JP2001254110A - Method of producing metallic particulate powder - Google Patents
Method of producing metallic particulate powderInfo
- Publication number
- JP2001254110A JP2001254110A JP2000066724A JP2000066724A JP2001254110A JP 2001254110 A JP2001254110 A JP 2001254110A JP 2000066724 A JP2000066724 A JP 2000066724A JP 2000066724 A JP2000066724 A JP 2000066724A JP 2001254110 A JP2001254110 A JP 2001254110A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- particle powder
- spherical
- nickel
- particulate powder
- 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.)
- Pending
Links
- 239000000843 powder Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 10
- 150000001879 copper Chemical class 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- 150000002815 nickel Chemical class 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000002923 metal particle Substances 0.000 claims description 32
- 238000005118 spray pyrolysis Methods 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 19
- 239000012159 carrier gas Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 3
- 239000000443 aerosol Substances 0.000 description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000012717 electrostatic precipitator Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】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 metal particle powder capable of obtaining a dense and high-purity spherical metal particle powder having excellent dispersibility.
【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
サなどの電極材料に用いられる金属粒子粉末についても
特性改善が要求されている。2. Description of the Related Art In recent years, with the miniaturization, higher performance and lighter weight of various electronic devices, there has been a demand for improved characteristics of metal particle powders used for electrode materials of electronic device components, for example, multilayer capacitors.
【０００３】特に、前記用途に供せられるニッケル粒子
粉末や銅粒子粉末としては、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。[0003] In particular, nickel particle powder and copper particle powder used for the above applications are excellent in dispersibility without aggregation,
In addition, it is required to be dense and have high purity.
【０００４】一方、周知の通り、球状金属粒子粉末の製
造方法の一つとして噴霧熱分解法が知られている。[0004] On the other hand, as is well known, a spray pyrolysis method is known as one method of producing spherical metal particle powder.
【０００５】噴霧熱分解法とは、原料溶液をノズルや超
音波によって噴霧して微小液滴とし該微小液滴の溶媒を
蒸発させて熱分解により目的の粒子粉末を得る方法であ
る。[0005] The spray pyrolysis method is a method in which a raw material solution is sprayed with a nozzle or ultrasonic waves to form fine droplets, and the solvent of the fine droplets is evaporated to obtain target particle powder by thermal decomposition.
【０００６】従来、噴霧熱分解法によってニッケル粒子
粉末などの金属粒子粉末を得る方法として、特開平８−
１７０１１２号公報、特開平１１−８０８１８号公報及
び特開平１１−２３６６０７号公報に記載の各方法が知
られている。Conventionally, a method of obtaining metal particle powder such as nickel particle powder by a spray pyrolysis method is disclosed in
Each method described in JP-A-170112, JP-A-11-80818, and JP-A-11-236607 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。That is, Japanese Patent Application Laid-Open No. Hei 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.
【０００９】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。The spray pyrolysis method described in JP-A-11-80818 uses a carrier gas containing a reducing gas in an amount of 1 to 35 vol% (16.7 vol% in the embodiment). Disadvantageous.
【００１０】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 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.
【００１１】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工
業的に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 industrially produce dense and high-purity spherical metal particles having excellent dispersibility by a spray pyrolysis method.
【００１２】[0012]
【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.
【００１３】即ち、本発明は、ニッケル塩水溶液又は銅
塩水溶液と該水溶液中のニッケル塩又は銅塩に対してモ
ル比で０．０１〜１０の炭酸水素塩を含有する水溶液と
の混合水溶液を噴霧熱分解溶液として用いて噴霧熱分解
法により金属粒子粉末を得ることを特徴とする球状金属
粒子粉末の製造法である。That is, the present invention provides a mixed aqueous solution of a nickel salt aqueous solution or a copper salt aqueous solution and an aqueous solution containing a hydrogen carbonate in a molar ratio of 0.01 to 10 with respect to the nickel salt or the copper salt in the aqueous solution. A method for producing spherical metal particle powder, characterized in that metal particle powder is obtained by a spray pyrolysis method using a spray pyrolysis solution.
