JPH0352401B2 - - Google Patents
Info
- Publication number
- JPH0352401B2 JPH0352401B2 JP22840386A JP22840386A JPH0352401B2 JP H0352401 B2 JPH0352401 B2 JP H0352401B2 JP 22840386 A JP22840386 A JP 22840386A JP 22840386 A JP22840386 A JP 22840386A JP H0352401 B2 JPH0352401 B2 JP H0352401B2
- Authority
- JP
- Japan
- Prior art keywords
- ultrafine
- arc discharge
- oxide particles
- ruo
- sio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000002245 particle Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 238000010891 electric arc Methods 0.000 claims description 13
- 239000007769 metal material Substances 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000008016 vaporization Effects 0.000 claims description 2
- 239000011882 ultra-fine particle Substances 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- -1 graphite in advance Chemical compound 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
- B01J12/02—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor for obtaining at least one reaction product which, at normal temperature, is in the solid state
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Silicon Compounds (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、酸化物超微粒子の生成法に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a method for producing ultrafine oxide particles.
（従来の技術）
従来の酸化物超微粒子の生成法としては、酸素
を含んだ雰囲気下で高融点の金属材料を金属製電
極間のアーク放電で加熱蒸発させ、その金属酸化
物超微粒子を生成することが知られている。例え
ば、タングステンなどの金属を陰極とし、ルテニ
ウムやシリコンをアーク放電で加熱蒸発させ、
RuO2やSiO2などの金属酸化物超微粒子の集積体
が生成される。(Prior art) The conventional method for producing ultrafine oxide particles involves heating and vaporizing a high-melting point metal material in an oxygen-containing atmosphere using arc discharge between metal electrodes to generate ultrafine metal oxide particles. It is known to do. For example, a metal such as tungsten is used as a cathode, and ruthenium or silicon is heated and evaporated by arc discharge.
An aggregate of ultrafine metal oxide particles such as RuO 2 and SiO 2 is generated.
（発明が解決しようとする問題点）
上記従来の生成法では、アーク放電において、
タングステン陰極が徐々に少しづつ加熱酸化し、
その酸化が生成し、この酸化物は、金属に比べて
蒸気圧が高いために超微粒子化し蒸発しRuO2や
SiO2などの目的とする生産物である酸化物超微
粒子集積体中に混入した生産物となることが不可
避であつた。(Problems to be solved by the invention) In the above conventional generation method, in arc discharge,
The tungsten cathode is gradually heated and oxidized,
The oxidation is generated, and since this oxide has a higher vapor pressure than the metal, it becomes ultrafine particles and evaporates, producing RuO 2 and other oxides.
It was inevitable that the product would be mixed into the oxide ultrafine particle aggregate, which is the desired product such as SiO 2 .
（問題点を解決するための手段）
本発明は、かかる上記の欠点を除去し、不純な
金属酸化物の混入しない目的とする金属酸化物の
超微粒子集積体のみを製造し得るようにした酸化
物超微粒子の生成法に関するもので、酸素を含ん
だ雰囲気下で金属材料を電極間のアーク放電で加
熱蒸発させ、その金属酸化物超微粒子を製造する
方法において、アーク放電の電極の少くとも陰極
をカーボンで構成してアーク放電を行なうように
したことを特徴とする。(Means for Solving the Problems) The present invention is an oxidation method that eliminates the above-mentioned drawbacks and makes it possible to produce only the target ultrafine particle aggregate of metal oxides without contamination with impure metal oxides. This relates to a method for producing ultrafine metal oxide particles, in which a metal material is heated and evaporated by arc discharge between electrodes in an oxygen-containing atmosphere to produce ultrafine metal oxide particles. It is characterized in that it is made of carbon and is configured to perform arc discharge.
