JP2662986B2 - Method for producing ultrafine tungsten or tungsten oxide particles - Google Patents
Method for producing ultrafine tungsten or tungsten oxide particlesInfo
- Publication number
- JP2662986B2 JP2662986B2 JP63154868A JP15486888A JP2662986B2 JP 2662986 B2 JP2662986 B2 JP 2662986B2 JP 63154868 A JP63154868 A JP 63154868A JP 15486888 A JP15486888 A JP 15486888A JP 2662986 B2 JP2662986 B2 JP 2662986B2
- Authority
- JP
- Japan
- Prior art keywords
- tungsten
- plasma
- gas
- ultrafine
- ultrafine particles
- 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 - Fee Related
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は高温プラブマを用いてタングステン粉末原料
からタングステン超微粒子を，また酸化タングステン粉
末原料から酸化タングステン・タングステン混在超微粒
子を連続的に製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention continuously produces tungsten ultrafine particles from a tungsten powder raw material and tungsten oxide / tungsten mixed ultrafine particles from a tungsten oxide powder raw material using a high-temperature plasma. About the method.
（従来の技術および問題点） 超微粒子はそれが有する顕著な特性に注目され、各種
成分系超微粒子の製造法が研究・開発されつつある。タ
ングステン超微粒子も例えば焼結材への添加成分等とし
ての需要が見込まれ、また酸化タングステン超微粒子も
還元法により容易にタングステン超微粒子とすることが
可能であるので、前段階物質として同様である。(Conventional technology and problems) Ultrafine particles are noted for their outstanding properties, and methods for producing various component-based ultrafine particles are being researched and developed. Tungsten ultrafine particles are also expected to be demanded, for example, as an additive component to a sintered material, and tungsten oxide ultrafine particles can be easily converted into tungsten ultrafine particles by a reduction method. .
ところで、超微粒子を得るための方法は種々あるが、
バルクや通常粒径粉末のタングステン（以下元素記号の
Ｗを用いる）ないし酸化タングステン（以下化合物記号
のWO3を用いる）から超微粒子を得んとする場合、Ｗが
特に高融点金属として知られているところから、直ちに
高温プラズマを用いる方法が好ましいと想到される。By the way, there are various methods for obtaining ultrafine particles,
In the case of obtaining ultrafine particles from tungsten of a bulk or powder having a normal particle diameter (hereinafter, using W of an element symbol) or tungsten oxide (hereinafter, using WO 3 of a compound symbol), W is particularly known as a high melting point metal. From this point, it is thought that a method using high-temperature plasma is immediately preferable.
而して高温プラズマを発生させ、当該高温プラズマを
用いて素材から超微粒子を生成可能な従来法としては、
アークプラズマ法，高周波プラズマ法，直流プラズマジ
エツト法，あるいはハイプリツドプラズマ法等が挙げら
れる。これらの方法は周知の如く常圧（大気圧）状態下
で高温プラズマを発生させ得るが、以下に概要を述べる
とともに、従来技術をそのままＷやWO3の超微粒子化に
用いた場合に生ずる問題点を指摘する。As a conventional method capable of generating high-temperature plasma and generating ultrafine particles from a material using the high-temperature plasma,
Examples thereof include an arc plasma method, a high-frequency plasma method, a direct current plasma jet method, and a hybrid plasma method. These methods may generate a high temperature plasma at atmospheric pressure under (atmospheric pressure) conditions as is well known, together with the outlined below, the problem arising when using the ultrafine particles of the prior art as it is W or WO 3 Point out the point.
アークプラズマ法は，第２図（ａ）に示す如く，水冷
銅ハースＨ上に被溶解材バルクＢを載置して陽極と
し、その上方所定間隙を隔てて陰極である棒状電極CA
の先端を位置させ、両極間に電圧を印加して高温のアー
クプラズマP1を発生させ、当該アークプラズマP1によつ
てバルクＢを溶融・蒸発せしめ、発生する蒸気を冷却し
て超微粒子を得るようにしている。In the arc plasma method, as shown in FIG. 2 (a), a material B to be melted is placed on a water-cooled copper hearth H to serve as an anode, and a bar-shaped electrode CA serving as a cathode is provided with a predetermined gap therebetween.
