JPS6156209A - Production of ultrafine noble metal particle - Google Patents
Production of ultrafine noble metal particleInfo
- Publication number
- JPS6156209A JPS6156209A JP17654884A JP17654884A JPS6156209A JP S6156209 A JPS6156209 A JP S6156209A JP 17654884 A JP17654884 A JP 17654884A JP 17654884 A JP17654884 A JP 17654884A JP S6156209 A JPS6156209 A JP S6156209A
- Authority
- JP
- Japan
- Prior art keywords
- noble metal
- ultrafine
- nitrogen
- particles
- atmosphere
- 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.)
- Granted
Links
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は粒径１μｍ以下の貴金属超微粒子の製造法に関
する。更に詳しくは、触媒材料や導電材料として広く利
用される周期表におけるＩｂ族に属するｋｆＸＡｕ、■
ａ族に属するＢｅ、■族に属するＲｕＸＲｈ、 Ｉ’ｄ
、 Ｏｓ、 Ｉｒ、 Ｐｔ等の貴金属またはその合金の
超微粒子を製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing ultrafine noble metal particles having a particle size of 1 μm or less. More specifically, kfXAu, which belongs to group Ib in the periodic table and is widely used as a catalyst material and a conductive material,
Be belonging to group a, RuXRh belonging to group ■, I'd
, Os, Ir, Pt, or other noble metals or their alloys.
従来技術
従来の貴金属超微粒子の製造法としては、貴金属塩を水
溶液中で液相還元し、該貴金属を超微粒子として沈殿さ
せ、沈殿を濾過、洗浄、乾燥する方法が行われている。BACKGROUND ART Conventional methods for producing ultrafine noble metal particles include reducing a noble metal salt in an aqueous solution in a liquid phase, precipitating the noble metal as ultrafine particles, and filtering, washing, and drying the precipitate.
この方法は製造工程が極めて煩雑であるばかりでなく、
塩素等の有害な物質を含む多量の廃液を生じ、また薬品
による超微粒子の汚染を完全に除去することが極めて困
難であるなどの欠点があった。This method not only requires an extremely complicated manufacturing process, but also
There are disadvantages such as the generation of a large amount of waste liquid containing harmful substances such as chlorine, and the fact that it is extremely difficult to completely remove ultrafine particle contamination caused by chemicals.
発明の目的
本発明は従来法の欠点をかくすべくなされたものであり
、その目的は簡易な設備により、無公害的手段によって
高純度の貴金属またはその合金の超微粒子を極めて高能
率にかつ容易に製造する方法を提供することにある。Purpose of the Invention The present invention was made in order to hide the drawbacks of conventional methods, and its purpose is to produce ultrafine particles of high-purity precious metals or their alloys very efficiently and easily using simple equipment and non-polluting means. The purpose is to provide a manufacturing method.
発明の構成
本発明者らは、前記目的を達成すべく研究の結果、窒素
ガスまたは窒素ガスと不活性ガスの混合ガスあるいはｉ
＊ ｓ套７１−シ粂諧ｔｔ７１からなる雰囲気中で熱プ
ラズマを発生させ、該熱プラズマフレームにより周期表
１ｂ族、■ａ族及び■族から選ばれた貴金属またはその
合金（以下貴金属と総称する。）を溶融すると該金属の
超微粒化が生ずることを知見し、この知見に基いて本発
明を完成した。Structure of the Invention As a result of research to achieve the above object, the present inventors discovered that nitrogen gas, a mixed gas of nitrogen gas and an inert gas, or i
* A thermal plasma is generated in an atmosphere consisting of s-71-shi-kei-tt71, and the thermal plasma flame is used to generate precious metals selected from groups 1b, ) was found to cause ultrafine graining of the metal, and based on this knowledge, the present invention was completed.
との貴金属超微粒子の生成機構の詳細は明らかでは々い
が、大路次のように考えられる。Although the details of the formation mechanism of precious metal ultrafine particles are not clear, it is thought to be as follows.
