JPS6385006A - Formation of ultrafine particle of oxide - Google Patents
Formation of ultrafine particle of oxideInfo
- Publication number
- JPS6385006A JPS6385006A JP22840386A JP22840386A JPS6385006A JP S6385006 A JPS6385006 A JP S6385006A JP 22840386 A JP22840386 A JP 22840386A JP 22840386 A JP22840386 A JP 22840386A JP S6385006 A JPS6385006 A JP S6385006A
- Authority
- JP
- Japan
- Prior art keywords
- cathode
- oxygen
- anode
- arc discharge
- ultrafine
- 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
- 239000011882 ultra-fine particle Substances 0.000 title abstract description 15
- 230000015572 biosynthetic process Effects 0.000 title 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010891 electric arc Methods 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 239000007769 metal material Substances 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 2
- 230000008016 vaporization Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 abstract description 4
- 239000010937 tungsten Substances 0.000 abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 14
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 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
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000008018 melting Effects 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 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
- 239000000203 mixture Substances 0.000 description 1
- 239000000843 powder Substances 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
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
Abstract
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Ｓｉｎ、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 is to heat and evaporate a high melting point metal material by arc discharge between metal electrodes in an oxygen-containing atmosphere, and then generate ultrafine metal oxide particles. known to produce. For example, by using a metal such as tungsten as a cathode and heating and vaporizing ruthenium or silicon by arc discharge, an aggregate of ultrafine metal oxide particles such as RuO2 or Sin 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５ｉ０２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った。(Problems to be Solved by the Invention) In the above conventional production method, the tungsten cathode is heated and oxidized little by little during arc discharge, and the oxidation is produced, and this oxide has a vapor pressure higher than that of metal. Because of its high content, it was inevitable that it would become ultrafine particles and evaporate, resulting in products that were mixed into the oxide ultrafine particle aggregates, which were the desired products such as RuO2 and 5i02.
（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特（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、 ＡＩ、Ｓｎ。(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. (Embodiment) Next, embodiments 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 that also serves as a water-cooled copper hearth that faces inside the vacuum vessel (1), and (3) is a water-cooled copper torch (
A is a carbon cathode formed by screwing a carbon cylinder (3b) made of graphite onto the tip of the anode (3a), and a is Ru, Si, AI, Sn housed on the upper surface of the anode (2).
Ｖ 、Ｔｉなどの金属材料、（４）は、陰陽極間を接続
する放電アーク用直流電源、（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
１４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％０□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 、 ２
５Ｖ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Ｉｔ
ｕＯ２や５ｉｎ２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
予め作成しであるので、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、ＲｕＯ□や５ｉｎ
２などの目的とする金Ｂ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１１ｕ０２や５ｉ０２な
どの金属酸化物超微粒子のみの生産が可能となる。(4) is a DC power source for a discharge arc that connects the cathode and anode; (5) is a mixed gas of inert gas and oxygen that is supplied to the container ( 1)
The gas inlet pipe (7) is an exhaust pipe that connects the inside of the vacuum container (1) with the vacuum pump (9) via the 14-node 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), and the inside of the vacuum container (1) is evacuated through the gas introduction pipe (5). A mixed gas of argon + 30% 0□ is introduced into the vacuum vessel (1) so that a mixed gas pressure of 100 Torr is maintained in the vacuum vessel (1), and in this state, for example, 25A, 2
Activate the 5V DC power supply (4) and connect the cathode and anode (2) (3>
An arc discharge is generated in between to heat and evaporate the metal material,
The oxide such as It is brought into contact with the oxygen gas atmosphere.
Desired ultrafine particles such as uO2 and 5in2 are produced. According to the present invention, since the cathode (3) is made of carbon such as graphite in advance, ultrafine oxide particles are not generated, and even when oxidized, it becomes CO2 gas, and the cathode (3) is made of carbon such as graphite. The ultrafine oxide particles of the cathode are RuO□ and 5in.
There is no fear that the gold B oxide ultrafine particles will be mixed into the target gold B oxide ultrafine particle aggregate such as No. 2, and it is possible to produce only pure ultrafine metal oxide particles such as 11u02 and 5i02.
上記の製法で得られたＲｕＯ２やＳｉＯ□の夫々の超微
粒子集積体につき、ＴＥＮ写真やＳＥＷ写真をとり、黒
鉛の混入が全くなく、平均粒径２００人の超微粒子のＲ
ｕＯ□、 ＳｉＯ□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
ゲット／フィルタ（モノクロ）二Ｃｕ、 ？ｌ１ＪＩ／
ｆｆｉ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。TEN and SEW photographs were taken of each of the ultrafine particle aggregates of RuO2 and SiO□ obtained by the above manufacturing method.
It was confirmed that aggregates of uO□ and SiO□ were obtained. X-ray diffraction of RuO2 ultrafine particle aggregate (target/filter (monochrome) 2Cu, ?l1JI/
Figure 2 shows the results for ffi current: 50 KV, 200 mA). In addition to the RuO2 peak, a small Ru peak was also detected, but no graphite was detected.
尚この生成されたＲｕＯ２超微粒子集合体を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った。５ｉ０２超微粒子のＸ
線回折によれば、５ｉｎ２のピークはブロードでありア
モルファスのようであったが、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１０
８Ωα以上の高比抵抗値を示したことにより、生成粒子
は、Ｓｉｎ。It has been found that when the RuO2 ultrafine particle aggregate thus produced is subjected to heat treatment at 600°C, the peak of Ru disappears and only the peak of RuO2 appears. 5i02 ultrafine particle X
According to line diffraction, the peak of 5in2 was broad and appeared to be amorphous, but a Si peak was confirmed by fluorescent X-ray analysis. In addition, the compacted powder of white produced fine particles was 10
Since the produced particles showed a high specific resistance value of 8Ωα or more, it was determined that they were Sin.
であると同定した。It was identified that
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 described above, if at least the cathode is made of carbon, the material is easier to obtain and a manufacturing apparatus can be constructed at a lower cost than when the electrode is made of a high melting point metal material such as tungsten or tantalum.
（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った
ので、従来のようなダンゲ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 arc discharge is performed using an electrode, the ultrafine oxide particles do not mix into the aggregate of ultrafine oxide particles of the target metal material, unlike the conventional Dungesten cathode. A product is obtained, and the above-mentioned disadvantages of the conventional production method are overcome.
第１図は、本発明を実施する一例の製造表装置線図、第
２図は、その製品酸化物超微粒子のＸ線回折結果のグラ
フを示ず。
（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 production table equipment diagram of an example of carrying out the present invention, and FIG. 2 does not show a graph of the X-ray diffraction results of the product ultrafine oxide particles. (1)...Vacuum container (2)...Anode (3)
...Carbon anode (4) ...DC power supply (5)
...Oxygen gas introduction pipe (9) ...Vacuum pump a...
Metal material
Claims (1)
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。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, the arc discharge is performed with at least the cathode of the arc discharge electrode made of carbon. 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 true JPS6385006A (en) | 1988-04-15 |
| JPH0352401B2 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) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2003028142A1 (en) | 2001-09-19 | 2005-01-13 | 川崎重工業株式会社 | Three-dimensional battery, electrode structure thereof, and method for manufacturing electrode material of three-dimensional battery |
-
1986
- 1986-09-29 JP JP22840386A patent/JPS6385006A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0352401B2 (en) | 1991-08-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |