JP2002294311A - Method for producing metal grain powder - Google Patents
Method for producing metal grain powderInfo
- Publication number
- JP2002294311A JP2002294311A JP2001096834A JP2001096834A JP2002294311A JP 2002294311 A JP2002294311 A JP 2002294311A JP 2001096834 A JP2001096834 A JP 2001096834A JP 2001096834 A JP2001096834 A JP 2001096834A JP 2002294311 A JP2002294311 A JP 2002294311A
- Authority
- JP
- Japan
- Prior art keywords
- particle powder
- nickel
- solution
- aqueous solution
- copper
- 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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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、微細で分散性に優れた
緻密で純度が高い球状金属粒子粉末を生産性よく得るこ
とができる金属粒子粉末の製造法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a metal particle powder capable of obtaining a fine, high-dispersion spherical metal particle powder having excellent dispersibility with high productivity.
【０００２】[0002]
【従来の技術】近年、各種電子機器の小型化、高性能化
及び軽量化に伴い、電子機器部品、例えば積層コンデン
サなどに対しても小型化、高容量化の要求が強まってい
る。2. Description of the Related Art In recent years, with the miniaturization, high performance, and light weight of various electronic devices, there has been an increasing demand for miniaturization and high capacitance of electronic device components such as multilayer capacitors.
【０００３】そして、前記積層コンデンサの主要部は、
複数の誘電体層と内部電極が交互に積層されたコンデン
サ本体と外部電極から構成されており、積層コンデンサ
の小型化及び高容量化を図るために、誘電体層と内部電
極を薄くして多層化する手法が知られている。The main part of the multilayer capacitor is as follows:
It consists of a capacitor body and external electrodes in which a plurality of dielectric layers and internal electrodes are alternately stacked.To reduce the size and increase the capacitance of the multilayer capacitor, the dielectric layers and internal electrodes are thinned to form a multilayer. There is a known technique.
【０００４】そして、前記積層コンデンサに供せられる
ニッケル粒子粉末や銅粒子粉末は、通常ペースト化して
用いられるため、薄く、均一な皮膜が形成できること、
デラミネーション（層間剥離現象）等の発生を抑制する
ために焼成時の収縮が小さいこと及び電気抵抗が小さい
こと等の理由から、凝集がなく分散性に優れ、しかも緻
密で純度が高いことが要求されている。[0004] Since the nickel particle powder and copper particle powder to be provided to the multilayer capacitor are usually used in the form of a paste, a thin and uniform film can be formed.
In order to suppress the occurrence of delamination (delamination phenomenon) and the like, it is required that there is no coagulation, excellent dispersibility, denseness and high purity due to small shrinkage during firing and low electrical resistance. Have been.
【０００５】また、従来の内部電極層は通常１〜２μｍ
程度であったため、これに用いられるニッケル粒子粉末
や銅粒子粉末の粒子サイズは、０．１〜１μｍ程度の粒
子サイズのものが用いられていたが、近時における積層
コンデンサの小型化及び高容量化の要求から、内部電極
の薄層化による積層コンデンサの多層化が進んでおり、
それに伴いニッケル粒子粉末や銅粒子粉末の粒子サイズ
の微粒子化が望まれている。Further, the conventional internal electrode layer usually has a thickness of 1-2 μm.
Therefore, the particle size of the nickel particle powder and the copper particle powder used for this was about 0.1 to 1 μm, but recently the miniaturization and high capacity of the multilayer capacitor have been used. Demand for the use of multilayer capacitors has been increasing by increasing the thickness of the internal electrodes.
Accordingly, it is desired to reduce the particle size of the nickel particle powder and the copper particle powder.
【０００６】上記のような特性を有する金属粒子粉末の
製造法としては、特開平５−１０５９２２号公報に開示
されている熱分解法又は特開平８−１７０１１２号公
報、特開平１１−８０８１８号公報及び特開平１１−２
３６６０７号公報に開示されている噴霧熱分解法が知ら
れている。[0006] As a method for producing the metal particle powder having the above-mentioned characteristics, the thermal decomposition method disclosed in JP-A-5-105922 or JP-A-8-170112 and JP-A-11-80818 are disclosed. And JP-A-11-2
A spray pyrolysis method disclosed in 36607 is known.
【０００７】[0007]
【発明が解決しようとする課題】前掲各公報記載の球状
ニッケル粒子粉末や球状銅粒子粉末を工業的に製造する
場合には、次のような問題点がある。The following problems arise when the spherical nickel particle powder and the spherical copper particle powder described in the above-mentioned publications are manufactured industrially.
【０００８】即ち、特開平５−１０５９２２号公報に
は、無水ギ酸ニッケルを非酸化性雰囲気下又は減圧下に
おいて１６０〜３００℃で熱分解して０．０５〜０．３
μｍのニッケル微粒子粉末を得る方法が記載されている
が、得られるニッケル粒子は真球状を呈しておらず、ま
た、原料中に含まれる不純物を含んでいるため、純度が
要求される用途においては不利となる。That is, Japanese Patent Application Laid-Open No. H05-105922 discloses that nickel formate anhydride is thermally decomposed at 160 to 300 ° C. in a non-oxidizing atmosphere or under reduced pressure to a temperature of 0.05 to 0.3.
