JPH089726B2 - Plasma gas phase reactor - Google Patents
Plasma gas phase reactorInfo
- Publication number
- JPH089726B2 JPH089726B2 JP63319429A JP31942988A JPH089726B2 JP H089726 B2 JPH089726 B2 JP H089726B2 JP 63319429 A JP63319429 A JP 63319429A JP 31942988 A JP31942988 A JP 31942988A JP H089726 B2 JPH089726 B2 JP H089726B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- plasma
- fine particles
- exhaust port
- reaction gas
- 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 - Lifetime
Links
- 238000006243 chemical reaction Methods 0.000 claims description 70
- 239000010419 fine particle Substances 0.000 claims description 33
- 239000012495 reaction gas Substances 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 19
- 238000010574 gas phase reaction Methods 0.000 claims description 14
- 230000006837 decompression Effects 0.000 claims description 13
- 239000012808 vapor phase Substances 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 description 17
- 239000011553 magnetic fluid Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000000084 colloidal system Substances 0.000 description 7
- 239000000956 alloy Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- -1 alkyl Naphthalene Chemical compound 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002699 waste material Substances 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0894—Processes carried out in the presence of a plasma
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/19—Details relating to the geometry of the reactor
- B01J2219/194—Details relating to the geometry of the reactor round
- B01J2219/1941—Details relating to the geometry of the reactor round circular or disk-shaped
- B01J2219/1942—Details relating to the geometry of the reactor round circular or disk-shaped spherical
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
- H01J2237/32—Processing objects by plasma generation
- H01J2237/33—Processing objects by plasma generation characterised by the type of processing
- H01J2237/332—Coating
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Chemical Vapour Deposition (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） この発明は、プラズマ気相反応装置に関するものであ
る。さらに詳しくは、この発明は、金属または合金、金
属酸化物、金属窒化物等の微粒子や、これら微粒子の磁
性流体もしくはコロイドの製造に有用な、プラズマ放電
の安定性に優れ、かつ放電を長時間持続させることので
きる新しい低温プラズマ気相反応装置に関するものであ
る。TECHNICAL FIELD The present invention relates to a plasma gas phase reactor. More specifically, the present invention is useful for the production of fine particles of metals or alloys, metal oxides, metal nitrides, etc., and magnetic fluids or colloids of these fine particles, which have excellent stability of plasma discharge and discharge for a long time. The present invention relates to a new low temperature plasma gas phase reactor which can be sustained.
（従来の技術） 従来より様々な方式の低温プラズマ気相反応装置が知
られており、機能性薄膜の製造等に広く用いられてい
る。(Prior Art) Various types of low-temperature plasma vapor phase reactors have been conventionally known, and are widely used for producing functional thin films and the like.
これらの真空反応装置は、いずれも反応容器を固定し
た形式のものであり、外部より反応性ガスを導入し、ま
たは蒸着物質を蒸発させて基板に薄膜を形成することを
特徴としている。All of these vacuum reactors are of a type in which a reaction container is fixed, and are characterized in that a reactive gas is introduced from the outside or a vapor deposition substance is evaporated to form a thin film on a substrate.
しかしながら、このような従来の反応装置の場合に
は、プラズマ反応によって微粒子を製造するには適して
いないという欠点があった。すなわち、微粒子を製造す
る場合には、微粒子が真空反応容器内のいたる所に付着
し、その捕集が困難で回収率も悪く、また反応温度も真
空内で不均一であるため、堆積する場所によって生成物
質の組成が均一でないという欠点があった。However, such a conventional reactor has a drawback that it is not suitable for producing fine particles by plasma reaction. That is, in the case of producing fine particles, the fine particles adhere everywhere in the vacuum reaction vessel, and it is difficult to collect the fine particles, the recovery rate is poor, and the reaction temperature is non-uniform in the vacuum. However, the composition of the product is not uniform.
また、さらに、従来の反応装置においては、生成した
微粒子を磁性流体やコロイドとして液体中に捕集しよう
とすることも極めて困難であった。Further, in the conventional reaction apparatus, it has been extremely difficult to collect the produced fine particles in the liquid as a magnetic fluid or a colloid.
