜１．５μｍの範囲のニッケル粉末を得
ようとするにあたりＣ１還元剤のアルカリ濃度の操作で
粒径の制御ができるという利点を有し〔１ハる。Furthermore, when attempting to obtain nickel powder in the range of 0.2 to 1.5 μm, there is an advantage that the particle size can be controlled by controlling the alkali concentration of the C1 reducing agent.
（実施例） 以下、この発明を実施例に従つ′Ｃ詳細に説明する。(Example) Hereinafter, this invention will be explained in detail according to embodiments.
実施列１゜
１００ｇの硫酸ニッケルを純水５００ｍ１Ｋ溶解したも
のを第１液とした。Example 1: A first solution was prepared by dissolving 100 g of nickel sulfate in 500 ml of pure water.
また、５０９のピクリン酸ナトリウムと１４０ｍＪの２
８チアンモニア水を７００ ｍｔ’の純水に溶解しＣ第
２液とした。Also, 509 sodium picrate and 140 mJ of 2
8 Thiammonia water was dissolved in 700 mt' of pure water to prepare C second liquid.
さらに、１５９の水素化ｉ４素ナトリウムを、あらかじ
め１０９の水酸化ナトリウムを純水に溶解した溶・灰に
溶かしＣ第５液とした。Furthermore, 159 sodium hydride i4 was dissolved in a solution/ash prepared by dissolving sodium hydroxide 109 in pure water in advance to obtain a fifth liquid C.
久Ｉへで、第１液と第２液を混合し゛〔ニッケルの４４
を作り、５５〜６０Ｃの！度になるまで加温した。この
ときのｐＨは１０．５前麦で６りた。液温か５５〜６０
Ｃに達したとき第５液を分液ロートを用１へＣ第１液と
第２液の混合液に滴下した。反応液が背色から無色透明
になった時点で第５液の滴下を止めた。沈澱物を５０〜
ｂｏｃの温水で洗浄、−過し、１００Ｃ以下で加熱、乾
燥し、Ｎｉ−Ｂ共沈粉末ムを得た。このＮｉ−Ｂ共沈粉
末ムについＣＸ線回折を行い、その結果を第１図に示し
た。Mix the first and second liquids at
Make 55~60C! It was heated until it reached ℃. The pH at this time was 10.5 and 6 for Maemugi. Liquid temperature 55-60
When the liquid C was reached, the fifth liquid was dropped into the liquid mixture of the first liquid C and the second liquid using a separating funnel. The dropping of the fifth liquid was stopped when the reaction liquid changed from a dark color to colorless and transparent. 50~
The mixture was washed with BOC warm water, filtered, heated at 100C or less, and dried to obtain a Ni-B coprecipitated powder. This Ni--B co-precipitated powder was subjected to CX-ray diffraction, and the results are shown in FIG.
次いで、Ｎｉ−Ｂ共沈粉求人を酸化性雰囲気（空気中）
で６５０℃に加熱した石英管中に通しＣ急熱処理を行い
、Ｎｉ、Ｂの粉末Ｂを得た。Next, the Ni-B co-precipitated powder was placed in an oxidizing atmosphere (in air).
The powder was passed through a quartz tube heated to 650° C. and subjected to rapid heat treatment to obtain powder B of Ni and B.
また、Ｎｉ−Ｂ共沈粉末ムを窒素雰囲気の石英管中で６
５０′ｃまでの温度に徐々に加熱し、Ｎｉ、Ｈの粉末Ｃ
を得た。このＮｉ、Ｂの粉末Ｃについ゛（Ｘ線回折を行
い、その結果を第２図に示した。In addition, Ni-B co-precipitated powder was placed in a quartz tube in a nitrogen atmosphere for 6 hours.
By gradually heating to a temperature of up to 50'C, Ni and H powder C
I got it. This Ni, B powder C was subjected to X-ray diffraction, and the results are shown in FIG.