Although a method of obtaining a nickel fine particle powder of μm is described, the obtained nickel particles do not exhibit a true spherical shape, and also contain impurities contained in the raw material, so that in applications where purity is required, Disadvantageous.
【０００９】また、特開平８−１７０１１２号公報に
は、噴霧熱分解を特定の加熱温度領域で行う方法が記載
されているが、特定の加熱温度領域におけるキャリアガ
スの流速などの滞留時間が考慮されておらず、粒径の揃
った緻密な球状ニッケル粒子粉末や球状銅粒子粉末を工
業的に得ることは困難である。Japanese Patent Application Laid-Open No. 8-170112 discloses a method in which spray pyrolysis is performed in a specific heating temperature range, but the residence time such as the flow rate of the carrier gas in the specific heating temperature range is taken into consideration. However, it is difficult to industrially obtain dense spherical nickel particle powder or spherical copper particle powder having a uniform particle diameter.
【００１０】また、特開平１１−８０８１８号公報記載
の噴霧熱分解法は、還元性ガスを１〜３５ｖｏｌ％（実
施例では１６．７ｖｏｌ％）含ませたキャリアガスを用
いているので、工業的に不利である。In the spray pyrolysis method described in Japanese Patent Application Laid-Open No. H11-80818, a carrier gas containing a reducing gas in an amount of 1 to 35 vol% (16.7 vol% in the embodiment) is used. Disadvantageous.
【００１１】また、特開平１１−２３６６０７号公報記
載の噴霧熱分解法では、添加剤としてアンモニア又は過
酸化水素溶液を用いて錯体化することにより、還元性ガ
スを用いることなく金属粒子粉末を製造しているが、錯
体を形成する必要があることから工業的とは言い難いも
のである。In the spray pyrolysis method described in JP-A-11-236607, a metal particle powder is produced without using a reducing gas by complexing with an ammonia or hydrogen peroxide solution as an additive. However, it is difficult to say that it is industrial because it is necessary to form a complex.
【００１２】また、特開平８−１７０１１２号公報、特
開平１１−８０８１８号公報及び特開平１１−２３６６
０７号公報には、噴霧熱分解における噴霧方法として、
二流体ノズルや超音波噴霧が記載されているが、各公報
の実施例に示されている通り、これらの方法で得られる
球状金属粒子粉末は、粒子サイズが０．６〜１．３μｍ
と大きいものである。そのため、粒子サイズの小さい金
属粒子粉末を得るためには原料溶液濃度を薄くする等の
製造条件を制御することが必要となるため生産性が悪
く、微細化にも限度がある。Also, JP-A-8-170112, JP-A-11-80818 and JP-A-11-2366.
No. 07 discloses a spray method in spray pyrolysis.
Although two-fluid nozzles and ultrasonic spraying are described, the spherical metal particles obtained by these methods have a particle size of 0.6 to 1.3 μm, as shown in the examples of each publication.
It is a big one. Therefore, in order to obtain a metal particle powder having a small particle size, it is necessary to control production conditions such as reducing the concentration of a raw material solution, so that productivity is poor and miniaturization is limited.
【００１３】なお、特開平３−１３１５６０号公報に
は、超伝導体を構成する各種金属粉体をそれぞれ噴霧熱
分解によって個々の金属酸化物粒子粉末を得た後、加熱
焼結して超伝導体を製造する方法が記載されているが、
銅化合物として酢酸銅（Ｃｕ（ＣＨ３ＣＯＯ）２）を用
いると共に酸素をキャリアガスとして用いて噴霧熱分解
法によって酸化銅（ＣｕＯ）を得ており、還元雰囲気下
で金属粒子粉末を得ることについては考慮されていな
い。Japanese Patent Application Laid-Open No. 3-131560 discloses that various metal powders constituting a superconductor are individually obtained by spray pyrolysis to obtain individual metal oxide particle powders, which are then sintered by heating and sintering. Although a method of manufacturing the body is described,
Copper oxide (CuO) is obtained by a spray pyrolysis method using copper acetate (Cu (CH 3 COO) 2 ) and oxygen as a carrier gas as a copper compound, and obtaining metal particle powder in a reducing atmosphere. Is not taken into account.
【００１４】そこで、本発明は、分散性に優れた緻密で
純度が高い球状金属粒子粉末を噴霧熱分解法によって生
産性よく製造することを技術的課題とする。Accordingly, it is a technical object of the present invention to produce dense and high-purity spherical metal particle powder having excellent dispersibility by spray pyrolysis with good productivity.
【００１５】[0015]
【課題を解決する為の手段】前記技術的課題は、次の通
りの本発明によって達成できる。The above technical object can be achieved by the present invention as described below.