The tip is positioned, and to generate an arc plasma P 1 of high temperature by applying a voltage between the electrodes, the arc plasma P 1 to allowed melting and evaporating the Yotsute bulk B, and by cooling the steam generated ultrafine particles I'm trying to get.
同法に従つてWO3超微粒子を製造する場合には、WO3の
バルクＢとＷからなる棒状電極CAとで両極を構成し、常
圧下で酸素ガスのアークプラズマP1によりWO3超微粒子
を生成させることができる。また、ＷのバルクＢと棒状
電極CAとを用い、水素ガスのアークプラズマP1によりＷ
超微粒子を生成可能である。然し乍ら、アークプラズマ
法は発生するアークプラズマP1の直径が極めて小さく、
生成率が極度に低く工業的生産には程遠いという欠点が
あるとともに、バルクＢが蒸発し尽くせば生産は停止さ
れ、さらには棒状電極CAも消耗するので、連続生産には
不向きという欠点がある。When manufacturing the Supporting connexion WO 3 ultrafine particles law, constitutes a bipolar with a rod electrode CA consisting of bulk B and W of WO 3, oxygen gas under normal pressure arc plasma P 1 by WO 3 ultrafine particles Can be generated. Further, using the bulk B and the rod-shaped electrode CA of W, W by arc plasma P 1 of hydrogen gas
Ultra fine particles can be produced. However, the arc plasma method is extremely small diameter of the arc plasma P 1 occurring,
The production rate is extremely low and it is far from industrial production, and if the bulk B evaporates completely, the production is stopped and the rod-shaped electrode CA is also consumed, so that it is not suitable for continuous production.
高周波プラズマ法は，第２図（ｂ）に示す如く，所定
雰囲気かつ常圧を維持する反応室CH、当該反応室CHに開
口するプラズマトーチＴ、当該プラズマトーチＴの外周
を巻回する高周波コイルＣ、および当該高周波コイルＣ
へ給電する高周波電源Ｅを備えた装置を用いる。プラズ
マトーチＴ内へ供給されるコアガス（プラズマの生成に
供されるガスを云う）Ｇを高周波電磁エネルギーにより
高温プラズマP2化し、当該高温プラズマフレームP2中へ
粉末原料をキヤリヤガスCGにのせて連続供給し、粉末原
料をプラズマフレームP2内で溶融・蒸発させ、かつ雰囲
気ガスと反応させる。反応により生成した粒子はプラズ
マフレームP2外に移行する過程で凝集して超微粒子とな
つて雰囲気ガス中に浮遊するので、雰囲気ガス排出路上
に設けた回収器に捕集するようにしている。As shown in FIG. 2 (b), the high-frequency plasma method uses a reaction chamber CH that maintains a predetermined atmosphere and normal pressure, a plasma torch T that opens into the reaction chamber CH, and a high-frequency coil that winds around the outer periphery of the plasma torch T. C and the high-frequency coil C
A device having a high-frequency power supply E for supplying power to the power supply is used. Continuous plasma torch core gas supplied into the T (referred gas used for generating plasma) G-temperature plasma P 2 turned into a high-frequency electromagnetic energy, by placing the powder material in Kiyariyagasu CG to the high temperature plasma flame P 2 in supplied, the powder raw material was melted and vaporized in the plasma flame P 2, and is reacted with the atmospheric gas. Since particles produced by the reaction is suspended in atmospheric gas aggregate during the process of transition to the outer plasma flame P 2 Te summer and ultrafine particles, so that collecting the collector provided in the atmospheric gas discharge path.
本発明者は、本発明をなすに先立つて同法に従つてＷ
ないしWO3粉末原料を超微粒子化せんとする実験を行つ
た。当該実験ではアルゴン等の不活性ガスをコアガスＧ
とし、粉末原料をコアガスＧと同質のキヤリヤガスCGに
のせてプラズマフレームP2の中間位置へ向けて供給する
ようにしたが、殆ど超微粒子化されないという実験結果
に終わつた。Prior to making the present invention, the present inventor
An experiment was conducted in which WO 3 powder raw material was converted into ultrafine particles. In this experiment, an inert gas such as argon was used as the core gas G.
And then, but put the powder material in Kiyariyagasu CG core gas G the same quality and to supply toward the intermediate position of the plasma flame P 2, Owa almost experimental results that are not ultrafine particles ivy.
また、上記実験の不首尾が粉末原料をプラズマフレー
ムP2の低温域plに供給する設定としたため、Ｗの高融点
・高沸点特性（融点:3387℃，沸点:5927℃）やプラズマ
領域内での滞留時間の短かさに起因するやも知れぬと想
定し、コアガスＧに粉末原料をのせてプラズマフレーム
P2中心高温域ph（10000K）に送り込むようにしたが、そ
の供給量を極度に僅少としない限り，高温プラズマフレ
ームP2が不安定となるという実験結果が得られ、当該試
みも失敗に終わつた。Further, failure of the experiment for the powder raw material was supplied set to a low temperature region pl of plasma flame P 2, high melting and high-boiling characteristics of W (melting point: 3387 ° C., boiling point: 5927 ° C.) and in the plasma region Assuming that it is likely to be due to the short residence time, the powder material is placed on the core gas G and the plasma flame
Was as fed into P 2 around the high temperature zone ph (10000K), unless insignificant the supply quantity to extreme, the experimental results that the high temperature plasma flame P 2 becomes unstable is obtained, the attempt also Owa failed I got it.
直流プラズマジエツト法は、第３図（ｃ）に示す如
く，水冷陰極CAと水冷陽極AN、コアガスＧの供給路T1、
および粉末原料をのせるキヤリヤガスCGの供給路T2を備
えたプラズマジエツトガンPGを用いて高温プラズマP3を
発生させるもので、通常は肉盛り，熔接等に使用され
る。同法はプラズマフレームP3の高温域phに粉末原料を
送り込んでもプラズマP3の不安定を招来しないという利
点がある。In the DC plasma jet method, as shown in FIG. 3 (c), a water-cooled cathode CA, a water-cooled anode AN, a supply path T 1 for a core gas G,
And the supply path T 2 of the Kiyariyagasu CG placing the powder material by using a plasma jet gun PG with those which generate high temperature plasma P 3, usually padding is used for welding or the like. Law has the advantage be fed to the powder material to a high temperature range ph plasma frame P 3 is not lead to instability of the plasma P 3.
同法に従つてＷないしWO3粉末原料を超微粒子化せん
として、陰極CAをＷ材製，陽極ANを銅材製とし、コアガ
スＧおよびキヤリヤガスCGに不活性ガスを用いて実験し
てみたが、プラズマP3の流速があまりにも高速のため、
粉末原料がプラズマフレームP3の中心高温域phを通過す
るにも拘わらず、充分に溶融・蒸発する暇なくプラズマ
フレームP3外に排出され、超微粒子化するに到らなかつ
た。According to the same method, W or WO 3 powder raw material was made into ultrafine particles, the cathode CA was made of W material, the anode AN was made of copper material, and the core gas G and the carrier gas CG were tested using an inert gas. , because of the high speed the flow velocity of the plasma P 3 is too,
Powder source despite passing through the center hot zone ph plasma frame P 3, are sufficiently melted and discharged leisure without outer plasma flame P 3 evaporates, has failed lead to super fine particles.
ハイプリツドプラズマ法は図示を省略するが、上記高
周波プラズマ法と直流プラズマジエツト法とを組合せた
もので、プラズマジエツトの流速が高速のため、直流プ
ラズマジエツト法における場合と同様にＷないしWO3の
超微粒子化には不適であつた。Although not shown, the hybrid plasma method is a combination of the high-frequency plasma method and the DC plasma jet method, and the flow rate of the plasma jet is high, so that W or W is the same as in the DC plasma jet method. It has been made unsuitable for ultra-fine particles of WO 3.