【００１４】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.
【００１５】本発明に用いる噴霧熱分解溶液は、ニッケ
ル塩水溶液又は銅塩水溶液と該水溶液中のニッケル塩又
は銅塩に対してモル比で０．０１〜１０の炭酸水素塩を
含有する水溶液からなり、当該水溶液を用いて噴霧熱分
解を行うことにより、還元性ガスを用いることなく目的
とする球状金属粒子粉末を得ることができる。The spray pyrolysis solution used in the present invention comprises an aqueous solution of a nickel salt or an aqueous solution of a copper salt and an aqueous solution containing a hydrogen carbonate in a molar ratio of 0.01 to 10 with respect to the nickel or copper salt in the aqueous solution. By performing spray pyrolysis using the aqueous solution, the desired spherical metal particle powder can be obtained without using a reducing gas.
【００１６】ニッケル塩水溶液又は銅塩水溶液として
は、硝酸ニッケル水溶液、硝酸銅水溶液、硫酸ニッケル
水溶液、硫酸銅水溶液、塩化ニッケル水溶液水溶液、塩
化銅水溶液等を用いることができる。得られる金属粒子
粉末の高純度化を考慮すれば、硝酸ニッケル水溶液、硝
酸銅水溶液が好ましい。As the nickel salt aqueous solution or the copper salt aqueous solution, a nickel nitrate aqueous solution, a copper nitrate aqueous solution, a nickel sulfate aqueous solution, a copper sulfate aqueous solution, a nickel chloride aqueous solution, a copper chloride aqueous solution and the like can be used. Considering high purity of the obtained metal particle powder, an aqueous solution of nickel nitrate and an aqueous solution of copper nitrate are preferred.
【００１７】炭酸水素塩としては、炭酸水素アンモニウ
ム（（ＮＨ４）ＨＣＯ３）、炭酸水素ナトリウム（Ｎａ
ＨＣＯ３）、炭酸水素カリウム（ＫＨＣＯ３）等を用い
ることができる。得られる金属粒子粉末の純度を考慮す
れば、炭酸水素アンモニウムが好ましい。As the hydrogen carbonate, ammonium hydrogen carbonate ((NH 4 ) HCO 3 ), sodium hydrogen carbonate (Na
HCO 3 ), potassium hydrogen carbonate (KHCO 3 ), or the like can be used. In consideration of the purity of the obtained metal particle powder, ammonium hydrogen carbonate is preferable.
【００１８】炭酸水素塩の添加量が金属塩に対してモル
比で０．０１未満の場合には、加熱炉中で十分な熱分解
が起こらず、得られる球状金属粒子粉末の結晶性が低下
したり、金属酸化物が混在したりする場合がある。１０
を超える場合には、効果が飽和するので必要以上に添加
する意味がない。得られる球状金属粒子粉末の結晶性、
純度及び工業性、経済性を考慮すれば、０．０５〜５が
好ましい。When the amount of the hydrogencarbonate added is less than 0.01 in terms of molar ratio with respect to the metal salt, sufficient thermal decomposition does not occur in a heating furnace, and the crystallinity of the obtained spherical metal particles decreases. Or metal oxides may be mixed. 10
If the amount exceeds, the effect is saturated, and there is no point in adding more than necessary. Crystallinity of the obtained spherical metal particles powder,
In consideration of purity, industrial efficiency, and economy, 0.05 to 5 is preferable.
【００１９】噴霧熱分解溶液の金属塩の濃度は０．００
１〜０．５ｍｏｌ／ｌが好ましい。０．００１ｍｏｌ／
ｌ未満の場合には、得られる球状金属粒子粉末の粒子サ
イズが小さくなりすぎる。０．５ｍｏｌ／ｌを超える場
合には、粒子サイズが大きくなり、粒度分布が悪くなる
傾向にある。より好ましくは０．０１〜０．４ｍｏｌ／
ｌである。The concentration of the metal salt in the spray pyrolysis solution is 0.00
1 to 0.5 mol / l is preferred. 0.001 mol /
If it is less than 1, the particle size of the obtained spherical metal particle powder becomes too small. If it exceeds 0.5 mol / l, the particle size tends to be large and the particle size distribution tends to be poor. More preferably 0.01 to 0.4 mol /
l.