（実施例）
次に本発明の実施例につき説明する。添付図面
の第１図は、本発明を実施する一例の製造装置を
示す。図面で１は真空容器、２は真空容器１内に
対向した水冷銅ハースを兼ねた陽極、３は、水冷
銅トーチ３ａの先端に黒鉛から成るカーボン筒体
３ｂを螺着して成るカーボン陰極、ａは該陽極２
の上面に収容したRu、Si、Al、Sn、Ｖ、Tiなど
の金属材料、４は、陰陽極間を接続するアーク放
電用直流電源、５は不活性ガスと酸素との混合ガ
スを調節バルブ６を介して該容器１内に供給する
ガス導入管、７は真空容器１内と調節弁８を介し
て真空ポンプ９とを接続する排気用導管を示す。
上記の装置を使用し、本発明を実施するには、真
空容器１内を、該真空ポンプ８により真空排気す
る一方、ガス導入管５を介して真空容器１内にア
ルゴン＋30％O2の混合ガスを導入し、100トール
の混合ガス圧が真空容器１内に維持されるように
し、この状態で例えば、25A、25V直流電源４を
作動し、該陰陽極２，３間にアーク放電を発生さ
せ、金属材料を加熱蒸発させ、その酸素ガス雰囲
気と接触させてその酸化物例えばRuO2やSiO2な
ど所望の超微粒子が生成される。本発明によれ
ば、その陰極３を黒鉛などのカーボンで予め作成
してあるので、その酸化物超微粒子の生成がな
く、酸化してもCO2ガスとなり、従来のような金
属材料から成る陰極の酸化物超微粒子が、RuO2
やSiO2などの目的とする金属酸化物超微粒子集
積体中に混入するおそれが全くなく、純粋な
RuO2やSiO2などの金属酸化物超微粒子のみの生
産が可能となる。(Example) Next, an example of the present invention will be described. FIG. 1 of the accompanying drawings shows an example of a manufacturing apparatus for carrying out the present invention. In the drawing, 1 is a vacuum vessel, 2 is an anode which also serves as a water-cooled copper hearth, and 3 is a carbon cathode formed by screwing a carbon cylinder 3b made of graphite to the tip of a water-cooled copper torch 3a. a is the anode 2
Metal materials such as Ru, Si, Al, Sn, V, and Ti are housed on the top surface, 4 is a DC power source for arc discharge that connects the cathode and anode, and 5 is a control valve for controlling the mixed gas of inert gas and oxygen. 6 is a gas introduction pipe for supplying gas into the container 1, and 7 is an exhaust conduit connecting the inside of the vacuum container 1 and a vacuum pump 9 via a control valve 8.
In order to carry out the present invention using the above-mentioned apparatus, the inside of the vacuum container 1 is evacuated by the vacuum pump 8, while argon + 30% O 2 is mixed into the vacuum container 1 through the gas introduction pipe 5. Gas is introduced so that a mixed gas pressure of 100 torr is maintained in the vacuum vessel 1, and in this state, for example, a 25A, 25V DC power supply 4 is activated to generate an arc discharge between the anodes 2 and 3. The metal material is heated and evaporated, and brought into contact with the oxygen gas atmosphere to produce desired ultrafine particles of its oxides, such as RuO 2 and SiO 2 . According to the present invention, since the cathode 3 is made of carbon such as graphite in advance, ultrafine particles of the oxide are not generated, and even when oxidized, CO 2 gas is generated. The ultrafine oxide particles of RuO 2
There is no risk of contamination with the target metal oxide ultrafine particle aggregate such as SiO 2 and pure
It becomes possible to produce only ultrafine particles of metal oxides such as RuO 2 and SiO 2 .
上記の製法で得られたRuO2やSiO2の夫々の超
微粒子集積体につき、TEM写真やSEM写真をと
り、黒鉛の混入が全くなく、平均粒径200Åの超
微粒子のRuO2、SiO2の夫々の集積体が得られて
いることを確認した。RuO2超微粒子集積体のＸ
線回折（ターゲツト／フイルタ（モノクロ）：
Cu、電圧／電流：50KV、200mA）の結果を第
２図に示す。RuO2のピークの他にRuのピークも
少し検出されているが、黒鉛の混入は認められな
い。 TEM and SEM photographs were taken of each of the ultrafine particle aggregates of RuO 2 and SiO 2 obtained by the above manufacturing method, and they were found to be ultrafine particles of RuO 2 and SiO 2 with no graphite contamination and an average particle size of 200 Å. It was confirmed that each aggregate was obtained. RuO 2 ultrafine particle aggregate X
Linear diffraction (target/filter (monochrome):
Figure 2 shows the results for Cu, voltage/current: 50KV, 200mA). In addition to the RuO 2 peak, a small Ru peak was also detected, but no graphite was detected.
尚この生成されたRuO2超微粒子集積体を600℃
で加熱処理を施すと、Ruのピークがなくなり
RuO2だけのピークになることが分つた。SiO2超
微粒子のＸ線回折によれば、SiO2のピークはブ
ロードでありアモルフアスのようであつたが、蛍
光Ｘ線分析でSiのピークが確認された。又白色の
生成微粒子の圧粉体が108Ωcm以上の高比抵抗値
を示したことにより、生成粒子は、SiO2である
と同定した。 The generated RuO 2 ultrafine particle aggregate was heated to 600℃.