（発明の目的） 本発明はＷ超微粒子もしくはWO3超微粒子を製造する
場合、高温プラズマが得られる各従来法に存する上述の
問題点を解決するためになされたもので、粉末原料がＷ
ならばＷ超微粒子,WO3ならばWO3・Ｗ混在超微粒子を100
％生成率で連続生産可能とするタングステンもしくは酸
化タングステン超微粒子の製造方法を提供することを目
的とする。If INVENTION An object of the present invention is to produce a W ultrafine particles or WO 3 ultrafine particles, which has been made to solve the above problems existing in the prior art high temperature plasma is obtained, the powder material is W
If W ultra-fine particles, the WO 3 if WO 3 · W mixed ultrafine particles 100
It is an object of the present invention to provide a method for producing ultrafine particles of tungsten or tungsten oxide which enables continuous production at a% production rate.
（発明の構成） 本発明の構成は、 （１）100％窒素ガス，もしくは主成分が窒素ガスでア
ルゴンを添加したコアガスならびに雰囲気ガスを用い、 （２）微減圧雰囲気中に高温プラズマを発生せしめ、 （３）当該プラズマフレーム中へタングステン，もしく
は酸化タングステンの粉末原料を上記ガスと同質のキヤ
リヤガスにのせて連続供給することにより、 （４）上記粉末原料から超微粒子を生成せしめ、 （５）上記微減圧雰囲気を維持するために吸引される雰
囲気ガス流中に浮遊する超微粒子を連続的に捕集・回収
するようにした ことを特徴とするタングステンもしくは酸化タングステ
ン超微粒子の製造方法にある。(Structure of the Invention) The structure of the present invention is as follows: (1) 100% nitrogen gas or a core gas containing nitrogen gas as a main component and an atmosphere gas, and (2) high-temperature plasma is generated in a slightly reduced pressure atmosphere. (3) By continuously supplying a powder material of tungsten or tungsten oxide to the plasma frame on a carrier gas having the same quality as the above gas, (4) generating ultrafine particles from the powder material; A method for producing ultrafine tungsten or tungsten oxide particles, characterized in that ultrafine particles floating in an atmosphere gas flow sucked to maintain a slightly reduced pressure atmosphere are continuously collected and collected.
（発明の作用） 本発明法の特徴は、窒素ガス（以下分子記号N2と記
す）をコアガス，キヤリヤガスおよび雰囲気ガスとして
使用し、当該窒素ガスをa,超微粒子化反応に関与させる
とともに、b,プラズマの流速を不活性ガス使用時の場合
のそれより抑制するようにし、常圧で高温プラズマを
発生可能，かつ連続生産を可能とする従来法，即ち高周
波プラズマ法，直流プラズマジエツト法，あるいはハイ
ブリツドプラズマ法等におけるプラズマフレームを敢え
て微減圧した反応容器内で発生させることにより、上記
ａとの相乗効果でプラズマフレーム領域，特に尾炎部
領域を拡大させるようにした点にある。Feature of the present invention method (the action of the invention), nitrogen gas (hereinafter referred to as molecular symbol N 2) a core gas, used as Kiyariyagasu and atmospheric gas, the nitrogen gas a, together with to participate in micronized reaction, b The conventional method that suppresses the plasma flow rate from that in the case of using an inert gas and can generate high-temperature plasma at normal pressure and enables continuous production, that is, high-frequency plasma method, DC plasma jet method, Alternatively, a plasma flame in a hybrid plasma method or the like is intentionally generated in a reaction vessel which is slightly depressurized, so that the plasma flame region, particularly the tail flame region, is enlarged by a synergistic effect with the above-mentioned a.
上記構成によつて、プラズマフレームは高エンタルピ
ー化され、N2分子の解離により活性化した単原子となつ
たＮが供給される粉末原料の溶融・蒸発を促進し、さら
にはＮが拡大したプラズマフレーム領域内でＷないしWO
3蒸気と会合して超微粒子化反応をするに充分な時間を
確保し得る作用を発揮することとなる。According to the above configuration, the plasma flame has a high enthalpy, promotes the melting and evaporation of the powder raw material to which N, which is activated as a single atom activated by dissociation of N 2 molecules, is supplied, and further, the plasma in which N is expanded W or WO in the frame area
(3) An effect capable of securing a sufficient time for performing the ultrafine particle-forming reaction in association with the vapor is exerted.