【００１６】即ち、本発明は、酢酸ニッケル水溶液若し
くはギ酸ニッケル水溶液又は酢酸銅水溶液若しくはギ酸
銅水溶液を噴霧熱分解溶液として用いて噴霧熱分解法に
よって球状金属粒子粉末を得る金属粒子粉末の製造法に
おいて、前記噴霧熱分解溶液を減圧して噴霧することを
特徴とする金属粒子粉末の製造法である。That is, the present invention relates to a method for producing metal particle powder by a spray pyrolysis method using an aqueous nickel acetate solution or an aqueous nickel nickel solution or an aqueous copper acetate solution or an aqueous copper formate solution as a spray pyrolysis solution. And spraying the spray pyrolysis solution under reduced pressure.
【００１７】本発明の構成を詳述すれば、次の通りであ
る。The structure of the present invention will be described below in detail.
【００１８】本発明に用いる噴霧熱分解溶液は、酢酸ニ
ッケル水溶液若しくはギ酸ニッケル水溶液又は酢酸銅水
溶液若しくはギ酸銅水溶液であり、当該各水溶液を減圧
噴霧して噴霧熱分解を行うことにより、キャリアガス中
に含有させる還元性ガスの使用量を低減することができ
ると共に、目的とする球状金属粒子粉末を生産性よく得
ることができる。The spray pyrolysis solution used in the present invention is an aqueous solution of nickel acetate or nickel nickel formate, or an aqueous solution of copper acetate or copper formate. In addition to reducing the amount of reducing gas to be contained, the desired spherical metal particle powder can be obtained with high productivity.
【００１９】噴霧熱分解溶液の濃度は、目的とする金属
粒子粉末の粒子サイズとマイクロフィルターの細孔径に
応じて決めればよく、０．００１ｍｏｌ／ｌ以上が好ま
しく、より好ましくは０．００５ｍｏｌ／ｌ以上であ
る。０．００１ｍｏｌ／ｌ未満の場合には、得られる球
状金属粒子粉末の収量が低く、生産性が低下するため好
ましくない。得られる球状金属粒子粉末の粒度分布を考
慮すれば、噴霧熱分解溶液の濃度の上限値は好ましくは
０．５ｍｏｌ／ｌであり、より好ましくは０．４ｍｏｌ
／ｌである。The concentration of the spray pyrolysis solution may be determined according to the particle size of the target metal particles and the pore size of the microfilter, and is preferably 0.001 mol / l or more, more preferably 0.005 mol / l. That is all. If the amount is less than 0.001 mol / l, the yield of the obtained spherical metal particles is low, and the productivity is undesirably reduced. Considering the particle size distribution of the obtained spherical metal particles, the upper limit of the concentration of the spray pyrolysis solution is preferably 0.5 mol / l, more preferably 0.4 mol / l.
/ L.
【００２０】本発明における噴霧熱分解法では、噴霧熱
分解溶液を減圧雰囲気下、マイクロフィルターを通すこ
とによって噴霧する。マイクロフィルターの細孔径は、
目的とする金属粒子粉末の粒子径に応じて決めればよい
が、１〜１００μｍが好ましい。また、系内の圧力は、
常に一定になるようコントロールする必要があり、１．
３３〜９３．１ｋＰａの間が好ましい。In the spray pyrolysis method of the present invention, the spray pyrolysis solution is sprayed by passing through a microfilter under a reduced pressure atmosphere. The pore size of the microfilter is
It may be determined according to the particle size of the target metal particle powder, but it is preferably 1 to 100 μm. The pressure in the system is
It is necessary to control so that it is always constant.
It is preferably between 33 and 93.1 kPa.
【００２１】マイクロフィルターを通して噴霧した液滴
は、還元性ガスを含有するキャリアガスによって加熱炉
中に導入される。還元性ガスとしては水素ガス、ＣＯガ
ス、アンモニアガス等を用いることができるが、工業的
には水素ガスが好ましい。キャリアガスとしては不活性
ガスであれば特に限定されるものではないが、好ましく
は窒素である。The droplets sprayed through the microfilter are introduced into a heating furnace by a carrier gas containing a reducing gas. As the reducing gas, hydrogen gas, CO gas, ammonia gas and the like can be used, but hydrogen gas is preferable from an industrial viewpoint. The carrier gas is not particularly limited as long as it is an inert gas, but is preferably nitrogen.
【００２２】本発明においては酢酸塩水溶液又はギ酸塩
水溶液を用いるため、還元性ガスを少なくすることがで
きる。還元性ガスの濃度は１．０ｖｏｌ％未満が好まし
く、より好ましくは０．９ｖｏｌ％以下である。In the present invention, since an aqueous solution of acetate or aqueous solution of formate is used, the amount of reducing gas can be reduced. The concentration of the reducing gas is preferably less than 1.0 vol%, more preferably 0.9 vol% or less.