ここで、第１図のＮｉ−に３共沈粉末Ａ、ｌ！：第２図
のＮｉ、Ｈの粉末Ｂの各Ｘ線ｔｇＩ祈図を比較しＣ明ら
かなように、Ｎｉ−Ｂ共沈粉末を熱処理することによつ
゛（ＮｉｊＢ粉末が得られることが理解できる。Here, the three coprecipitated powders A, l! : Comparing the X-ray tgI diagrams of Ni and H powder B in Figure 2, it is clear that by heat-treating the Ni-B coprecipitated powder, NijB powder can be obtained. .
これら各粉末Ａ、ＢおよびＣについＣ１ペーストにする
ための成分である有機質ビヒクルとの濡れ性を向上させ
るためにまたとえばステアリン酸などの高級脂肪酸で表
面処理をしたつこののち第１表に示す割合でガラスフリ
ツｉとともに有機質ビヒクルに分散させ゛Ｃペースト状
とした。このペーストをステンレススクリーンを用ｈＣ
アルミナ基板の上に所定のパターンに印刷し、ベルト炉
で最高温度６００ｔ：％維持時間１０分の条件によシ空
気中で焼付けを行った。得られた導電パターンについ゛
Ｃ比抵抗を測定し、その結果を第１表に併せＣ示した。Each of these powders A, B, and C was surface-treated with a higher fatty acid such as stearic acid to improve wettability with an organic vehicle, which is a component for forming C1 paste, and the results are shown in Table 1. It was dispersed in an organic vehicle together with glass frit I to form a paste. Apply this paste using a stainless steel screen.
A predetermined pattern was printed on an alumina substrate and baked in air using a belt furnace at a maximum temperature of 600 t and a maintenance time of 10 minutes. The specific resistance of the obtained conductive pattern was measured, and the results are shown in Table 1.
なお、ガラスフリットには作業温度が５５０〜７９０″
Ｃのホウケイ酸鉛亜鉛系のものを用すた。In addition, the working temperature for glass frit is 550~790''.
A lead-zinc borosilicate type material of C was used.
また、有機質ビヒクルにはテルピネオールに１０慢のエ
チルセルロースを溶解させたものを用−た。The organic vehicle used was a solution of 100% ethyl cellulose in terpineol.
実験４１のＭｉ−Ｂ共沈粉末ムを用りたペーストはこの
粉末ムの吸油量が高いため、実験轟２．実験＆３と同じ
混合割合で調製することができなかった。また粉末ムは
経時変化が大きく、調合した３日後にゲル化した。実験
遥２．実験黒３は第１表から明らかなように、良好な導
電性を示す比抵抗が得られた。特に、窒素雰囲気で熱処
理した実験＆３のものは空気中で熱処理した実験Ａ２と
比較し〔よシ低い比抵抗を示し〔いる。The paste using the Mi-B co-precipitated powder in Experiment 41 had a high oil absorption capacity, so it was used in Experiment 2. It was not possible to prepare at the same mixing ratio as in Experiment &3. In addition, the powdered product changed significantly over time, and gelled three days after it was prepared. Experiment Haruka 2. As is clear from Table 1, Experimental Black 3 had a specific resistance showing good conductivity. In particular, Experiment &3, which was heat-treated in a nitrogen atmosphere, showed a much lower resistivity than Experiment A2, which was heat-treated in air.
実施例Ｚ
実施例１におい“Ｃ得られたＮｉ−Ｂ共沈粉末Ａについ
Ｃ１酸化性算囲気（空気中）での熱処理温度を変化させ
［Ｎｉ５Ｂｌ＆末を得た。熱処理の方法は実施例１でｌ
ｉｉ、Ｂ粉末Ｂを得たと同様に、各温度に加熱した石英
ｊ中に通しＣ急熱逃理を行い、ＮｉｊＢ粉末を得た。Example Z The heat treatment temperature of the Ni-B co-precipitated powder A obtained in Example 1 in C1 oxidizing atmosphere (in air) was varied to obtain Ni5Bl powder.The heat treatment method was the same as in Example 1. De l
ii. B In the same manner as in obtaining powder B, NijB powder was obtained by passing it through quartz j heated to various temperatures and performing rapid heat release.
各ＮｉＪＢ＃末を実施列１の実験）に２と同様にしＣペ
ースト状とし、七の後も同様にしＣ４ｔパタ〜−ンを作
成し、比抵抗を測定した。Each NiJB# powder was made into a C paste in the same manner as in Experiment 2 in Example 1, and a C4t pattern was prepared in the same manner after Example 7, and the specific resistance was measured.
第２表には１ｉｉ−Ｂ共沈粉末の熱処理温度と」ｊ定し
た各比抵抗を示した。Table 2 shows the specific resistance determined by the heat treatment temperature of the 1ii-B coprecipitated powder.
第２表においＣ１実験ムロ〜実験ム１１が面積抵抗に換
算し゛（１ｎ／口／ｍｉｄ以下の範囲に入るものである
。熱処理温度が５５０ｃ未満では十分な熱処理が行えず
、ｉｉｉ、Ｈの結晶構造にすることができない。一方、
９００ｒ：を越えると、ＮｉＯが生成されるため比抵抗
の上昇が認められる。したがり′〔、酸化性雰囲気の熱
処理温度は５５０Ｃ＝９．ＯＱｒ：、望ましくは５８０
〜７０（１’の温度範囲で選択すればよい。In Table 2, C1 Experiment Muro to Experiment M11 are converted into sheet resistance (are within the range of 1n/mouth/mid or less.If the heat treatment temperature is less than 550c, sufficient heat treatment cannot be performed, and iii. cannot be made into a structure.On the other hand,
When the temperature exceeds 900r, an increase in specific resistance is observed because NiO is generated. The heat treatment temperature in the oxidizing atmosphere is 550C=9. OQr:, preferably 580
It may be selected within the temperature range of ~70 (1').
実施例３゜
実施例１にお−〔得られたＮｉ−Ｂ共沈粉末Ａについ〔
、不活性雰囲気である窒素雰囲気での熱処理温度を変化
させ（ＮｉｊＢ粉末を得た。熱処理の方法は実施例１で
Ｎｉ、Ｂ粉末Ｃを得たと同様に、Ｎｉ−Ｂ共沈粉末ムを
窒素雰囲気の石英管中で各熱ｌ！５１１理温度にまで徐
々に加熱し、Ｎｉ、Ｂ粉末を得た各Ｎｉ５Ｂ粉末を実施
例１の実験＆３と同様にしＣペースト状とし、その後も
同様にしＣ４亀パターンを作成し、比抵抗を測定した。Example 3゜In Example 1-[About the obtained Ni-B co-precipitated powder A]
The heat treatment temperature was changed in an inert nitrogen atmosphere (NijB powder was obtained. The heat treatment method was the same as in Example 1 to obtain Ni, B powder C. Each Ni5B powder was heated gradually to a temperature of 1511 in a quartz tube in an atmosphere to obtain Ni and B powders, and was made into a C paste in the same manner as in Experiment &3 of Example 1. A turtle pattern was created and the specific resistance was measured.
第６表にはＮｉ−Ｂ共沈粉末の熱処理温度と測定した各
比抵抗を示した。Table 6 shows the heat treatment temperature of the Ni-B co-precipitated powder and the measured specific resistance.
不活性雰囲気での熱処理では徐々に加熱するため、酸化
性雰囲気での熱処理に異なシ、３００ｔ：からＮｉ５Ｂ
の結晶構造からなる粉末が得られる。Since heat treatment in an inert atmosphere involves gradual heating, heat treatment in an oxidizing atmosphere differs from 300t: to Ni5B.
A powder consisting of the crystal structure is obtained.
熱処理温度の上昇とともに比抵抗が上昇するが、多少の
酸素が含まれるため、ＮｉＯの存在量が多くなシその結
果比抵抗の上昇が見られる。The specific resistance increases as the heat treatment temperature increases, but since some oxygen is included, the amount of NiO present is large, and as a result, the specific resistance increases.