この場合の微減圧は、実験結果から少なくとも700tor
r以下ならばプラズマフレームの領域拡大作用を齎す。In this case, the decompression is at least 700 torr based on the experimental results.
If it is less than r, an effect of expanding the area of the plasma frame is brought about.
また、粉末原料がＷである場合にはＷ超微粒子が、WO
3である場合にはWO3・Ｗ混在超微粒子が生成され、その
生成率はいずれの場合でも供給原料の100％である。When the powder material is W, W ultrafine particles are
If it is 3 WO 3 · W mixed ultrafine particles are produced, the production rate is 100% of the feedstock either case.
プラズマフレーム領域内での化学反応式は現時点で同
定されないが、以下のように推定される。即ち，例えば
供給粉末原料がＷの場合には、高温域でN2から解離した
単原子ＮがＷ蒸気と結合し、一時的に大きさが原子ない
し分子レベルのWN2,もしくはWN等の中間生成物蒸気とな
る。当該中間生成物蒸気は不定性であるので,3000K以下
の低温域でＮのN2への結合力が中間生成物結合力に勝
り、N2となると同時にＷが解離されるものと思われる。
また、供給粉末原料がWO3の場合には、中間生成物蒸気
の組成は不明なるも、少なくとも低温域でＮのN2への結
合力がＷとＯとの結合力に勝ることが実験結果から明確
にされるところである。Although the chemical reaction formula in the plasma flame region has not been identified at this time, it is estimated as follows. That is, for example, when the supply powder raw material is W, a single atom N dissociated from N 2 in a high temperature region is combined with W vapor, and temporarily has an intermediate size such as WN 2 or WN of an atomic or molecular level. It becomes product vapor. Since the intermediate product vapor is indefinite, it is considered that the binding force of N to N 2 exceeds the intermediate product binding force in a low temperature region of 3000 K or less, and W is dissociated simultaneously with N 2 .
When the feed powder material is WO 3 , although the composition of the intermediate product vapor is unknown, the experimental results show that at least in the low temperature region, the bonding force of N to N 2 exceeds the bonding force of W and O. Is to be clarified from.
而して、ＷないしWO3の超微粒子化にはN2の高温プラ
ズマが奏功するが、本発明者が本発明に先立つて行つた
アルゴン（Ar）100％の高温プラズマを用いた実験では
超微粒子化に失敗しており、少なくとも単原子Ｎの分子
N2への再結合が超微粒子化に寄与するとする推定が当を
得ていることを裏付けしている。Thus, high-temperature plasma of N 2 is effective in converting W or WO 3 into ultrafine particles. However, in experiments conducted by the present inventor prior to the present invention using high-temperature plasma of 100% argon (Ar), ultra-high-temperature plasma was used. Failure to atomize, at least a molecule of monoatomic N
This suggests that the presumption that recombination to N 2 contributes to ultrafine particle formation is correct.
（実施例） 本発明を例えば直流プラズマジエツト法に実施した場
合を第１図に示す。(Example) FIG. 1 shows a case where the present invention is applied to, for example, a DC plasma jet method.
図において、１は直流電源、２は第２図（ｃ）に示し
た同様な構造からなる上記直流電源１に接続するプラズ
マジエツトガン、３は上記プラズマジエツトガン２の先
端が挿入状態で配置されている反応容器、４は粉末原料
供給装置、５および６はN2およびArの供給源、７は反応
容器３に一方端が開口し，外周を冷却水Waで冷却される
水冷導管、８は上記水冷導管７の他方端が接続され，例
えば超微粒子を捕捉可能なメツシユのフイルタを備えた
回収器、９は上記回収器８に連接配置されたポンプであ
る。In the drawing, 1 is a DC power supply, 2 is a plasma jet gun connected to the DC power supply 1 having the same structure as shown in FIG. 2 (c), and 3 is a plasma jet gun 2 with its tip inserted. A reaction vessel 4 disposed therein, a powder raw material supply apparatus, 5 and 6 supply sources of N 2 and Ar, 7 a water-cooled conduit having one end open to the reaction vessel 3 and an outer periphery cooled by cooling water Wa, Reference numeral 8 denotes a collector connected to the other end of the water-cooled conduit 7 and provided with, for example, a mesh filter capable of capturing ultrafine particles. Reference numeral 9 denotes a pump connected to the collector 8.
上記プラズマジエツトガン２には、管路T1を介して例
えばN2・Ar混合ガスがコアガスＧとして供給され、また
管路T2を介して粉末原料供給装置４から単位時間当たり
所定量の粉末原料がN2・Ar混合ガスからなるキヤリヤガ
スCGにのせられて供給される。The plasma jet gun 2 is supplied with, for example, an N 2 .Ar mixed gas as a core gas G via a pipe T 1, and a predetermined amount per unit time from the powder raw material supply device 4 via a pipe T 2 . The powder raw material is supplied by being carried on a carrier gas CG comprising a N 2 .Ar mixed gas.
上記構成からなる装置により超微粒子を製造する場合
を以下に述べる。The case where ultrafine particles are produced by the apparatus having the above configuration will be described below.
まず、ポンプ９を始動させて反応容器3,水冷導管7,お
よび回収器８それぞれのエア抜きをするとともに、管路
T1を介してコアガスＧを反応容器３内に流入させてエア
雰囲気をコアガスＧ雰囲気に置換し、次いでコアガスＧ
の流入量とポンプ９の吸引力との関係において反応容器
３内の圧力が700torr以下の所定圧を維持する如く制御
・調整のうえ、プラズマジエツトガン２を点火する。プ
ラズマジエツトガン２の反応容器３内に位置する先端開
口から発生するプラズマフレームＰは、N2もしくは主成
分がN2のコアガスを用い，かつ反応容器３内が微減圧状
態としてあるので、従来法に比べてプラズマの流速は抑
制されるとともに、プラズマフレーム領域，特に低温域
plが広範囲に拡大している。この状態において管路T2を
開とし、粉末原料をキヤリヤガスCGにのせて供給する。
粉末原料は前掲作用の項で述べたとおりプラズマフレー
ムＰ内で蒸気となり、当該蒸気は活性化したＮと反応し
たのち、凝集しつつ超微粒子となつてプラズマフレーム
Ｐ外へ移行し、反応容器３内の雰囲気ガス中に浮遊す
る。反応容器３の雰囲気ガスは順次導管７を介して回収
器８へと導かれるので、雰囲気ガス中に浮遊する超微粒
子は回収器８内のフイルタに捕捉され、回収される。First, the pump 9 is started to evacuate the reaction vessel 3, the water-cooled conduit 7, and the recovery unit 8 respectively,
The core gas G is caused to flow into the reaction vessel 3 through T 1 to replace the air atmosphere with the core gas G atmosphere.
The plasma jet gun 2 is ignited after controlling and adjusting the pressure in the reaction vessel 3 to maintain a predetermined pressure of 700 torr or less in relation to the inflow amount of the pump 9 and the suction force of the pump 9. The plasma frame P generated from the tip opening located in the reaction vessel 3 of the plasma jet gun 2 uses a core gas of N 2 or a main component of N 2 and the inside of the reaction vessel 3 is in a slightly reduced pressure state. The plasma flow rate is suppressed as compared with the plasma method,
pl is widespread. The conduit T 2 is opened in this state, supplies topped with powdered raw material Kiyariyagasu CG.
The powdered raw material is converted into vapor in the plasma flame P as described in the section of the above-mentioned action, and the vapor reacts with the activated N, and then aggregates into ultra-fine particles to move out of the plasma flame P, and the reaction vessel 3 It floats in the atmosphere gas inside. Since the atmosphere gas in the reaction vessel 3 is sequentially led to the collection device 8 through the conduit 7, the ultrafine particles floating in the atmosphere gas are captured by the filter in the collection device 8 and collected.
（実験例） 本発明者が上記装置を用いて行つた多数の実験中の一
例を以下に開示する。(Experimental Examples) An example of a number of experiments performed by the inventor using the above-described apparatus will be disclosed below.
○実験条件 ＊粉末原料:WO3 平均粒径……20μｍ ＊プラズマガス（コアガス，キヤリヤガス） 成分および流量:N2……15/min Ar…… 5/min ＊プラズマ入力：電圧…… 60V 電流……100V ○実験結果 上記条件に従つて超微粒子を得た。その結果を下記す
る。○ Experimental conditions * Powder material: WO 3 average particle size ... 20 μm * Plasma gas (core gas, carrier gas) Composition and flow rate: N 2 ... 15 / min Ar ... 5 / min * Plasma input: voltage ... 60 V current ... … 100 V ○ Experimental results Under the above conditions, ultrafine particles were obtained. The results are described below.
＊超微粒子粒径……0.05μｍ ＊超微粒子化率……100％ ＊超微粒子組成： WO3……90％ W ……10％ 尚、得られた超微粒子をＸ線回折検査に付し、超微粒子
中にＮの存在，即ちWN2ないしWNの生成の有無を調査し
た。当該検査で、Ｎは全く検出されなかつた。* Ultra-fine particle size: 0.05 μm * Ultra-fine particle conversion rate: 100% * Ultra-fine particle composition: WO 3 ... 90% W ... 10% The obtained ultra-fine particles were subjected to an X-ray diffraction test. The existence of N in the ultrafine particles, that is, the presence or absence of WN 2 to WN was investigated. In the test, N was not detected at all.
上記実験結果は本発明方法がWO3超微粒子製造に画期
的に奏功することを立証した。The above experimental results the present invention a method is established that remarkably successful in WO 3 ultrafine particles produced.
また、上記装置を使用して粉末原料をＷとした実験例
ではＷ超微粒子が生成され、その超微粒子化率も100％
であり、Ｘ線回折検査でもＮの存在は皆無であることが
確認されている。Further, in the experimental example in which the powder material was W using the above apparatus, W ultrafine particles were generated, and the ultrafine particle formation rate was 100%.
X-ray diffraction inspection has confirmed that N is completely absent.
（他の実施例） 上記実施例および開示実施例では、プラズマガスとし
てN2・Ar混合ガスであつたが、Arはプラズマ安定用であ
り、例えば点火時にArを少量混入し、プラズマが安定し
たら順次Arの供給を絞つてゆき、N2のみを供給するよう
にしてもよい。この場合でも超微粒子の生成に何等の支
障も生じない。(Other Embodiments) In the above embodiments and the disclosed embodiments, the N 2 · Ar mixed gas was used as the plasma gas. However, Ar is used for stabilizing the plasma. The supply of Ar may be sequentially reduced to supply only N 2 . Even in this case, there is no hindrance to the generation of ultrafine particles.
また、上記実施例はプラズマジエツトガン２を用いて
高温プラズマを発生させる直流プラズマジエツト法に本
発明法を適用した場合であつたが、本発明法は高周波プ
ラズマ法やハイブリツドプラズマ法により高温プラズマ
を発生させる場合にも適用可能である。ただし、高周波
プラズマ法に適用する場合には、キヤリヤガスCGを可及
的にプラズマの根本部に近い位置に吹き込む設定とし、
高融点，高沸点特性を有する粉末原料がプラズマフレー
ムの中心高温域ph内を確実に通過する如く供給する配慮
が必要である。In the above embodiment, the method of the present invention is applied to a DC plasma jet method for generating high-temperature plasma using the plasma jet gun 2, but the method of the present invention is applied to a high-frequency plasma method or a hybrid plasma method. The present invention is also applicable when generating plasma. However, when applied to the high-frequency plasma method, the carrier gas CG should be blown as close to the base of the plasma as possible.
Care must be taken to ensure that the powder raw material having high melting point and high boiling point characteristics passes through the high temperature region ph of the center of the plasma frame without fail.
（発明の効果） 本発明法は、粉末原料がＷならばＷ超微粒子を,WO3な
らばWO3・Ｗ混在超微粒子を100％の生成率で極めて容易
に連続生産し得るので、ＷもしくWO3超微粒子の需要に
対し工業的生産規模，即ち大量かつ廉価で応ずることが
可能となり、本発明法が齎す効果は甚大である。The present invention method (Effect of the invention), the powder raw material W if W ultrafine particles, since it can be very easily continuously produced in WO 3 if WO 3 · W mixed ultrafine particles 100% production rate, W also Thus, it is possible to respond to the demand for WO 3 ultrafine particles on an industrial production scale, that is, in large quantities and at low cost, and the effect of the present invention is enormous.
第１図は本発明法の一実施例概要を示す正面図、第２図
（ａ）〜（ｃ）はそれぞれ高温プラズマを発生し得る従
来法による装置例の正面図ないし断面正面図である。FIG. 1 is a front view showing an outline of one embodiment of the method of the present invention, and FIGS. 2 (a) to 2 (c) are front views or cross-sectional front views of an apparatus according to a conventional method capable of generating high-temperature plasma.
Claims (4)
スでアルゴンを添加したコアガスならびに雰囲気ガスを
用い、微減圧雰囲気中に高温プラズマを発生せしめ、当
該プラズマフレーム中へタングステン，もしくは酸化タ
ングステンの粉末原料を上記ガスと同質のキヤリヤガス
にのせて連続供給することにより、上記粉末原料から超
微粒子を生成せしめ、上記微減圧雰囲気を維持するため
に吸引される雰囲気ガス流中に浮遊する超微粒子を連続
的に捕集・回収するようにしたことを特徴とするタング
ステンもしくは酸化タングステン超微粒子の製造方法。A high-temperature plasma is generated in a slightly reduced-pressure atmosphere using a core gas and an atmosphere gas containing 100% nitrogen gas or nitrogen as a main component and argon added, and tungsten or tungsten oxide is introduced into the plasma frame. By continuously supplying the powder raw material on a carrier gas of the same quality as the above gas, ultrafine particles are generated from the powder raw material, and the ultrafine particles floating in the atmosphere gas flow sucked to maintain the slightly reduced pressure atmosphere are removed. A method for producing ultrafine tungsten or tungsten oxide particles, wherein the fine particles are continuously collected and collected.
求項１記載のタングステンもしくは酸化タングステン超
微粒子の製造方法。2. The method for producing ultrafine tungsten or tungsten oxide particles according to claim 1, wherein the slightly reduced pressure is at least 700 torr or less.
ングステン超微粒子が生成される請求項１記載のタング
ステンもしくは酸化タングステン超微粒子の製造方法。3. The method for producing ultrafine tungsten or tungsten oxide particles according to claim 1, wherein ultrafine tungsten particles are produced when the powder raw material is tungsten.
は酸化タングステン・タングステン混在超微粒子が生成
される請求項１記載のタングステンもしくは酸化タング
ステン超微粒子の製造方法。4. The method for producing tungsten or tungsten oxide ultrafine particles according to claim 1, wherein when the powder raw material is tungsten oxide, tungsten oxide / tungsten mixed ultrafine particles are generated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63154868A JP2662986B2 (en) | 1988-06-24 | 1988-06-24 | Method for producing ultrafine tungsten or tungsten oxide particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63154868A JP2662986B2 (en) | 1988-06-24 | 1988-06-24 | Method for producing ultrafine tungsten or tungsten oxide particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH026339A JPH026339A (en) | 1990-01-10 |
| JP2662986B2 true JP2662986B2 (en) | 1997-10-15 |
Family
ID=15593679
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63154868A Expired - Fee Related JP2662986B2 (en) | 1988-06-24 | 1988-06-24 | Method for producing ultrafine tungsten or tungsten oxide particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2662986B2 (en) |
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| Publication number | Publication date |
|---|---|
| JPH026339A (en) | 1990-01-10 |
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