このような欠点を解消するために、この発明の発明者
らは、すでに新しい形式の低温プラズマ気相反応装置を
開発し、その実用化の利点を確認してもいる（特開昭63
−31536号公報）。この装置を例示したものが第２図で
ある。In order to overcome such drawbacks, the inventors of the present invention have already developed a new type of low temperature plasma gas phase reactor and confirmed the advantages of its practical use (Japanese Patent Laid-Open No. 63-63,631).
-31536). An example of this device is shown in FIG.
このプラズマ気相反応装置は、上記した微粒子を製造
する場合には、生成物質の組成が均一で粒径のそろった
微粒子を高い回収率で製造でき、またそれらの微粒子等
の磁性流体やコロイドを製造するについては、液状媒質
を使用するための特別の装置を必要とせず簡便に製造で
きるという利便性にも優れたものである。In the case of producing the above-mentioned fine particles, this plasma vapor phase reaction apparatus can produce fine particles having a uniform composition of the produced substance and having a uniform particle size at a high recovery rate, and can produce a magnetic fluid or colloid such as those fine particles. Regarding the production, it is excellent in convenience that it can be easily produced without requiring a special device for using a liquid medium.
第２図に例示したように、このプラズマ気相反応装置
は、内壁が曲面形状の真空容器（ア）を有しており、こ
の真空容器（ア）に開口部（イ）を設け、バルブ（ウ）
を介して真空ポンプ（エ）を接続している。この開口部
（イ）には、ガス導入管としての機能を備えた高周波電
極（オ）を挿入しており、この高周波電極（オ）の先端
を真空容器（ア）内に配置してもいる。また、高周波電
極（オ）と対向するように、真空容器（ア）内には、接
地電極（カ）を配備してもいる。As illustrated in FIG. 2, this plasma vapor phase reaction apparatus has a vacuum container (a) having an inner wall with a curved shape, and the vacuum container (a) is provided with an opening (a) and a valve ( C)
The vacuum pump (D) is connected via. A high-frequency electrode (e) having a function as a gas introduction tube is inserted into the opening (a), and the tip of the high-frequency electrode (e) is arranged inside the vacuum container (a). . Further, a ground electrode (f) is provided in the vacuum container (a) so as to face the high frequency electrode (e).
このプラズマ気相反応装置を用いて、プラズマ気相反
応を行うには、まず、真空容器（ア）内部を真空ポンプ
（エ）により排気し、真空容器（ア）をたとえば図中の
矢印の方向に回転させる。次いで、水素、アルゴン等雰
囲気ガス（キ）および原料ガス（ク）を真空容器（ア）
内の高周波電極（オ）の先端部のガス吹出口（ケ）より
噴出させる。高周波電源（コ）により高周波電圧を印加
し、高周波電極（オ）および接地電極（カ）の両電極間
にプラズマ（サ）を発生させ、所望の金属、合金または
セラミック等の微粒子を生成させる。In order to perform a plasma gas phase reaction using this plasma gas phase reaction apparatus, first, the inside of the vacuum container (a) is evacuated by a vacuum pump (d), and the vacuum container (a) is moved in the direction of the arrow in the figure, for example. Rotate to. Then, the atmosphere gas (g) such as hydrogen and argon and the source gas (g) are put into a vacuum container (a).
The gas is discharged from the gas outlet (K) at the tip of the high-frequency electrode (E) inside. A high-frequency voltage is applied by a high-frequency power source (U), plasma (SA) is generated between both electrodes of the high-frequency electrode (E) and the ground electrode (F), and fine particles of a desired metal, alloy, ceramic or the like are generated.
これらの微粒子を含む磁性流体もしくはオロイドなど
を製造する場合には、真空容器（ア）内に液状媒質
（シ）を装入し、真空容器（ア）を回転させながら、プ
ラズマ気相反応させて、生成する微粒子を、液状媒質
（シ）の媒体中に捕集する。こうすることにより、微粒
子の生成と同時に磁性流体またはコロイドなどを製造す
ることができる。When manufacturing a magnetic fluid or an oloid containing these fine particles, a liquid medium (SI) is charged in the vacuum container (A) and a plasma gas phase reaction is performed while rotating the vacuum container (A). The generated fine particles are collected in the liquid medium (Si). By doing so, a magnetic fluid or a colloid can be produced at the same time as the generation of the fine particles.