【００２０】噴霧熱分解法では、噴霧した液滴径によっ
て得られる球状金属粒子粉末の粒子径が変化するため、
液滴の大きさが均一になるように噴霧する。具体的に
は、２流体ノズル、超音波又は静電気等の方法によって
液滴をつくることができ、好ましくは超音波によって噴
霧する方法である。In the spray pyrolysis method, the particle diameter of the obtained spherical metal particles changes depending on the diameter of the sprayed droplet.
Spray so that the size of the droplet is uniform. Specifically, droplets can be formed by a two-fluid nozzle, a method such as ultrasonic waves or static electricity, and preferably a method of spraying by ultrasonic waves.
【００２１】本発明においては還元性ガスを用いること
なく金属粒子粉末を得ることができるため、噴霧した液
滴はキャリアガスのみによって加熱炉中に導入される。
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。キャリアガ
スの流速は１．０〜１０ｃｍ／ｓｅｃが好ましい。In the present invention, since the metal particle powder can be obtained without using a reducing gas, the sprayed droplets are introduced into the heating furnace only by the carrier gas.
The carrier gas is not particularly limited as long as it is an inert gas, but is preferably nitrogen. The flow rate of the carrier gas is preferably 1.0 to 10 cm / sec.
【００２２】加熱炉は、５段以上設けることが好まし
く、３段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 particle powder.
【００２３】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.
【００２４】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 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.
【００２５】熱分解が終了した金属粒子粉末は、常法に
従い電気集じん機などによって集める。The thermally decomposed metal particle powder is collected by an electric precipitator or the like according to a conventional method.
【００２６】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、平均粒子径が０．０１〜１．０μｍで
あり（必要に応じて０．０５〜０．８μｍ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 nickel particle powder obtained by the present invention has a spherical shape, an average particle diameter of 0.01 to 1.0 μm (can be 0.05 to 0.8 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.
【００２７】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０．０１〜１．０μｍであり
（必要に応じて０．０５〜０．８μｍ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１．０〜５．０×１０３
Ω・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 0.01 to 1.0 μm (can be 0.05 to 0.8 μm if necessary), and a geometric standard deviation value. Is 2.0 or less (1.8 or less if necessary), the BET specific surface area is 1 to 100 m 2 / g (1.5 to 80 m 2 / g if necessary), and the density ratio Is 0.75-1.0 (0.8-
1.0), and the volume resistivity is 1.0 to 9.5 ×
10 3 Ω · cm (1.0 to 5.0 × 10 3 as necessary
Ω · cm). The crystallinity is 4000 or more.
【００２８】[0028]
【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.
【００２９】粒子粉末の平均粒子径は、電子顕微鏡写真
（×２０，０００）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 determined by measuring the particle diameter of about 350 particles shown in a photograph obtained by magnifying an electron micrograph (× 20,000) four times in the vertical and horizontal directions, respectively. The average value was shown.
【００３０】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.
【００３１】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.
【００３２】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 was determined by measuring the density of each powder using a “Multi Volume Densitometer Model 1305” (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.
【００３３】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）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 is measured by using an "X-ray diffractometer RAD-IIA" (manufactured by Rigaku Corporation) (tube:
Fe), 2θ is measured in the range of 3 to 105 °,
The peak intensity of the obtained strongest line was shown.
【００３４】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.
【００３５】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, the sample to be measured (cylindrical) was exposed to an environment of 25 ° C. and a relative humidity of 60% for 12 hours or more. Then, 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).
【００３６】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).
【００３７】[0037]
【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.