熱プラズマ（大略１０，０ＯＯＫ以上）の高温下におい
ては、窒素ガスの大部分は解離し、窒素原子あるいは窒
素イオンの状態とな抄、通常の金属の溶融温度（約３０
００℃以下）における窒素（分子状９素）に比べて著し
く反応性の高い活性化状態にある。この活性化した窒素
を含む熱プラズマにより金属を溶融した場合、例えばお
ける再結合や溶融金属中への溶解など）が生ずる。Ｌ、
かじ、該金属が貴金属の場合、上記界面における窒素原
子の再結合と共に、溶融貴金属中への溶解した窒素も全
て再結合して二分子状窒素へ変換するため、窒素原子の
再結合エネルギーが効率よく溶融貴金属に付与される。Under the high temperature of thermal plasma (approximately 10,000 OOK or higher), most of the nitrogen gas dissociates and becomes nitrogen atoms or nitrogen ions.
It is in an activated state with significantly higher reactivity than nitrogen (molecular 9 elements) at temperatures below 00°C. When metal is melted by this activated thermal plasma containing nitrogen, recombination in the molten metal, dissolution into the molten metal, etc.) occur. L,
However, if the metal is a noble metal, at the same time as the nitrogen atoms recombine at the interface, all the nitrogen dissolved in the molten precious metal is also recombined and converted into bimolecular nitrogen, so the recombination energy of the nitrogen atoms is efficiently used. Often applied to molten precious metals.
その結果、溶融貴金属の強制蒸発現象が誘起され、貴金
属の超微粒子化が生ずるものと考えられる。As a result, a forced evaporation phenomenon of the molten precious metal is induced, and it is considered that the precious metal becomes ultra-fine particles.
本発明において超微粒子化される金属は、周期表のＴｂ
ｓ■ａおよび■族に属する貴金属、すなわち、Ａ ｆ
、 Ａ ｕ ＸＲｅ 、 Ｔｔ、１１、Ｒｈ、 Ｐｄ、
Ｏｓ。The metal to be made into ultrafine particles in the present invention is Tb of the periodic table.
Noble metals belonging to the s■a and ■groups, namely A f
, A u XRe , Tt, 11, Rh, Pd,
Os.
Ｔｒ、Ｐｔの金属および合金が挙げられる。Examples include metals and alloys of Tr and Pt.
本発明における貴金属超微粒子の発生速度は雰囲気窒素
濃度の高い程大きいため、この点よ松すれば窒素ガスの
みが好ましい。しかし、発生じた超微粒子の二次成長を
抑制（粒径制御）したり、熱プラズマの安定維持等の目
的で、Ａ ｒ −。Since the rate of generation of ultrafine precious metal particles in the present invention increases as the atmospheric nitrogen concentration increases, in this respect, only nitrogen gas is preferable. However, for the purpose of suppressing the secondary growth of generated ultrafine particles (particle size control), maintaining stability of thermal plasma, etc., Ar −.
Ｈｅ等の不活性ガスや水素ガスで希釈してもよい。It may be diluted with an inert gas such as He or hydrogen gas.
々お、超微粒子の水素吸着あるいは吸蔵を極力避けるた
め、前記窒素あるいは窒素と不活性ガ （スの混
合ガス中への水素の添加量は最大でも１０チ以下である
ことが望ましい。In order to avoid hydrogen adsorption or occlusion by the ultrafine particles as much as possible, it is desirable that the amount of hydrogen added to the nitrogen or the mixed gas of nitrogen and inert gas is at most 10% or less.
本発明における雰囲気ガスの圧力は、熱プラズマが安定
に発生しうる圧力であればよく、通常その圧力の下限は
約５０Ｔｏｒｒ程度である。The pressure of the atmospheric gas in the present invention may be any pressure at which thermal plasma can be stably generated, and the lower limit of the pressure is usually about 50 Torr.
本発明を実施する装置としては、通常のアーク溶解炉や
プラズマ溶解炉を使用することができる。しかし、生成
した貴金属超微粒子の粒径制御や捕集効率の向上などの
ためには、本発明者らの発明に係わる特公昭５８−０５
４１６６号公報記載の装置を使用することが好ましい。An ordinary arc melting furnace or plasma melting furnace can be used as an apparatus for carrying out the present invention. However, in order to control the particle size and improve the collection efficiency of the produced ultrafine precious metal particles, it is necessary to
It is preferable to use the apparatus described in Publication No. 4166.
その具体例を第１図に示す。同図において、１は密閉容
器であり、該容器上部には熱プラズマ発生用トーチ２が
設けられ、下部には貴金属溶解台５が配置されている。A specific example is shown in FIG. In the figure, reference numeral 1 denotes a closed container, in which a thermal plasma generating torch 2 is provided in the upper part of the container, and a noble metal melting table 5 is arranged in the lower part.
貴金属超微粒子の製造は、該トーチにより発生した熱プ
ラズマフレーム３によね貴金属試料４を加熱する。これ
により、貴金属試料は溶融され、同時に溶融貴金属は熱
プラズマフレーム中の活性化された窒素により、該貴金
属の強制蒸発が生じ貴金属超微粒子が発生する。該溶融
貴金属から発生した超微粒子は、該溶融貴金属の周囲に
設けられた吸引器６よね雰囲気ガスとともに吸引され、
冷却器７で冷却された後、捕集器９で捕集される。To manufacture ultrafine noble metal particles, a noble metal sample 4 is heated by a thermal plasma flame 3 generated by the torch. As a result, the noble metal sample is melted, and at the same time, the molten noble metal undergoes forced evaporation due to activated nitrogen in the thermal plasma flame, generating ultrafine noble metal particles. The ultrafine particles generated from the molten precious metal are sucked together with the atmospheric gas by a suction device 6 provided around the molten precious metal,
After being cooled by the cooler 7, it is collected by the collector 9.
すなわち、生成した貴金属超微粒子を速やかに冷却・捕
集できるような装置であることが好ましい。That is, it is preferable that the device be capable of quickly cooling and collecting the generated ultrafine precious metal particles.
発明の効果
窒素が使用されるため、極めて安全性も高く、かつその
製造装置々らびに製造工程も簡単で操業性も容易である
優れた効果を有する。そして得られた貴金属超微粒子は
、触媒材料や導電材料として使用することによね、それ
らの性能を一段と向上させるととができる。Effects of the Invention Since nitrogen is used, the invention has excellent effects such as extremely high safety, simple manufacturing equipment and manufacturing process, and easy operability. The obtained ultrafine noble metal particles can be used as catalyst materials or conductive materials to further improve their performance.
実施例
以下の実施例においては、熱プラズマの発生方法として
は直流アークプラズマ（正極性、電流は１気圧とした。EXAMPLES In the following examples, the thermal plasma generation method was direct current arc plasma (positive polarity, current was 1 atm).
表お、直流アークに変え、プラズマジェットや高周波プ
ラズマなどにより発生させた熱プラズマを使用してもは
寸同様な結果が得られる。However, similar results can be obtained by using thermal plasma generated by a plasma jet or high-frequency plasma instead of a DC arc.
実施例１
貴金属として銀を、雰囲気として３０ ％Ｎ２−７０
％Ａｒを使用し、優越微粒子を製造した。得られた優越
微粒子の最大粒径は約０．５μｍで、平均粒径は約０．
１μｍであった。啼た、超微粒子の形態は第２図に示す
ように、球状もしくは球状粒子の連なった状態であった
。なお、本実施例における優越微粒子の発生速度は大略
６９／ｈであった。Example 1 Silver as the noble metal, 30%N2-70 as the atmosphere
%Ar was used to produce superior microparticles. The maximum particle size of the obtained superior fine particles was about 0.5 μm, and the average particle size was about 0.5 μm.
It was 1 μm. As shown in FIG. 2, the shape of the ultrafine particles was spherical or a series of spherical particles. Note that the generation rate of superior fine particles in this example was approximately 69/h.
実施例２
貴金属として銀を、雰囲気として１００％歯を使用１２
、優越微粒子を製造した。得られた優越微粒子の最大粒
径は約０．５μｍで、平均粒径は約０２μｍであった。Example 2 Using silver as the precious metal and 100% tooth as the atmosphere12
, produced superior microparticles. The maximum particle size of the obtained superior fine particles was about 0.5 μm, and the average particle size was about 0.2 μm.
超微粒子の形態は、実施例１と同様に、球状もＬ ＜は
球状粒子の連なった状態であった。As in Example 1, the shape of the ultrafine particles was spherical, and L<< was a series of spherical particles.
また、優越微粒子の発生速度は約７，５ｆ／ｈであった
。Further, the generation rate of superior fine particles was about 7.5 f/h.
実施例３
貴金属と１．て白金を、雰囲気として１００チＮ２を使
用し、白金超微粒子を製造ｌ〜だ。得られた白金超微粒
子の最大粒径は約０．１μｍであり、平均粒径は約００
３μｍであった。第３図に示すように、粒子の形状は主
と１〜て球形であり、一部には多角形の形状を有する粒
子も認められた。なお、本実施例における白金超微粒子
の発生速度は約１（１／ｈであった。Example 3 Precious metals and 1. Ultrafine platinum particles were produced using platinum and 100 cm of N2 as an atmosphere. The maximum particle size of the obtained ultrafine platinum particles was about 0.1 μm, and the average particle size was about 0.00 μm.
It was 3 μm. As shown in FIG. 3, the particles were mainly spherical in shape, and some particles were also found to have a polygonal shape. Note that the generation rate of ultrafine platinum particles in this example was approximately 1 (1/h).
第１図は本発明の方法を実施する装置の１例を示しだも
のである。
第２図は優越微粒子の透過電子顕微鏡写真。
第３図は白金超微粒子の透過電子顕微鏡写真。
１；密閉容器 ２：熱プラズマ発生用トーチ
３：熱プラズマフレーム
４；貴金属試料 ５：貴金属溶解台
６：吸引器 ７：冷却器
８．８′：雰囲気ガス導入口
９：捕集器 ｌＯ：吸引ポンプ
特許出願人 科学技術庁金属材料技術研究所長中 川
龍 −
′＠１目FIG. 1 shows an example of an apparatus for carrying out the method of the invention. Figure 2 is a transmission electron micrograph of superior fine particles. Figure 3 is a transmission electron micrograph of ultrafine platinum particles. 1; Sealed container 2: Torch for thermal plasma generation 3: Thermal plasma flame 4; Precious metal sample 5: Precious metal melting table 6: Suction device 7: Cooler 8.8': Atmospheric gas inlet 9: Collector 1O: Suction Pump patent applicant: Ryu Kawa, Director, Metal Materials Technology Research Institute, Science and Technology Agency - '@1me
Claims (1)
はこれらのガスに水素を混合したガスからなる雰囲気中
で熱プラズマを発生させ、該熱プラズマフレームにより
周期表 I ｂ族、VIIａ族及びVIII族から選ばれた貴金属
またはその合金を溶融することを特徴とする貴金属超微
粒子の製造法。A thermal plasma is generated in an atmosphere consisting of nitrogen gas, a mixture of nitrogen gas and an inert gas, or a mixture of these gases and hydrogen, and the thermal plasma flame is used to generate plasma from groups Ib, VIIa, and VIII of the periodic table. A method for producing ultrafine precious metal particles, which comprises melting a selected precious metal or its alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17654884A JPS6156209A (en) | 1984-08-27 | 1984-08-27 | Production of ultrafine noble metal particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17654884A JPS6156209A (en) | 1984-08-27 | 1984-08-27 | Production of ultrafine noble metal particle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6156209A true JPS6156209A (en) | 1986-03-20 |
| JPS6139372B2 JPS6139372B2 (en) | 1986-09-03 |
Family
ID=16015506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17654884A Granted JPS6156209A (en) | 1984-08-27 | 1984-08-27 | Production of ultrafine noble metal particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6156209A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7384448B2 (en) | 2004-02-16 | 2008-06-10 | Climax Engineered Materials, Llc | Method and apparatus for producing nano-particles of silver |
| KR101009656B1 (en) | 2008-09-17 | 2011-01-19 | 희성금속 주식회사 | Method of Ultra Fine Powder of Precious Metals |
| KR101024971B1 (en) | 2008-12-12 | 2011-03-25 | 희성금속 주식회사 | A Method of Powder and Target of Precious Metals by Thermal Plasma |
| KR101118635B1 (en) * | 2009-12-14 | 2012-03-06 | 희성금속 주식회사 | Method of an enhanced platinum materials using a thermal plasma process |
| WO2012121444A1 (en) * | 2011-03-10 | 2012-09-13 | 희성금속 주식회사 | Plasma-aided manufacturing method for oxide-dispersion-strengthened platinum material |
| WO2012124840A1 (en) * | 2011-03-11 | 2012-09-20 | 희성금속 주식회사 | Method for manufacturing titanium powder for manufacturing oxide-dispersion strengthening-type titanium material |
| WO2013147337A1 (en) * | 2012-03-26 | 2013-10-03 | 희성금속 주식회사 | Method for manufacturing oxide dispersion-strengthened platinum-gold alloy |
| JP2016028176A (en) * | 2014-02-14 | 2016-02-25 | 三井金属鉱業株式会社 | Method for manufacturing copper powder |
| JP2019094555A (en) * | 2017-11-20 | 2019-06-20 | 国立大学法人弘前大学 | Production method of high strength silver sintered body and high strength silver sintered body |
-
1984
- 1984-08-27 JP JP17654884A patent/JPS6156209A/en active Granted
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7384448B2 (en) | 2004-02-16 | 2008-06-10 | Climax Engineered Materials, Llc | Method and apparatus for producing nano-particles of silver |
| GB2425779B (en) * | 2004-02-16 | 2008-08-06 | Climax Engineered Mat Llc | Method and apparatus for producing nano-particles of silver |
| US7575711B2 (en) | 2004-02-16 | 2009-08-18 | Climax Engineered Materials, Llc | Apparatus for producing nano-particles of silver |
| KR101009656B1 (en) | 2008-09-17 | 2011-01-19 | 희성금속 주식회사 | Method of Ultra Fine Powder of Precious Metals |
| KR101024971B1 (en) | 2008-12-12 | 2011-03-25 | 희성금속 주식회사 | A Method of Powder and Target of Precious Metals by Thermal Plasma |
| KR101118635B1 (en) * | 2009-12-14 | 2012-03-06 | 희성금속 주식회사 | Method of an enhanced platinum materials using a thermal plasma process |
| WO2012121444A1 (en) * | 2011-03-10 | 2012-09-13 | 희성금속 주식회사 | Plasma-aided manufacturing method for oxide-dispersion-strengthened platinum material |
| WO2012124840A1 (en) * | 2011-03-11 | 2012-09-20 | 희성금속 주식회사 | Method for manufacturing titanium powder for manufacturing oxide-dispersion strengthening-type titanium material |
| WO2013147337A1 (en) * | 2012-03-26 | 2013-10-03 | 희성금속 주식회사 | Method for manufacturing oxide dispersion-strengthened platinum-gold alloy |
| KR101419443B1 (en) * | 2012-03-26 | 2014-07-14 | 희성금속 주식회사 | Method of an oxide dispersion strengthened platinum-gold alloy |
| JP2016028176A (en) * | 2014-02-14 | 2016-02-25 | 三井金属鉱業株式会社 | Method for manufacturing copper powder |
| JP2019094555A (en) * | 2017-11-20 | 2019-06-20 | 国立大学法人弘前大学 | Production method of high strength silver sintered body and high strength silver sintered body |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6139372B2 (en) | 1986-09-03 |
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