（発明が解決しようとする課題） しかしながら、このような優れた操作機能性を有する
プラズマ気相反応装置ではあるものの、依然として解決
しなければならない課題が残されてもいた。(Problems to be Solved by the Invention) However, although the plasma vapor phase reactor has such excellent operating functionality, there still remains a problem to be solved.
すなわち、たとえば第２図に例示したような横回転型
のプラズマ気相反応装置においては、開口部（イ）を真
空ポンプ（エ）等の排気系とともにガス導入管兼用の高
周波電極（オ）の挿入部ともしているため、高周波電極
（オ）の周辺に減圧した空間が広く依存し、これによっ
て微粒子の生成反応に関与しない減圧空間においても放
電が発生するのが避けられない。That is, for example, in a horizontal rotation type plasma gas phase reaction device as illustrated in FIG. 2, the opening (a) is provided with an exhaust system such as a vacuum pump (d) and a high frequency electrode (e) also serving as a gas introduction pipe. Since it also serves as an insertion portion, the decompressed space widely depends on the periphery of the high-frequency electrode (e), and thus discharge is unavoidable even in the decompressed space that is not involved in the reaction for producing fine particles.
このため、微粒子の生成反応に関与しない空間での放
電に電力が消費され、これにともない微粒子の生成反応
域のプラズマ放電の状態が不安定となり、反応原料ガス
の流れも複雑で、反応生成物の粒径や性状が不均一にな
るという欠点があった。For this reason, electric power is consumed for the discharge in the space that is not involved in the particle generation reaction, the plasma discharge state in the particle generation reaction region becomes unstable accordingly, and the flow of the reaction raw material gas is complicated. However, there was a defect that the particle size and properties of were not uniform.
また、この現象によって長時間のプラズマ気相反応の
持続も不可能となり、装置の運転操作が面倒でもあっ
た。また、さらには、微粒子の生成反応域以外で放電が
発生することにより、電極部材などの消耗が著しいとい
う問題もあった。Further, this phenomenon also makes it impossible to sustain the plasma gas-phase reaction for a long time, which makes the operation of the apparatus troublesome. Further, there is also a problem that the electrode member and the like are significantly consumed due to the occurrence of discharge in a region other than the reaction region for producing fine particles.
この発明は、以上のような事情に鑑みてなされたもの
であり、良好な操作機能性を有する横回転型のプラズマ
気相反応装置の特徴を生かし、しかも放電状態の不安定
性を解消し、プラズマ放電を長時間安定して持続でき、
金属または合金の微粒子、金属酸化物または金属窒化物
等の微粒子やこれらの微粒子からなる磁性流体もしくは
コロイド等を高効率で製造することができる改良された
プラズマ気相反応装置を提供することを目的としてい
る。The present invention has been made in view of the above circumstances, takes advantage of the characteristics of a horizontal rotation type plasma gas phase reactor having good operating functionality, and eliminates the instability of the discharge state, plasma Discharge can be stably maintained for a long time,
An object of the present invention is to provide an improved plasma gas phase reaction apparatus capable of highly efficiently producing metal or alloy fine particles, metal oxide or metal nitride fine particles, and magnetic fluids or colloids made of these fine particles. I am trying.