実施例４
実施例１におい〔、還元液である水素化硼化物としＣ１
１５ｇの水素化硼素ナトリウムを、あらかじめ１０９の
水酸化す） ＩＪウムを純水に溶解した溶液に溶かしＣ
第５液とし′Ｃ作成した。。Example 4 In Example 1 [C1
Dissolve 15g of sodium borohydride in a solution of IJium (109 hydroxide) dissolved in pure water.
The fifth solution was prepared as 'C'. .
この実施列では、水素化硼化物からなる還元液のアルカ
リ濃度を変えるため、水酸化ナトリウム（Ｎａ０Ｈ）の
量を変化させ、この還元工程で得られるＮｉ−Ｂ共沈粉
末の粒径に与える影響を調べた。In this example, in order to change the alkaline concentration of the reducing solution made of boron hydride, the amount of sodium hydroxide (NaOH) was changed, and the effect on the particle size of the Ni-B co-precipitated powder obtained in this reduction process was I looked into it.
第４表は水酸化ナトリウム量を変化させたときのタップ
密度とＮｉ−Ｂ共沈粉末の粒径を示したものである。Table 4 shows the tap density and the particle size of the Ni-B co-precipitated powder when the amount of sodium hydroxide was changed.
実験７１Ｌ２０は水素化硼素ナトリウム量ζよる還元反
応で反応速度を１ｌｊｎＬうる水酸化ナトリウム量の限
界で、水酸化す） ＩＪウムがこれより少ない盪になる
とＮｉ−Ｂの共沈粉末が得られず、Ｎｉ単独の沈澱が生
じる。また実験＆２７は水酸化す） リクム量が多く、
アルカリ過多となつ°（Ｎｉ（ＯＪ雪の白色沈澱を生じ
、Ｎｉ−Ｂ共沈粉末の生成ができなくなる。なお、実験
ム２２は実施例１における第３液に相当する０
第４表から明らかなように、アルカリ量を変化させるこ
とによｆｉ、１ｆｉ−Ｂ共沈粉末の粒径制御に有効であ
る。また、還元剤である水素化硼素化合物の櫨類によつ
〔アルカリ量の上限、下限があることを付記しＣおく。In Experiment 71L20, hydration is carried out at the limit of the amount of sodium hydroxide that increases the reaction rate by 1 ljnL in a reduction reaction based on the amount of sodium boron hydride.) If the amount of IJ is less than this, Ni-B coprecipitated powder cannot be obtained. , Ni alone precipitates. In addition, experiment & 27 is hydroxylated) The amount of recum is large,
Excessive alkali content causes a white precipitate (Ni (OJ) and makes it impossible to produce Ni-B co-precipitated powder. Experiment 22 corresponds to the third solution in Example 1. It is clear from Table 4. As shown, it is effective to control the particle size of fi, 1fi-B co-precipitated powder by changing the amount of alkali.Also, it is effective to control the particle size of fi, 1fi-B coprecipitated powder by changing the amount of alkali. , please note that there is a lower limit.
実施例５
この実施列では、ニッケル塩の溶ｆＬｔ−水素化硼化物
の還元液で液相還元する場合、反応時における＠度を制
御することにより、得られるＮｉ−Ｂ共沈粉末の粒径を
制御する例を明らかにしたものであろう
１００１Ｆの硫酸ニッケルを純水３００ｍ１に溶解した
ものを第」液とした。Example 5 In this example, when liquid-phase reduction is carried out using a reducing solution of nickel salt solution fLt-hydroboride, the particle size of the obtained Ni-B co-precipitated powder can be adjusted by controlling the degree of reaction during the reaction. The first liquid was prepared by dissolving 1001F nickel sulfate in 300 ml of pure water.
また、５０ｇのピロリン酸ナトリウムと１４０ｆｆ１４
の２８チアンモニア水を７００ｍＡ’の純水に溶解しＣ
第２液とした。Also, 50g of sodium pyrophosphate and 140ff14
Dissolve 28 thiammonia water in 700 mA' pure water and
This was used as the second liquid.
さらに、ｊ５ｆｌの水素化硼素ナトリウムを、あらかじ
め３０すの水酸化ナトリウムｅ！水５００ｍｇに溶解し
た溶液に溶かしＣ第３液とした。Furthermore, add 5 fl of sodium borohydride to 30 fl of sodium hydroxide in advance! It was dissolved in a solution of 500 mg of water to obtain a third solution.
次いで、第１液と第２液を混合しＣニッケルの錯塩を作
り、４０ｔ、５０ｔｌ’および６０ ”Ｃの温度条件に
それぞれ加温し、マイクロチューブポンプを用（＾Ｃ第
３液を徐々に滴下した。滴下速度は６５０〜３５０ｍｔ
ｌ／ムｒとしたつ反応液が青色から無色透明になった時
点で第３液の滴下を止めた。反応液を室温まで冷却し、
沈澱物を純水で洗浄、−過し１２０Ｃで乾燥し゛〔各Ｎ
ｉ−Ｂ共沈粉末を得た。Next, the first and second liquids were mixed to form a complex salt of C nickel, heated to 40t, 50tl' and 60''C, respectively, and using a microtube pump (the third liquid was gradually added to the mixture). The dropping speed was 650 to 350 mt.
The dropping of the third liquid was stopped when the reaction liquid changed from blue to colorless and transparent. Cool the reaction solution to room temperature,
The precipitate was washed with pure water, filtered and dried at 120C.
An i-B coprecipitated powder was obtained.
これら各１ｆ ｉ −Ｂ共沈粉末につＩＱ（、タップ密
度Ｎｉ−Ｂ共沈粉末の粒径を測定し、その結果を第５表
に示した。The IQ (and tap density) of each of these 1f i -B coprecipitated powders were measured, and the particle size of the Ni-B coprecipitated powders was measured, and the results are shown in Table 5.
上記した実施例では反応温度の下退値を４０Ｃとしたが
、これより低い！度では）ｒｉ−Ｂ共沈粉末は得られず
、Ｎｉ！とし・〔析出することが確認できた。In the above example, the reaction temperature drop value was set at 40C, but it is lower than this! ) ri-B co-precipitated powder was not obtained, and Ni! It was confirmed that the mixture was precipitated.
また、実験＆２８〜５０の各Ｎｉ−Ｂ共沈扮末につい〔
、走査型屈子顕４Ｌ境写真でその生成状態をそれぞれ第
６図〜第５図に示したつ
実施列に
の実施例では、ニッケル塩の溶液を水素化硼化物の還元
液で液相還元する場合、ニッケル塩の溶液に水素化硼化
物の還元液を加える速度を制御することにより、得られ
るＮｉ−Ｂ共沈粉末の粒径を制御する例を明らかにした
ものである。In addition, regarding each Ni-B coprecipitation powder of experiments &28 to 50 [
In the example shown in FIGS. 6 to 5, the formation state is shown in 4L scanning electron microscopy photographs, a solution of nickel salt is reduced in liquid phase with a reducing solution of boron hydride. In this case, an example is clarified in which the particle size of the obtained Ni-B co-precipitated powder is controlled by controlling the rate at which a boron hydride reducing solution is added to a nickel salt solution.
１５０９の流酸ニッケルを純水６００ｍｔ’に溶博した
ものを第１液とした。The first liquid was prepared by dissolving nickel fluoride No. 1509 in 600 mt' of pure water.
また、７５ｇのどロリン酸ナトリウムと２１０ｍ１の２
８％アンモニア水を１０１０５Ｏ’の純水に溶、弄しご
第２液とした。Also, 75 g of sodium phlophosphate and 210 ml of 2
8% ammonia water was dissolved in 10105 O' pure water and stirred to obtain a second solution.
さらに、２２．５ｆＦの水素化１ｄｌｌ！素ナトリウム
を、あらかじめ４５９の水酸化ナトリウムを純水７５０
ｍ１に８８！液に婆かし〔第６液とした。In addition, 1 dll hydrogenated at 22.5 fF! Add 459 parts of sodium hydroxide to 750 parts of pure water in advance.
88 on m1! Add the liquid to the liquid (set as the 6th liquid).
次かで、第１液と第２液を混合しごニッケルの錯塩を作
シ、５５〜６０Ｃに加温する。■温しＣ−る混合液を攪
拌しながら、第３液を３６０ ｍ１ｆｉｒ、１５０ｍ１
！／ｈｒ、 １０００ｍｔ！／ｈｒ％および６００ｍら
／ｋｌｒの各滴下速度で滴下した。反応液が背色から無
色透明になった時点で第５液の滴下を止めた。反応液を
室温にまで冷却し、沈澱物を純水で洗浄、−過し、１２
０Ｃで乾燥し〔各Ｎｉ−Ｂ共沈粉末を得たこれら各Ｎｉ
−Ｂ共沈粉末につい乙タップ密度Ｎｉ−Ｂ共沈粉末の粒
径を測定し、その結果を第６表に示した。Next, the first liquid and the second liquid are mixed to form a nickel complex salt, and heated to 55 to 60C. ■While stirring the heated C-mixture, add the third liquid to 360 ml, 150 ml
! /hr, 1000mt! /hr% and 600m/klr, respectively. The dropping of the fifth liquid was stopped when the reaction liquid changed from a dark color to colorless and transparent. The reaction solution was cooled to room temperature, and the precipitate was washed with pure water and filtered.
These Ni-B co-precipitated powders were dried at 0C.
-B coprecipitated powder - Tap density The particle size of the Ni-B coprecipitated powder was measured, and the results are shown in Table 6.
第６表
得られた実験＆６１〜３４の各ＩＪｉ−Ｂ 共沈粉末に
ついＣ１走査型電子顕微鏡写真でその生成状態をそれぞ
れ第６図〜第９図に示した。Table 6 The formation state of each of the IJi-B coprecipitated powders obtained in experiments &61 to 34 is shown in FIGS. 6 to 9 using C1 scanning electron micrographs, respectively.
第６図〜第９図から明らかなように、第３液の滴下速度
を制御することにより、得られる旧−Ｂ共沈粉末の結晶
粒径を制御できることが理解できるＯAs is clear from FIGS. 6 to 9, it can be seen that by controlling the dropping speed of the third liquid, the crystal grain size of the obtained former-B coprecipitated powder can be controlled.
第１図、第２図は実施列１にンい〔得られたＮ↓−Ｂ共
沈粉末のＸ線回折図である。
第６図〜第５図は実施列５におい〔得られたＮｉ−Ｂ共
沈粉末の走査ＥＬＫ子ｇ＠鏡写真である０第６図〜第９
図は実施例乙におい°Ｃ得られた５Ｊｉ−Ｂ共沈粉末の
走査型電子ａ微鏡写真である。FIGS. 1 and 2 are X-ray diffraction patterns of the N↓-B coprecipitated powder obtained in Example 1. Figures 6 to 5 are scanned ELK photographs of the obtained Ni-B co-precipitated powder in Example 5.
The figure is a scanning electron-a micrograph of the 5Ji-B coprecipitated powder obtained at °C in Example B.
Claims (6)
相還元し、該還元工程で得られたＮｉ−Ｂ共沈粉末を熱
処理することにより、Ｎｉ＿３Ｂからなるニッケル粉末
を得ることを特徴とするニッケル粉末の製造方法。(1) A nickel powder consisting of Ni_3B is obtained by reducing a nickel salt solution in a liquid phase with a boron hydride reducing solution and heat-treating the Ni-B coprecipitated powder obtained in the reduction process. Characteristic method for producing nickel powder.
℃望ましくは５８０〜７００℃の酸化性雰囲気で熱処理
する、特許請求の範囲第（１）項記載のニッケル粉末の
製造方法。(2) The heat treatment of the Ni-B co-precipitated powder is 550 to 900
The method for producing nickel powder according to claim 1, wherein the nickel powder is heat-treated in an oxidizing atmosphere at a temperature of preferably 580 to 700°C.
０℃、望ましくは３００〜８００℃の不活性雰囲気で熱
処理する、特許請求の範囲第（１）項記載のニッケル粉
末の製造方法。(3) The heat treatment of the Ni-B co-precipitated powder is 300 to 100
The method for producing nickel powder according to claim 1, wherein the nickel powder is heat-treated in an inert atmosphere at 0°C, preferably 300 to 800°C.
相還元するに際し、水素化硼化物の還元液のアルカリ濃
度を制御することにより、還元工程で得られるＮｉ−Ｂ
共沈粉末の粒径を制御する、特許請求の範囲第（１）項
記載のニッケル粉末の製造方法。(4) When a nickel salt solution is subjected to liquid phase reduction using a boron hydride reducing solution, by controlling the alkali concentration of the boron hydride reducing solution, the Ni-B obtained in the reduction process can be reduced.
The method for producing nickel powder according to claim (1), wherein the particle size of the coprecipitated powder is controlled.
相還元するに際し、反応時における温度を制御すること
により、還元工程で得られるＮｉ−Ｂ共沈粉末の粒径を
制御する、特許請求の範囲第（１）項記載のニッケル粉
末の製造方法。(5) When reducing a nickel salt solution in a liquid phase using a boron hydride reducing solution, the particle size of the Ni-B co-precipitated powder obtained in the reduction process is controlled by controlling the temperature during the reaction. , a method for producing nickel powder according to claim (1).
相還元するに際し、ニッケル塩の溶液に水素化硼化物の
還元液を加える速度を制御することにより、還元工程で
得られるＮｉ−Ｂ共沈粉末の粒径を制御する、特許請求
の範囲第（１）項記載のニッケル粉末の製造方法。(6) When a nickel salt solution is subjected to liquid phase reduction with a boron hydride reducing solution, by controlling the rate of adding the boron hydride reducing solution to the nickel salt solution, the Ni obtained in the reduction process can be reduced. -B The method for producing nickel powder according to claim (1), wherein the particle size of the co-precipitated powder is controlled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22104385A JPH0699143B2 (en) | 1985-10-02 | 1985-10-02 | Nickel powder manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22104385A JPH0699143B2 (en) | 1985-10-02 | 1985-10-02 | Nickel powder manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6280206A true JPS6280206A (en) | 1987-04-13 |
| JPH0699143B2 JPH0699143B2 (en) | 1994-12-07 |
Family
ID=16760593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22104385A Expired - Lifetime JPH0699143B2 (en) | 1985-10-02 | 1985-10-02 | Nickel powder manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0699143B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6585796B2 (en) | 2000-05-30 | 2003-07-01 | Murata Manufacturing Co., Ltd. | Metal powder, method for producing the same, conductive paste using the same, and monolithic ceramic electronic component |
| JP2003183703A (en) * | 2001-12-11 | 2003-07-03 | Murata Mfg Co Ltd | Production method for conductive powder, conductive powder, conductive paste, and laminated ceramic electronic part |
| JP2009013482A (en) * | 2007-07-06 | 2009-01-22 | Ist Corp | Nickel powder or nickel alloy powder, and production method therefor |
-
1985
- 1985-10-02 JP JP22104385A patent/JPH0699143B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6585796B2 (en) | 2000-05-30 | 2003-07-01 | Murata Manufacturing Co., Ltd. | Metal powder, method for producing the same, conductive paste using the same, and monolithic ceramic electronic component |
| JP2003183703A (en) * | 2001-12-11 | 2003-07-03 | Murata Mfg Co Ltd | Production method for conductive powder, conductive powder, conductive paste, and laminated ceramic electronic part |
| JP2009013482A (en) * | 2007-07-06 | 2009-01-22 | Ist Corp | Nickel powder or nickel alloy powder, and production method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0699143B2 (en) | 1994-12-07 |
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