【００２３】キャリアガスの流速は１．０〜１０ｃｍ／
ｓｅｃが好ましい。The flow rate of the carrier gas is 1.0 to 10 cm /
sec is preferred.
【００２４】加熱炉は、５段以上設けることが好まし
く、３段目以降で最高温度に達するように温度勾配を持
たせることが好ましい。１段目から高温で加熱した場合
には、急激な反応が生じるため緻密な球状金属粒子粉末
を得ることが困難となる。The heating furnace is preferably provided in five or more stages, and preferably has a temperature gradient so as to reach the maximum temperature in the third and subsequent stages. When heating at a high temperature from the first stage, a rapid reaction occurs, so that it is difficult to obtain dense spherical metal particle powder.
【００２５】加熱炉の温度は、具体的には１段目が２０
０〜４００℃であり、２段目が４５０〜６５０℃、３段
目以降が７５０〜１０００℃とすることが好ましい。The temperature of the heating furnace is, specifically, 20 at the first stage.
The temperature is preferably from 0 to 400 ° C, the second stage is preferably from 450 to 650 ° C, and the third and subsequent stages preferably from 750 to 1000 ° C.
【００２６】また、加熱炉の１段の長さＬと炉芯管の直
径Ｄの比Ｌ／Ｄは５以上であることが好ましい。Ｌ／Ｄ
が５未満の場合には、１つの加熱炉に滞留する時間が短
くなるため得られる球状金属粒子粉末の粒度分布が悪く
なる。工業的な生産性を考慮した場合、Ｌ／Ｄの上限値
は５０である。The ratio L / D of the length L of one stage of the heating furnace to the diameter D of the furnace core tube is preferably 5 or more. L / D
Is less than 5, the residence time in one heating furnace is shortened, so that the particle size distribution of the obtained spherical metal particle powder deteriorates. In consideration of industrial productivity, the upper limit of L / D is 50.
【００２７】熱分解が終了した金属粒子粉末は、常法に
従い、バグフィルター、電気集じん機などによって集め
る。The thermally decomposed metal particle powder is collected by a bag filter, an electric precipitator or the like according to a conventional method.
【００２８】本発明によって得られるニッケル粒子粉末
は、球状を呈しており、平均粒子径が０．００１〜０．
１μｍであり（必要に応じて０．００５〜０．０８μｍ
にできる）、幾何標準偏差値が２．０以下であり（必要
に応じて１．８以下にできる）、ＢＥＴ比表面積値が１
〜１００ｍ２／ｇであり（必要に応じて１．５〜８０ｍ
２／ｇにできる）、密度比が０．７５〜１．０であり
（必要に応じて０．８〜１．０にできる）、体積固有抵
抗値が１．０〜９．５×１０３Ω・ｃｍ（必要に応じて
１．０〜５．０×１０３Ω・ｃｍにできる）である。ま
た、結晶性は４０００以上である。The nickel particle powder obtained by the present invention has a spherical shape and an average particle diameter of 0.001 to 0.5.
1 μm (0.005 to 0.08 μm if necessary
), The geometric standard deviation value is 2.0 or less (it can be 1.8 or less if necessary), and the BET specific surface area value is 1
１００100 m 2 / g (1.5 to 80 m if necessary)
2 / g), the density ratio is 0.75 to 1.0 (can be 0.8 to 1.0 if necessary), and the volume resistivity is 1.0 to 9.5 × 10 3. Ω · cm (can be set to 1.0 to 5.0 × 10 3 Ω · cm if necessary). The crystallinity is 4000 or more.
【００２９】本発明によって得られる銅粒子粉末は、球
状を呈し、平均粒子径が０．００１〜０．１μｍであり
（必要に応じて０．００５〜０．０８μｍにできる）、
幾何標準偏差値が２．０以下（必要に応じて１．８以下
にできる）、ＢＥＴ比表面積値が１〜１００ｍ２／ｇで
あり（必要に応じて１．５〜８０ｍ２／ｇにできる）、
密度比が０．７５〜１．０であり（必要に応じて０．８
〜１．０にできる）、体積固有抵抗値が１．０〜９．５
×１０３Ω・ｃｍ（必要に応じて１．０〜５．０×１０
３Ω・ｃｍにできる）である。また、結晶性は４０００
以上である。The copper particle powder obtained by the present invention has a spherical shape, an average particle diameter of 0.001 to 0.1 μm (can be 0.005 to 0.08 μm if necessary),
The geometric standard deviation value is 2.0 or less (can be 1.8 or less if necessary), and the BET specific surface area value is 1 to 100 m 2 / g (if necessary, it can be 1.5 to 80 m 2 / g). ),
The density ratio is 0.75 to 1.0 (0.8 if necessary)
To 1.0), and the volume resistivity is 1.0 to 9.5.
× 10 3 Ω · cm (1.0 to 5.0 × 10 if necessary
3 Ω · cm). The crystallinity is 4000
That is all.
【００３０】[0030]
【発明の実施の形態】本発明の代表的な実施の形態は、
次の通りである。DESCRIPTION OF THE PREFERRED EMBODIMENTS A typical embodiment of the present invention is as follows.