（課題を解決するための手段） この発明は、上記の課題を解決するために、回転対称
形の曲面内壁を有し、液状媒質を装入した回転真空反応
容器の横方向回転軸の両端に、減圧用排気口と反応ガス
吹出口とが対向して設けられ、この減圧用排気口および
反応ガス吹出口の開口部には回転自在な封止機構が設け
られるとともに、反応容器の減圧用排気口より接地電極
が、また、反応ガス吹出口より低温プラズマ発生用電極
が挿入配設されており、低温グロー放電プラズマの発生
により生成された微粒子が反応容器内の液状媒質に捕集
されることを特徴とするプラズマ気相反応装置を提供す
る。(Means for Solving the Problem) In order to solve the above-mentioned problems, the present invention has a rotationally symmetric curved inner wall and is provided at both ends of a horizontal rotation shaft of a rotary vacuum reaction container charged with a liquid medium. The decompression exhaust port and the reaction gas outlet are provided to face each other, and a rotatable sealing mechanism is provided at the openings of the decompression exhaust port and the reaction gas outlet, and the decompression exhaust of the reaction container is also provided. A ground electrode is inserted from the mouth and a low temperature plasma generation electrode is inserted from the reaction gas outlet, and the fine particles generated by the generation of the low temperature glow discharge plasma are collected in the liquid medium in the reaction vessel. There is provided a plasma gas phase reaction device characterized by:
より具体的には、プラズマ発生用高周波電極は、反応
ガス吹出管として使用してもよく、高周波電極に複数の
反応ガス吹出口を形成し、反応ガスを反応容器内に導入
してもよい。More specifically, the plasma-generating high-frequency electrode may be used as a reaction gas blowing tube, or a plurality of reaction gas outlets may be formed in the high-frequency electrode to introduce the reaction gas into the reaction container.
また、反応ガス吹出管のみを反応容器内に配置する場
合には、プラズマ放電の発生手段として、反応容器の内
部にRF誘導コイルを設けることもできる。Further, when only the reaction gas blowing pipe is arranged in the reaction vessel, an RF induction coil can be provided inside the reaction vessel as a means for generating plasma discharge.
なお、反応ガス吹出管または反応ガス吹出管兼用の高
周波電極の表面積は、反応容器内に配置する接地電極の
表面積よりも小さいものとすることが好ましい。The surface area of the reaction gas blow-out tube or the high-frequency electrode that also serves as the reaction gas blow-out tube is preferably smaller than the surface area of the ground electrode arranged in the reaction vessel.
また、この発明においては、反応容器の曲面内壁を球
状、回転楕円形状あるいは円筒状とし、この液状媒質が
反応容器の内壁に一様に展開するようにする。Further, in the present invention, the curved inner wall of the reaction vessel is spherical, spheroidal or cylindrical, and the liquid medium is uniformly spread on the inner wall of the reaction vessel.
（作用） この発明のプラズマ気相反応装置においては、接地電
極を挿入配設した減圧用排気口と低温プラズマ発生用の
高周波電極を挿入配設した反応ガス吹出口とを、各々、
分離して回転軸の両端部に対向するように反応容器に配
設しているので、反応ガスの流れは接地電極と減圧用排
気口に向けて一方向であり、従来の装置のように微粒子
の生成反応域以外の領域に反応に関与しない減圧域は生
成せず、不必要、かつ反応にとって好ましくないプラズ
マ放電が発生することはなく、微粒子の生成反応域の放
電状態を高安定に保持することができる。(Operation) In the plasma vapor phase reaction apparatus of the present invention, the decompression exhaust port having the ground electrode inserted therein and the reaction gas outlet having the high frequency electrode for low temperature plasma generation inserted therein are respectively
Since they are separated and arranged in the reaction vessel so as to face both ends of the rotating shaft, the flow of the reaction gas is in one direction toward the ground electrode and the decompression exhaust port, and the particles are the same as in the conventional device. In the region other than the production reaction region, no decompressed region that does not participate in the reaction is produced, and unnecessary and unfavorable plasma discharge does not occur, and the discharge state in the production reaction region of fine particles is maintained highly stable. be able to.
これによって生成する微粒子の粒径や性状は均一とな
り、また高周波電力の浪費を防止できる。As a result, the particle size and properties of the fine particles generated are uniform, and waste of high frequency power can be prevented.
（実施例） 次に図面に沿って実施例を示し、この発明のプラズマ
気相反応装置についてさらに詳しく説明する。(Example) Next, an example will be described with reference to the drawings, and the plasma vapor phase reaction apparatus of the present invention will be described in more detail.
第１図は、この発明のプラズマ気相反応装置の一例を
示した構成断面図である。FIG. 1 is a sectional view showing the configuration of an example of the plasma vapor phase reaction apparatus of the present invention.
この例においては、反応容器（１）の横方向回転軸の
両端に減圧用排気口（２）および反応ガス吹出口（３）
を回転軸上に対向して設けている。減圧用排気口（２）
には、パルプ（４）を介して真空ポンプ（５）を接続
し、また、減圧用排気口（２）からは接地電極（６）を
挿入している。反応ガス吹出口（３）からは、反応ガス
吹出管兼用の高周波電極（７）を挿入している。この高
周波電極（７）の先端には複数の反応ガス吹出口（８）
を形成している。In this example, a pressure reducing exhaust port (2) and a reaction gas outlet port (3) are provided at both ends of the lateral rotation axis of the reaction vessel (1).
Are provided facing each other on the rotating shaft. Exhaust port for decompression (2)
A vacuum pump (5) is connected to this via a pulp (4), and a ground electrode (6) is inserted from the decompression exhaust port (2). A high-frequency electrode (7) which also serves as a reaction gas outlet pipe is inserted from the reaction gas outlet (3). A plurality of reaction gas outlets (8) are provided at the tip of the high frequency electrode (7).
Is formed.
このように、接地電極（６）と反応ガス吹出管兼用の
高周波電極（７）は、各々、減圧用排気口（２）および
反応ガス吹出口（３）より反応容器（１）内に挿入配置
しているので、互いに対向する位置関係にある。In this way, the ground electrode (6) and the high-frequency electrode (7) that also serves as the reaction gas blowing pipe are inserted and arranged in the reaction vessel (1) through the decompression exhaust port (2) and the reaction gas blowing port (3), respectively. Therefore, they are in a positional relationship of facing each other.
この第１図に示したように、接地電極（６）の表面積
は、高周波電極（７）のものよりも広くしている。この
ことにより、プラズマ気相反応はさらに高安定性、高効
率なものとなる。As shown in FIG. 1, the surface area of the ground electrode (6) is larger than that of the high frequency electrode (7). As a result, the plasma gas phase reaction becomes even more stable and highly efficient.
反応ガス吹出管兼用の高周波電極（７）は、様々な形
状のものとしてもよい。たとえば複数のガス吹出口を持
つコイル状の電極としてもよいし、あるいは先端に複数
のガス吹出口を有する平板状の反応ガス吹出管兼用の高
周波電極とすることもできる。The high-frequency electrode (7) which also serves as the reactive gas blowing tube may have various shapes. For example, a coil-shaped electrode having a plurality of gas outlets may be used, or a flat plate-shaped high-frequency electrode also serving as a reaction gas outlet tube having a plurality of gas outlets may be used.
反応ガス吹出管と高周波電極とを兼用しない場合に
は、反応容器（１）外周部にRF誘導コイルを設けること
もできる。When the reaction gas blowing tube and the high frequency electrode are not used together, an RF induction coil may be provided on the outer peripheral portion of the reaction vessel (1).
反応容器（１）の両端に設けた減圧排気口（２）およ
び反応ガス吹出口（３）には、回転自在な封止機構とし
てＯリング（９）を配備し、反応容器（１）内部を気密
に保持するとともに、反応容器（１）を回転できるよう
にしている。もちろん、このような回転自在な封止機構
はＯリング（９）に限定されることはない。また、この
例においては、反応容器（１）の内壁は球状の曲面とし
ているが、特にその形状に制限はなく、反応容器（１）
の底部に後述する液状媒質を装入することができ、反応
容器（１）の回転により液状媒質を反応容器（１）の内
壁に一様に展開させることのできる回転楕円形状または
円筒状等の回転対称形形状としてもよい。An O-ring (9) is provided as a rotatable sealing mechanism at the decompression exhaust port (2) and the reaction gas outlet port (3) provided at both ends of the reaction container (1) so that the inside of the reaction container (1) is The reaction vessel (1) is kept airtight and rotatable. Of course, such a rotatable sealing mechanism is not limited to the O-ring (9). Further, in this example, the inner wall of the reaction vessel (1) has a spherical curved surface, but the shape is not particularly limited, and the reaction vessel (1)
A liquid medium, which will be described later, can be charged into the bottom of the reaction vessel (1), and the liquid medium can be uniformly spread on the inner wall of the reaction vessel (1) by the rotation of the reaction vessel (1). It may have a rotationally symmetrical shape.