【００３８】＜球状金属粒子粉末の製造＞濃度が０．０
８ｍｏｌ／ｌの硝酸ニッケル水溶液に、硝酸ニッケルに
対してモル比で０．１になるように炭酸水素アンモニウ
ム水溶液を混合して、噴霧熱分解用水溶液を作製した。<Production of spherical metal particle powder>
An aqueous solution of ammonium bicarbonate was mixed with an aqueous solution of 8 mol / l of nickel nitrate so as to have a molar ratio of 0.1 with respect to nickel nitrate to prepare an aqueous solution for spray pyrolysis.
【００３９】上記噴霧熱分解用水溶液５００ｍｌを分取
し、超音波型噴霧器に入れた。超音波強度を５０ｍＷと
し、該水溶液の液面から、エアロゾルが発生しているこ
とを確認した後、キャリアガスとして窒素を使用し、管
内の流速が５ｃｍ／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３０
であった。500 ml of the above-mentioned aqueous solution for spray pyrolysis was taken and placed in an ultrasonic atomizer. After confirming that aerosol was generated from the liquid surface of the aqueous solution at an ultrasonic intensity of 50 mW, nitrogen was used as a carrier gas, and a ceramic heating furnace was used so that the flow rate in the tube was 5 cm / sec. Was introduced. The L / D of the heating furnace used was 30.
Met.
【００４０】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 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. 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.
【００４１】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０．１５μｍ、幾何標準偏差値が
１．４８、ＢＥＴ比表面積値が１４．６ｍ２／ｇ、密度
比が０．８７、結晶性が８３００、体積固有抵抗値が
３．９×１０２Ω・ｃｍであった。The obtained nickel particle powder has a spherical shape, an average particle diameter of 0.15 μm, a geometric standard deviation of 1.48, a BET specific surface area of 14.6 m 2 / g, and a density ratio of 0. 87, crystallinity was 8300, and volume resistivity was 3.9 × 10 2 Ω · cm.
【００４２】図１に、上記で得られた球状ニッケル粒子
粉末の電子顕微鏡写真（１００，０００倍）を示す。該
写真により真球状粒子が得られていることが確認でき
る。FIG. 1 shows an electron micrograph (× 100,000) of the spherical nickel particles obtained above. The photograph confirms that true spherical particles have been obtained.
【００４３】[0043]
【作用】本発明において最も重要な点は、噴霧熱分解溶
液中に炭酸水素塩を含有させることによって、キャリア
ガス中に還元性ガスを含有させることなく金属粒子粉末
を得ることができ、しかも、得られた金属粒子粉末は分
散性に優れ、且つ、緻密で球状を呈するという事実であ
る。The most important point in the present invention is that by adding bicarbonate to the spray pyrolysis solution, metal particle powder can be obtained without containing reducing gas in the carrier gas. This is the fact that the obtained metal particle powder has excellent dispersibility, and is dense and spherical.
【００４４】従来、金属粒子粉末を噴霧熱分解法によっ
て得る場合には、キャリアガス中に還元性ガスを含ませ
ておかなければ金属粒子粉末を得ることはできなかった
が、本発明においては、噴霧熱分解溶液中に炭酸水素塩
を含有させることによって、キャリアガス中に還元性ガ
スを全く含有させることなく金属粒子粉末を得ることが
できる。この理由は未だ明らかではないが、加熱炉中で
金属塩と共に炭酸水素塩も熱分解されて水素ガス及びＣ
Ｏガスが発生することによって還元性雰囲気になるため
と推定している。Conventionally, when the metal particle powder was obtained by the spray pyrolysis method, the metal particle powder could not be obtained unless the reducing gas was contained in the carrier gas. By including a bicarbonate in the spray pyrolysis solution, metal particle powder can be obtained without any reducing gas contained in the carrier gas. The reason for this is not clear yet, but the hydrogen carbonate and the metal salt are thermally decomposed together with the metal salt in the heating furnace, and hydrogen gas and C
It is estimated that the generation of O gas causes a reducing atmosphere.
【００４５】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推定し
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 presumed 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 not containing hollow particles.
【００４６】[0046]
【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.
【００４７】実施例１〜４、比較例１〜５：金属塩水溶
液における金属塩の種類及び濃度、炭酸水素塩の種類及
び添加量（金属塩に対するモル比）、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
及び加熱炉の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 1-5: Kind and concentration of metal salt in aqueous metal salt solution, kind and addition amount of hydrogen carbonate (molar ratio to metal salt), kind and flow rate of carrier gas, reduction Spherical metal particles were obtained in the same manner as in the embodiment of the invention except that the type and concentration of the reactive gas, the temperature of the heating furnace, and the L / D of the heating furnace were variously changed.
【００４８】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.
【００４９】[0049]
【表１】 [Table 1]
【００５０】[0050]
【表２】 [Table 2]
【００５１】[0051]
【発明の効果】本発明によれば、キャリアガス中に還元
性ガスを含有させることなく、分散性に優れた緻密で純
度の高い球状金属粒子粉末を工業的に容易に得ることが
できる。According to the present invention, dense and high-purity spherical metal particles having excellent dispersibility can be industrially easily obtained without containing a reducing gas in a carrier gas.
【図１】発明の実施の形態で得られたニッケル粒子粉末
の粒子形状を示す透過型電子顕微鏡写真（１００，００
０倍）FIG. 1 is a transmission electron micrograph (100,00) showing the particle shape of a nickel particle powder obtained in an embodiment of the invention.
0 times)
───────────────────────────────────────────────────── 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 BB05 BB06 CA01 DA08 EK05 4K018 BA02 BA04 BB03 BD10 5E001 AB03 AC09 AH00 AH01 AJ01 5E082 AB03 EE04 EE23 EE35 MM24 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Kikuo Okuyama 1-4-1 Kagamiyama, Higashihiroshima City, Hiroshima Pref. Hiroshima University Faculty of Engineering F-term (reference) AC09 AH00 AH01 AJ01 5E082 AB03 EE04 EE23 EE35 MM24
Claims (1)
溶液中のニッケル塩又は銅塩に対してモル比で０．０１
〜１０の炭酸水素塩を含有する水溶液との混合水溶液を
噴霧熱分解溶液として用いて噴霧熱分解法により球状金
属粒子粉末を得ることを特徴とする金属粒子粉末の製造
法。1. A nickel salt aqueous solution or copper salt aqueous solution and a molar ratio of 0.01 to nickel salt or copper salt in the aqueous solution.
A method for producing metal particle powder, characterized in that a spherical metal particle powder is obtained by spray pyrolysis using an aqueous mixed solution with an aqueous solution containing a hydrogen carbonate of from 10 to 10 as a spray pyrolysis solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000066724A JP2001254110A (en) | 2000-03-10 | 2000-03-10 | Method of producing metallic particulate powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000066724A JP2001254110A (en) | 2000-03-10 | 2000-03-10 | Method of producing metallic particulate powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001254110A true JP2001254110A (en) | 2001-09-18 |
Family
ID=18586037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000066724A Pending JP2001254110A (en) | 2000-03-10 | 2000-03-10 | Method of producing metallic particulate powder |
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| Country | Link |
|---|---|
| JP (1) | JP2001254110A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100503132B1 (en) * | 2002-11-08 | 2005-07-22 | 한국화학연구원 | Method for producing fine spherical particles of nickel metal |
| KR100507638B1 (en) * | 2002-11-29 | 2005-08-10 | 한국화학연구원 | A method for producing ultrafine spherical nickel particles |
-
2000
- 2000-03-10 JP JP2000066724A patent/JP2001254110A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100503132B1 (en) * | 2002-11-08 | 2005-07-22 | 한국화학연구원 | Method for producing fine spherical particles of nickel metal |
| KR100507638B1 (en) * | 2002-11-29 | 2005-08-10 | 한국화학연구원 | A method for producing ultrafine spherical nickel particles |
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