It is as follows.
【００３１】粒子粉末の平均粒子径は、電子顕微鏡写真
を縦方向及び横方向にそれぞれ４倍に拡大した写真に示
される粒子約３５０個について、粒子径を測定し、その
平均値で示した。The average particle diameter of the particle powder was obtained by measuring the particle diameter of about 350 particles shown in a photograph obtained by enlarging the electron micrograph four times in the vertical and horizontal directions, and indicating the average value.
【００３２】粒子粉末の粒子径の幾何標準偏差値は次の
方法により求めた値で示した。即ち、前記拡大写真に示
される粒子の粒子径を測定した値を、その測定値から計
算して求めた粒子の実際の粒子径と個数から、統計学的
手法に従って、対数正規確率紙上の横軸に粒子径を、縦
軸に所定の粒子径区間のそれぞれに属する粒子の累積個
数（積算フルイ下）を百分率でプロットした。そしてこ
のグラフから粒子の累積個数が５０％及び８４．１３％
のそれぞれに相当する粒子径の値を読み取り、幾何標準
偏差値＝（積算フルイ下８４．１３％における粒子径）
／（積算フルイ下５０％における粒子径（幾何平均
径））に従って算出した値で示した。幾何標準偏差値が
１に近いほど、粒子の粒子径の粒度が優れていることを
意味する。The geometric standard deviation of the particle diameter of the particle powder was shown by the value obtained by the following method. In other words, the value obtained by measuring the particle diameter of the particles shown in the enlarged photograph, the actual particle diameter and the number of particles calculated from the measured values, according to a statistical method, the horizontal axis on the lognormal probability paper , And the vertical axis plots the cumulative number of particles belonging to each of the predetermined particle diameter sections (under the integrated screen) in percentage. From this graph, the cumulative number of particles is 50% and 84.13%.
Is read, and the geometric standard deviation value = (particle size at 84.13% under the integrated screen)
/ (Particle diameter (geometric mean diameter) at 50% under the integrated screen). The closer the geometric standard deviation value is to 1, the better the particle size of the particles is.
【００３３】比表面積値はＢＥＴ法により測定した値で
示した。The specific surface area was indicated by a value measured by the BET method.
【００３４】粉体の密度比は、「マルチボリューム 密
度計 １３０５型」（マイクロメリティクス社製）を用
いて各粉体の密度を測定し、各金属粉体の真密度（Ｎｉ
＝８．８４５ｇ／ｃｍ３、Ｃｕ＝８．９２ｇ／ｃｍ３）
との比によって求めた。The density ratio of the powder is determined by measuring the density of each powder using a “multi-volume densitometer 1305 type” (manufactured by Micromeritics) and determining the true density (Ni
= 8.845 g / cm 3 , Cu = 8.92 g / cm 3 )
And the ratio was determined.
【００３５】金属粒子粉末の結晶性は、「Ｘ線回折装置
ＲＡＤ−ＩＩＡ」（理学電機工業株式会社製）（管
球：Ｆｅ）を使用し、２θが３〜１０５°の範囲で測定
し、得られた最強線のピーク強度で示した。The crystallinity of the metal particle powder was measured using an “X-ray diffractometer RAD-IIA” (manufactured by Rigaku Denki Kogyo Co., Ltd.) (tube: Fe) in a range of 2θ of 3 to 105 °. The peak intensity of the obtained strongest line was shown.
【００３６】金属粒子粉末の体積固有抵抗値は、先ず、
試料粒子粉末０．５ｇを秤り取り、ＫＢｒ錠剤成形器
（株式会社島津製作所製）を用いて、１．３７２×１０
７Ｐａ（１４０Ｋｇ／ｃｍ２）の圧力で加圧成形を行
い、円柱状の被測定試料を作製した。First, the volume resistivity value of the metal particle powder is as follows:
0.5 g of the sample particle powder was weighed out, and using a KBr tablet press (manufactured by Shimadzu Corporation), 1.372 × 10
Pressure molding was performed at a pressure of 7 Pa (140 kg / cm 2 ) to produce a cylindrical sample to be measured.
【００３７】次に、被測定試料（円柱状）を２５℃、相
対湿度６０％の環境下に１２時間以上曝露した後、この
被測定試料をステンレス電極の間にセットし、ホイート
ストンブリッジ（ＴＹＰＥ２７６８、横河北辰電機株式
会社製）で１５Ｖの電圧を印加して抵抗値Ｒ（Ω）を測
定する。Next, after the sample to be measured (columnar shape) was exposed to an environment of 25 ° C. and a relative humidity of 60% for 12 hours or more, the sample to be measured was set between stainless steel electrodes, and a Wheatstone bridge (TYPE 2768, A voltage of 15 V is applied by Yokogawa Hokushin Electric Co., Ltd.) to measure the resistance value R (Ω).
【００３８】次に、被測定試料の上面の面積Ａ（ｃ
ｍ２）と厚みｔ０（ｃｍ）を測定し、数１にそれぞれの
測定値を代入して、体積固有抵抗値（Ω・ｃｍ）を求め
た。Next, the area A (c) of the upper surface of the sample to be measured
m 2 ) and thickness t 0 (cm) were measured, and the respective measured values were substituted into Equation 1 to determine a volume specific resistance value (Ω · cm).
【００３９】[0039]
【数１】 体積固有抵抗値（Ω・ｃｍ）＝Ｒ×（Ａ／ｔ０） 但し、Ｒは実測の抵抗値である。[Formula 1] Volume specific resistance (Ω · cm) = R × (A / t 0 ) where R is an actually measured resistance.
【００４０】＜球状金属粒子粉末の製造＞濃度が０．１
５ｍｏｌ／ｌのギ酸ニッケル水溶液を細孔径３．０μｍ
のマイクロフィルターを通して、系内圧力が６６．５ｋ
Ｐａの雰囲気下の加熱炉中に噴霧し、系内の圧力を６
６．５ｋＰａで一定に制御して水素ガスを０．５ｖｏｌ
％含有する窒素ガスをキャリアガスとして流速５．０ｃ
ｍ／ｓｅｃで系内に導入した。なお、用いた加熱炉のＬ
／Ｄは３０であった。<Production of spherical metal particle powder>
5 mol / l aqueous solution of nickel formate with a pore diameter of 3.0 μm
66.5k through the micro filter
Spray into a heating furnace in an atmosphere of Pa, and set the pressure in the system to 6
Control the hydrogen gas constant at 6.5 kPa and supply 0.5 vol of hydrogen gas.
% Nitrogen gas as a carrier gas at a flow rate of 5.0 c
It was introduced into the system at m / sec. In addition, L of the heating furnace used
/ D was 30.
【００４１】加熱炉の一段目から五段目までの加熱温度
をそれぞれ３００℃、６００℃、８００℃、８００℃、
８００℃とし、エアロゾル中の溶剤を徐々に蒸発させた
後、熱処理を行って、エアロゾル中で熱分解反応を生じ
させた。加熱炉出口にバグフィルターを設置して粒子を
捕集した。The heating temperature from the first stage to the fifth stage of the heating furnace is 300 ° C., 600 ° C., 800 ° C., 800 ° C., respectively.
After setting the temperature to 800 ° C. and gradually evaporating the solvent in the aerosol, a heat treatment was performed to cause a thermal decomposition reaction in the aerosol. A bag filter was installed at the heating furnace outlet to collect particles.
【００４２】得られたニッケル粒子粉末は球状を呈して
おり、平均粒子径が０．０２５μｍ、幾何標準偏差値が
１．４８、ＢＥＴ比表面積値が４１．２ｍ２／ｇ、密度
比が０．８０、体積固有抵抗値が４．１×１０２Ω・ｃ
ｍ、結晶性が８１００であった。得られた球状ニッケル
粒子粉末の電子顕微鏡観察の結果、ほぼ真球状粒子が得
られていることが確認できた。The obtained nickel particle powder has a spherical shape, an average particle size of 0.025 μm, a geometric standard deviation of 1.48, a BET specific surface area of 41.2 m 2 / g, and a density ratio of 0. 80, the volume resistivity is 4.1 × 10 2 Ω · c
m and crystallinity were 8100. As a result of electron microscopic observation of the obtained spherical nickel particle powder, it was confirmed that substantially spherical particles were obtained.
【００４３】[0043]
【作用】本発明において最も重要な点は、噴霧熱分解の
噴霧方法として減圧噴霧法を用いることにより、従来の
二流体ノズルや超音波噴霧方法では非常に生産性の悪か
った０．１μｍ以下の微細な球状金属粒子粉末を生産性
よく得ることができること及び酢酸ニッケル水溶液若し
くはギ酸ニッケル水溶液又は酢酸銅水溶液若しくはギ酸
銅水溶液を噴霧熱分解溶液として用いたことによって、
還元性ガスの使用量を低減でき、しかも、分散性に優れ
た緻密で純度が高い球状金属粒子粉末を得ることができ
るという事実である。The most important point in the present invention is that the use of a reduced pressure spraying method as a spraying method for spray pyrolysis makes it possible to reduce the productivity to 0.1 μm or less, which was extremely poor in the conventional two-fluid nozzle or ultrasonic spraying method. By being able to obtain fine spherical metal particle powder with good productivity and by using an aqueous solution of nickel acetate or an aqueous solution of nickel formate or an aqueous solution of copper acetate or copper formate as a spray pyrolysis solution,
This is a fact that the amount of the reducing gas used can be reduced, and moreover, a dense and high-purity spherical metal particle powder excellent in dispersibility can be obtained.
【００４４】減圧噴霧法を用いることによって０．１μ
ｍ以下の微細な球状金属粒子粉末を生産性よく得ること
が可能となった理由について、本発明者は、従来の超音
波噴霧法等では、噴霧する液滴の大きさをコントロール
することができないため、液滴に含まれる原料成分の濃
度を低く抑えることによって微細な球状金属粒子粉末を
生成しているため、単位時間当たりの収量を上げること
が困難であったが、本発明においては、マイクロフィル
ターの細孔径を選択し、系内の圧力を一定にコントロー
ルすることによって、０．００１〜０．１μｍの微細な
球状金属粒子粉末を得ることができるため、原料溶液の
濃度を低く抑える必要がなく、そのため、単位時間当た
りの収量を上げることができたものと考えている。By using the reduced pressure spray method, 0.1 μm
The present inventors cannot control the size of droplets to be sprayed by a conventional ultrasonic spraying method or the like, because it is possible to obtain fine spherical metal particles having a particle size of m or less with good productivity. Therefore, it is difficult to increase the yield per unit time because the fine spherical metal particle powder is generated by suppressing the concentration of the raw material components contained in the droplet to be low. By selecting the pore size of the filter and controlling the pressure in the system to be constant, fine spherical metal particles of 0.001 to 0.1 μm can be obtained, so that it is necessary to keep the concentration of the raw material solution low. Therefore, we believe that the yield per unit time could be increased.
【００４５】還元性ガスの使用量が低減できる理由とし
て、本発明者は、酢酸ニッケル若しくはギ酸ニッケル又
は酢酸銅若しくはギ酸銅の熱分解時に還元性のＣＯガス
が発生することによるものと考えている。The present inventor believes that the amount of the reducing gas used can be reduced because the reducing CO gas is generated during the thermal decomposition of nickel acetate or nickel formate, or copper acetate or copper formate. .
【００４６】また、本発明においては、加熱炉の段数を
多くして温度調節をより厳密に行い、更に、加熱炉の３
段以降で最高温度になるように温度調節することによっ
て、球状粒子で粒度分布が優れ、しかも、中空粒子を含
まない緻密な粒子粉末を得ることができたものと考えて
いる。Further, in the present invention, the number of stages of the heating furnace is increased to more strictly control the temperature.
It is believed that by adjusting the temperature to the highest temperature after the step, it was possible to obtain a fine particle powder having excellent particle size distribution with spherical particles and containing no hollow particles.
【００４７】[0047]
【実施例】次に、実施例並びに比較例を挙げる。Next, examples and comparative examples will be described.
【００４８】実施例１〜４、比較例１〜４、参考例１：
出発原料の種類、原料溶液の濃度、マイクロフィルター
の細孔径、系内の圧力、キャリアガスの種類及び流速、
還元性ガスの種類及び濃度、加熱炉の温度及びＬ／Ｄを
種々変化させた以外は、前記発明の実施の形態と同様に
して球状金属粒子粉末を得た。Examples 1-4, Comparative Examples 1-4, Reference Example 1:
Type of starting material, concentration of material solution, pore size of micro filter, pressure in system, type and flow rate of carrier gas,
Spherical metal particles were obtained in the same manner as in the embodiment of the invention except that the type and concentration of the reducing gas, the temperature of the heating furnace, and the L / D were variously changed.
【００４９】このときの製造条件を表１に、得られた球
状金属粒子粉末の諸特性を表２に示す。The production conditions at this time are shown in Table 1, and various properties of the obtained spherical metal particles are shown in Table 2.
【００５０】参考例１ 濃度が０．０１ｍｏｌ／ｌの酢酸ニッケル水溶液５００
ｍｌを超音波型噴霧器に入れた。超音波強度を５０ｍＷ
とし、酢酸ニッケル水溶液の液面から、エアロゾルが発
生していることを確認した後、水素ガスを０．１ｖｏｌ
％含有する窒素ガスをキャリアガスとして使用し、管内
の流速が２ｃｍ／ｓｅｃになるように、セラミック製加
熱炉に導入した。なお、用いた加熱炉のＬ／Ｄは５０で
あった。Reference Example 1 An aqueous nickel acetate solution having a concentration of 0.01 mol / l 500
ml was placed in an ultrasonic nebulizer. Ultrasonic strength of 50mW
After confirming that aerosol was generated from the liquid surface of the nickel acetate aqueous solution, 0.1 vol of hydrogen gas was supplied.
% Nitrogen gas was used as a carrier gas and introduced into a ceramic heating furnace such that the flow rate in the tube was 2 cm / sec. The L / D of the heating furnace used was 50.
【００５１】加熱炉の一段目から五段目までの加熱温度
をそれぞれ２５０℃、５００℃、８００℃、８５０℃、
８５０℃とし、エアロゾル中の溶剤を徐々に蒸発させた
後、熱処理を行って、エアロゾル中で熱分解反応を生じ
させた。加熱炉出口に電気集塵器を設置して粒子を捕集
した。このとき集塵機入口のエアロゾルに対し、直流５
０００Ｖの電圧によるコロナ放電処理を行い、強制的に
荷電させて、電気集塵器での捕集効率を高めた。The heating temperature from the first stage to the fifth stage of the heating furnace is 250 ° C., 500 ° C., 800 ° C., 850 ° C., respectively.
After setting the temperature to 850 ° C. and gradually evaporating the solvent in the aerosol, a heat treatment was performed to cause a thermal decomposition reaction in the aerosol. An electric precipitator was installed at the outlet of the heating furnace to collect particles. At this time, DC 5
Corona discharge treatment was performed with a voltage of 000 V to force charging, thereby increasing the collection efficiency of the electrostatic precipitator.
【００５２】このときの製造条件を表１に、得られた球
状金属粒子粉末の諸特性を表２に示す。The production conditions at this time are shown in Table 1, and various characteristics of the obtained spherical metal particles are shown in Table 2.
【００５３】[0053]
【表１】 [Table 1]
【００５４】[0054]
【表２】 [Table 2]
【００５５】[0055]
【発明の効果】本発明によれば、分散性に優れた緻密で
純度の高い球状金属粒子粉末を生産性よく得ることがで
きる。According to the present invention, dense and high-purity spherical metal particles having excellent dispersibility can be obtained with high productivity.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 奥山 喜久夫 広島県東広島市鏡山１丁目４番１号広島大 学工学部内 Ｆターム(参考） 4K017 AA03 BA03 BA05 CA01 DA01 DA08 EJ02 EK05 FA02 FB06 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kikuo Okuyama 1-4-1 Kagamiyama, Higashihiroshima City, Hiroshima Pref. Hiroshima University Faculty of Engineering F-term (reference)
Claims (1)
ル水溶液又は酢酸銅水溶液若しくはギ酸銅水溶液を噴霧
熱分解溶液として用いて噴霧熱分解法によって球状金属
粒子粉末を得る金属粒子粉末の製造法において、前記噴
霧熱分解溶液を減圧して噴霧することを特徴とする金属
粒子粉末の製造法。1. A method for producing spherical metal particle powder by a spray pyrolysis method using a nickel acetate aqueous solution, a nickel nickel formate aqueous solution, a copper acetate aqueous solution or a copper formate aqueous solution as a spray pyrolysis solution. A method for producing metal particle powder, comprising spraying a decomposition solution under reduced pressure.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001096834A JP2002294311A (en) | 2001-03-29 | 2001-03-29 | Method for producing metal grain powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001096834A JP2002294311A (en) | 2001-03-29 | 2001-03-29 | Method for producing metal grain powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002294311A true JP2002294311A (en) | 2002-10-09 |
Family
ID=18950705
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001096834A Withdrawn JP2002294311A (en) | 2001-03-29 | 2001-03-29 | Method for producing metal grain powder |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004041427A1 (en) * | 2002-11-08 | 2004-05-21 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Inorganic fine particles, inorganic raw material powder, and method for production thereof |
| EP1484430A2 (en) * | 2003-06-03 | 2004-12-08 | Basf Aktiengesellschaft | Deposition of copper layers on substrates |
| JP2006327889A (en) * | 2005-05-27 | 2006-12-07 | Kyocera Corp | Method for producing barium titanate powder and barium titanate powder |
| JP2008111093A (en) * | 2006-10-03 | 2008-05-15 | Shinko Electric Ind Co Ltd | Method for producing copper membrane |
| JP2013112889A (en) * | 2011-11-30 | 2013-06-10 | Toda Kogyo Corp | Method of manufacturing nickel fine particle powder and nickel fine particle powder obtained by the same manufacturing method |
-
2001
- 2001-03-29 JP JP2001096834A patent/JP2002294311A/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004041427A1 (en) * | 2002-11-08 | 2004-05-21 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Inorganic fine particles, inorganic raw material powder, and method for production thereof |
| KR100890585B1 (en) * | 2002-11-08 | 2009-03-25 | 다이이치 고교 세이야쿠 가부시키가이샤 | Inorganic fine particles, inorganic raw material powder, and method for production thereof |
| EP1484430A2 (en) * | 2003-06-03 | 2004-12-08 | Basf Aktiengesellschaft | Deposition of copper layers on substrates |
| EP1484430A3 (en) * | 2003-06-03 | 2008-03-19 | Basf Se | Deposition of copper layers on substrates |
| JP2006327889A (en) * | 2005-05-27 | 2006-12-07 | Kyocera Corp | Method for producing barium titanate powder and barium titanate powder |
| JP4711744B2 (en) * | 2005-05-27 | 2011-06-29 | 京セラ株式会社 | Method for producing barium titanate powder and barium titanate powder |
| JP2008111093A (en) * | 2006-10-03 | 2008-05-15 | Shinko Electric Ind Co Ltd | Method for producing copper membrane |
| JP2013112889A (en) * | 2011-11-30 | 2013-06-10 | Toda Kogyo Corp | Method of manufacturing nickel fine particle powder and nickel fine particle powder obtained by the same manufacturing method |
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