このような反応容器（１）をその回転軸のまわりに回
転させる回転機構としては、減圧用排気口（２）の端部
に歯車（10）を設け、モータ（11）に装備したもつ一つ
の歯車（12）と歯合させ、また反応ガス導入口（３）端
部はＯリング（９）を有する軸受け（13）に連結する機
構としている。モータ（11）を駆動させることによっ
て、反応容器（１）を回転させることができる。さらに
この例においては、軸受け（13）をベローズ（14）を介
して固定してもいる。ベローズ（14）を用いることによ
り、反応容器（１）の回転による芯ぶれを吸収すること
ができ、反応容器（１）の回転を円滑に行うことができ
る。As a rotation mechanism for rotating such a reaction container (1) around its rotation axis, a gear (10) is provided at the end of the decompression exhaust port (2), and a motor equipped with a gear (10) is used. The mechanism is such that it meshes with the gear (12) and the end of the reaction gas introduction port (3) is connected to a bearing (13) having an O-ring (9). The reaction container (1) can be rotated by driving the motor (11). Further, in this example, the bearing (13) is fixed via the bellows (14). By using the bellows (14), it is possible to absorb core runout due to the rotation of the reaction container (1), and the reaction container (1) can be smoothly rotated.
たとえば、以上のように例示したプラズマ気相反応装
置を用いて、金属、合金またはセラミックスなどの微粒
子の構造は、次のような操作により行うことができる。For example, the structure of fine particles such as metal, alloy or ceramics can be formed by the following operations using the plasma vapor phase reaction apparatus exemplified above.
すなわち、真空ポンプ（５）により、反応容器（１）
内部を排気し減圧する。次いで、各種の反応ガス（15）
を反応容器（１）内に導入して吹出させる。この例にお
いては、反応ガス（15）は、反応ガス吹出管兼用の高周
波電極（７）に形成した反応ガス噴出口（８）より反応
容器（１）内に吹出させる。ここで、反応容器（１）を
モータ（11）の駆動によって回転させ、高周波電極（1
6）より接地電極（６）および高周波電極（７）の両電
極間に低温プラズマ（17）放電を発生させる。この低温
プラズマ（17）によって反応ガス（15）相互のプラズマ
気相反応が進行する。所望の金属、合金またはセラミッ
クスなどの微粒子（18）を生成させることができる。生
成したこれらの微粒子（18）は反応容器（１）の内壁に
一様に付着する。反応終了後、反応容器（１）内壁に付
着した微粒子（18）を採集する。That is, by the vacuum pump (5), the reaction vessel (1)
Evacuate the interior and reduce the pressure. Then various reaction gases (15)
Is introduced into the reaction vessel (1) and blown out. In this example, the reaction gas (15) is blown into the reaction container (1) from a reaction gas jet port (8) formed in the high-frequency electrode (7) which also serves as a reaction gas blow-out pipe. Here, the reaction container (1) is rotated by the drive of the motor (11), and the high frequency electrode (1
6) A low temperature plasma (17) discharge is generated between the ground electrode (6) and the high frequency electrode (7). The low temperature plasma (17) causes a plasma gas phase reaction between the reaction gases (15). Fine particles (18) of a desired metal, alloy or ceramic can be generated. The produced fine particles (18) uniformly adhere to the inner wall of the reaction container (1). After completion of the reaction, the fine particles (18) attached to the inner wall of the reaction container (1) are collected.
これらの微粒子（18）の磁性流体やコロイドなどを製
造する場合には、反応容器（１）に液状媒質（19）を装
入し、上述と同様な操作を行う。When producing a magnetic fluid or colloid of these fine particles (18), the liquid medium (19) is charged into the reaction vessel (1) and the same operation as described above is performed.
反応容器（１）を回転させると液状媒質（19）は、反
応容器（１）の内壁に一様に展開し、液体膜（20）を形
成する。この液体膜（20）に、プラズマ気相反応により
生成した金属、合金またはセラミックス等の微粒子が付
着し、反応容器（１）の回転により反応容器（１）底部
の液状媒質（19）に回収され、所望の磁性流体あるいは
コロイドが得られる。When the reaction container (1) is rotated, the liquid medium (19) spreads uniformly on the inner wall of the reaction container (1) to form a liquid film (20). Fine particles of metal, alloy, ceramics or the like generated by the plasma gas phase reaction adhere to the liquid film (20) and are collected in the liquid medium (19) at the bottom of the reaction container (1) by the rotation of the reaction container (1). , A desired magnetic fluid or colloid can be obtained.
以上のように、この発明の装置においては、高周波電
極（７）付近に従来装置のように微粒子生成反応域以外
の不必要な空間がないため、放電によるプラズマの発生
域は限定され、高周波電力を有効に気相反応に使用する
ことができ、また、微粒子生成反応域以外の領域におけ
る放電を防止することができることから、装置を長時間
運転してもプラズマの状態を高安定に保持することがで
きる。As described above, in the device of the present invention, unlike the conventional device, there is no unnecessary space other than the fine particle generation reaction region in the vicinity of the high frequency electrode (7), the plasma generation region by discharge is limited, and the high frequency power Can be effectively used in the gas phase reaction, and discharge can be prevented in a region other than the fine particle formation reaction region, so that the plasma state can be maintained highly stable even when the device is operated for a long time. You can
（磁性流体の製造） この第１図に例示したプラズマ気相反応装置を用い
て、磁性流体を製造した例を説明すると、まず、操作条
例としては次の通りとした。(Production of Magnetic Fluid) An example of producing a magnetic fluid by using the plasma vapor phase reaction apparatus illustrated in FIG. 1 will be described. First, the operation regulations are as follows.
反応ガス：Fe(CO)5 3cc/分 Ar 100cc/分 N2 20cc/分 反応容器内圧力:1mbar 高周波 :13.56MHz,100W 回転速度 :10回転／分 液状媒質 ：ポリブテニルコハク酸ポリアミンのア
ルキルナフタレン10％溶液（100cc） 反応時間 :20時間 この反応によって、Fe3N微粒子20gを含む磁性流体100
ccを得た。この磁性流体の飽和磁化は220ガウスであっ
た。反応を行っている間の放電状態は安定していた。放
電状態の調整は全く必要なかった。Reaction gas: Fe (CO) 5 3cc / min Ar 100cc / min N 2 20cc / min Reaction vessel pressure: 1mbar High frequency: 13.56MHz, 100W Rotation speed: 10 revolutions / min Liquid medium: Polybutenyl succinate polyamine alkyl Naphthalene 10% solution (100cc) Reaction time: 20 hours By this reaction, magnetic fluid 100 containing 20g of Fe 3 N particles
got cc. The saturation magnetization of this magnetic fluid was 220 gauss. The discharge state was stable during the reaction. No adjustment of the discharge state was necessary.
比較のために、第２図に示したような従来装置を用い
て上述の例と同様の条件で磁性流体を製造したが、約30
分〜１時間に１回の割合でプラズマ放電が停止した。長
時間の連続運転は不可能であった。For comparison, a magnetic fluid was manufactured under the same conditions as in the above example using a conventional device as shown in FIG.
The plasma discharge was stopped once every minute to 1 hour. Continuous operation for a long time was impossible.
（発明の効果） この発明のプラズマ気相反応装置によって、電力が有
効に利用され、高効率で微粒子を製造することができ
る。また、放電状態を高安定に保持することができるの
で、プラズマ気相反応を長時間連続して行わせることが
でき、装置の運転操作が極めて容易となり、無人運転す
ることも可能となる。また、微粒子生成反応が、放電状
態の安定により、高安定で促進され、プラズマ気相反応
により反応生成物の性状が均質となる。(Effects of the Invention) With the plasma vapor phase reaction device of the present invention, electric power is effectively used, and fine particles can be produced with high efficiency. Further, since the discharge state can be maintained highly stably, the plasma gas phase reaction can be continuously performed for a long time, the operation operation of the apparatus becomes extremely easy, and the unmanned operation can be performed. Further, the fine particle formation reaction is highly stable and promoted by the stable discharge state, and the properties of the reaction product become uniform by the plasma gas phase reaction.
さらには、放電発生域を限定することができるので、
電極部材などの消耗を著しく低減させることができる。Furthermore, since the discharge generation area can be limited,
It is possible to significantly reduce the consumption of the electrode members and the like.
第１図は、この発明のプラズマ気相反応装置の一例を示
した構成断面図である。 第２図は、従来装置の例を示した構成断面図である。 １……反応容器、２……減圧用排気口 ３……反応ガス吹出口、４……バルブ ５……真空ポンプ、６……接地電極 ７……反応ガス吹出管兼用高周波電極 ８……反応ガス噴出口、９……Ｏリング 10,12……歯車、11……モータ 13……軸受け、14……ベローズ 15……反応ガス、16……高周波電源 17……低温プラズマ、18……微粒子 19……液状媒質、20……液体膜FIG. 1 is a sectional view showing the configuration of an example of the plasma vapor phase reaction apparatus of the present invention. FIG. 2 is a sectional view showing the configuration of an example of a conventional device. 1 ... Reaction container, 2 ... Decompression exhaust port 3 ... Reaction gas outlet, 4 ... Valve 5 ... Vacuum pump, 6 ... Ground electrode 7 ... High-frequency electrode also serving as reaction gas outlet tube 8 ... Reaction Gas outlet, 9 …… O ring 10,12 …… Gear, 11 …… Motor 13 …… Bearing, 14 …… Bellows 15 …… Reaction gas, 16 …… High frequency power supply 17 …… Low temperature plasma, 18 …… Particles 19 ... Liquid medium, 20 ... Liquid film
Claims (2)
装入した回転真空反応容器の横方向回転軸の両端に、減
圧用排気口と反応ガス吹出口とが対向して設けられ、こ
の減圧用排気口および反応ガス吹出口の開口部には回転
自在な封止機構が設けられるとともに、反応容器の減圧
用排気口より接地電極が、また、反応ガス吹出口より低
温プラズマ発生用電極が挿入配設されており、低温グロ
ー放電プラズマの発生により生成された微粒子が反応容
器内の液状媒質に捕集されることを特徴とするプラズマ
気相反応装置。1. A pressure-reducing exhaust port and a reaction gas outlet are provided opposite to each other at both ends of a horizontal rotary shaft of a rotary vacuum reaction vessel having a rotationally symmetrical curved inner wall and charged with a liquid medium. The decompression exhaust port and the opening of the reaction gas outlet are provided with a rotatable sealing mechanism, and the decompression exhaust port of the reaction vessel is connected to the ground electrode, and the reaction gas outlet is used to generate low-temperature plasma. A plasma gas phase reaction device, wherein electrodes are inserted and arranged, and fine particles generated by generation of low-temperature glow discharge plasma are collected in a liquid medium in a reaction container.
を形成した請求項（１）記載のプラズマ気相反応装置。2. The plasma vapor phase reaction apparatus according to claim 1, wherein a reaction gas jet port is formed in the low temperature plasma generation electrode.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63319429A JPH089726B2 (en) | 1988-12-20 | 1988-12-20 | Plasma gas phase reactor |
| US07/451,766 US5012158A (en) | 1986-07-25 | 1989-12-18 | Plasma CVD apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63319429A JPH089726B2 (en) | 1988-12-20 | 1988-12-20 | Plasma gas phase reactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02164443A JPH02164443A (en) | 1990-06-25 |
| JPH089726B2 true JPH089726B2 (en) | 1996-01-31 |
Family
ID=18110097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63319429A Expired - Lifetime JPH089726B2 (en) | 1986-07-25 | 1988-12-20 | Plasma gas phase reactor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH089726B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20240024840A1 (en) * | 2020-09-18 | 2024-01-25 | Haydale Graphene Industries Plc | Methods and Apparatus for Delivering Feedstocks for Plasma Treatment |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5941772A (en) * | 1982-08-31 | 1984-03-08 | 井上金属工業株式会社 | Method of continuously drying organic solvent applied material |
| JPS62102827A (en) * | 1985-10-29 | 1987-05-13 | Natl Res Inst For Metals | Production of metallic or ceramic fine grain |
| JPS6333572A (en) * | 1986-07-25 | 1988-02-13 | Natl Res Inst For Metals | Plasma vapor reactor |
| JPS6331536A (en) * | 1986-07-25 | 1988-02-10 | Natl Res Inst For Metals | Plasma gaseous phase reaction apparatus |
-
1988
- 1988-12-20 JP JP63319429A patent/JPH089726B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02164443A (en) | 1990-06-25 |
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