When heat treated with
It was found that the peak was only for RuO 2 . According to X-ray diffraction of the SiO 2 ultrafine particles, the peak of SiO 2 was broad and appeared to be amorphous, but the peak of Si was confirmed by X-ray fluorescence analysis. Furthermore, since the green compact of the white produced fine particles showed a high specific resistance value of 10 8 Ωcm or more, the produced particles were identified as SiO 2 .
尚、電極中、陽極のハース部分も黒鉛などのカ
ーボンで構成してもよい。上記のように、少くと
も陰極をカーボンで作成すれば、タングステン、
タンタルなどの高融点金属材料を電極とするもの
に比し、材料の入手が容易で、且つ安価な製造装
置を構成できる。 Incidentally, in the electrode, the hearth portion of the anode may also be made of carbon such as graphite. As mentioned above, if at least the cathode is made of carbon, tungsten,
Compared to an electrode made of a high melting point metal material such as tantalum, the material is easily available and a manufacturing device can be constructed at low cost.
（発明の効果）
このように本発明によるときは、金属材料を酸
素雰囲気下でアーク放電により加熱酸化蒸発させ
てその酸化物超微粒子を生成するに当り、そのア
ーク放電電極の少くとも陰極をカーボン電極で構
成してアーク放電を行なつたので、従来のような
タングステン陰極のようなその酸化物超微粒子が
目的とする金属材料の酸化物超微粒子の集積体中
に混入することがなく、良質の製品が得られ、上
記従来の生成法の不都合を解消した等の効果を有
する。(Effects of the Invention) According to the present invention, at least the cathode of the arc discharge electrode is heated to oxidize and evaporate the metal material by arc discharge in an oxygen atmosphere to generate ultrafine oxide particles. Since the electrode is used to perform arc discharge, the ultrafine oxide particles do not mix into the aggregate of ultrafine oxide particles of the target metal material, unlike in conventional tungsten cathodes, resulting in high quality. A product is obtained, which has the effect of eliminating the disadvantages of the above-mentioned conventional production methods.
第１図は、本発明を実施する一例の製造装置の
線図、第２図は、その製品酸化物超微粒子のＸ線
回析結果のグラフを示す。
１……真空容器、２……陽極、３……カーボン
陽極、４……直流電源、５……酸素ガス導入管、
９……真空ポンプ、ａ……金属材料。
FIG. 1 is a diagram of an example of a manufacturing apparatus for carrying out the present invention, and FIG. 2 is a graph of the results of X-ray diffraction of the product ultrafine oxide particles. 1... Vacuum container, 2... Anode, 3... Carbon anode, 4... DC power supply, 5... Oxygen gas introduction tube,
9...Vacuum pump, a...Metal material.
Claims (1)
アーク放電で加熱蒸発させ、その金属酸化物超微
粒子を製造する方法において、アーク放電の電極
の少くとも陰極をカーボンで構成してアーク放電
を行なうようにしたことを特徴とする酸化物超微
粒子の生成法。1. In a method of producing ultrafine metal oxide particles by heating and vaporizing a metal material by arc discharge between electrodes in an oxygen-containing atmosphere, at least the cathode of the arc discharge electrode is made of carbon to generate arc discharge. A method for producing ultrafine oxide particles, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22840386A JPS6385006A (en) | 1986-09-29 | 1986-09-29 | Formation of ultrafine particle of oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22840386A JPS6385006A (en) | 1986-09-29 | 1986-09-29 | Formation of ultrafine particle of oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6385006A JPS6385006A (en) | 1988-04-15 |
| JPH0352401B2 true JPH0352401B2 (en) | 1991-08-09 |
Family
ID=16875918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22840386A Granted JPS6385006A (en) | 1986-09-29 | 1986-09-29 | Formation of ultrafine particle of oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6385006A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1947711A2 (en) | 2001-09-19 | 2008-07-23 | Kawasaki Jukogyo Kabushiki Kaisha | Three-dimensional battery and its electrode structure and method for producing electrode material of three-dimensional battery |
-
1986
- 1986-09-29 JP JP22840386A patent/JPS6385006A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1947711A2 (en) | 2001-09-19 | 2008-07-23 | Kawasaki Jukogyo Kabushiki Kaisha | Three-dimensional battery and its electrode structure and method for producing electrode material of three-dimensional battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6385006A (en) | 1988-04-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |