JPH02277759A - Formation of oxide film - Google Patents
Formation of oxide filmInfo
- Publication number
- JPH02277759A JPH02277759A JP1093225A JP9322589A JPH02277759A JP H02277759 A JPH02277759 A JP H02277759A JP 1093225 A JP1093225 A JP 1093225A JP 9322589 A JP9322589 A JP 9322589A JP H02277759 A JPH02277759 A JP H02277759A
- Authority
- JP
- Japan
- Prior art keywords
- film
- nitrate
- state
- acetate
- oxide
- 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.)
- Pending
Links
- 230000015572 biosynthetic process Effects 0.000 title abstract description 9
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000005507 spraying Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 8
- 239000003595 mist Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000010419 fine particle Substances 0.000 abstract description 4
- 239000007921 spray Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000007750 plasma spraying Methods 0.000 description 4
- 238000005422 blasting Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
Landscapes
- Coating By Spraying Or Casting (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、プラズマ溶射法による酸化物被膜の形成方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for forming an oxide film by plasma spraying.
［従来の技術］
酸化物セラミックスの被膜を形成する方法として、スパ
ッタリング法、イオンブレーティング法、プラズマ溶射
法等がある。スパッタリング法及びイオンブレーティン
グ法は、粒径５〜１０人の原子状粒子を基板の表面上に
堆積するものであるため緻密な膜が得られるが、成膜速
度が１〜３人／ｓｅｅと遅いため、実用的には０．５〜
５μｍ厚の膜を形成するのに使用している。また、固体
燃料電池用の電極や超電導部材等を作製する場合には多
元系セラミックスの膜を形成する必要があるが、スパッ
タリング法やイオンブレーティング法では膜の化学組成
を正確にコントロールすることが難しい。[Prior Art] Methods for forming oxide ceramic films include sputtering, ion blasting, plasma spraying, and the like. The sputtering method and the ion blating method deposit atomic particles with a particle size of 5 to 10 particles on the surface of the substrate, so a dense film can be obtained, but the deposition rate is 1 to 3 particles/see. Because it is slow, it is practically 0.5~
It is used to form a 5 μm thick film. Furthermore, when producing electrodes and superconducting members for solid fuel cells, it is necessary to form multi-component ceramic films, but with sputtering and ion blasting methods, it is not possible to precisely control the chemical composition of the film. difficult.
一方、プラズマ溶射法は、５〜１００μｍの粉末を溶融
して堆積するものであるため、成膜速度はスパッタリン
グ法やイオンブレーティング法に比べてはるかに大きく
、２〜３桁も大きい。膜厚は通常、５０〜５００μｍで
ある。しかも、膜の化学組成のコントロールも容易であ
る。しかし、膜の緻密性については劣っている。On the other hand, since the plasma spraying method melts and deposits powder with a size of 5 to 100 μm, the film formation rate is much higher than that of the sputtering method or the ion blasting method, and is 2 to 3 orders of magnitude higher. The film thickness is usually 50 to 500 μm. Furthermore, the chemical composition of the film can be easily controlled. However, the denseness of the film is inferior.
［発明が解決しようとする課題〕
このように従来の被膜形成方法には一長一短があり、緻
密性・化学組成の制御性に優れかつ成膜速度の大きい膜
を得るには問題がある。[Problems to be Solved by the Invention] As described above, conventional film forming methods have advantages and disadvantages, and there are problems in obtaining a film that is excellent in density, controllability of chemical composition, and has a high deposition rate.
本発明の目的は、プラズマ溶射法が持つ膜組成の制御性
が容易、成膜速度大なる特色を活かし、かつ緻密性に優
れた新規な被膜形成方法を提供することである。An object of the present invention is to provide a novel film forming method that takes advantage of the characteristics of plasma spraying, such as easy controllability of film composition and high film formation speed, and that has excellent density.
［課題を解決するための手段］
上記の目的を達成するため、本発明に係る酸化物被膜の
形成方法は、溶射トーチより噴射されるプラズマ化され
たガスジェット中に、硝酸塩あるいは酢酸塩等の水溶液
を霧状にして吹き込み、これによって基板の表面上に酸
化物被膜を形成するものである。[Means for Solving the Problems] In order to achieve the above object, the method for forming an oxide film according to the present invention includes adding nitrates, acetates, etc. to a plasma gas jet sprayed from a thermal spray torch. An oxide film is formed on the surface of a substrate by blowing an aqueous solution in the form of a mist.
本発明において使用する膜材料の酸化物は、単元系、多
元系のいずれでも良く、また、成膜時の雰囲気圧は大気
圧であり、膜の緻密性をさらに向上させるためには低圧
雰囲気下で成膜を行うとさらに良い。The oxide of the film material used in the present invention may be either mono-component or multi-component, and the atmospheric pressure during film formation is atmospheric pressure. It is even better if the film is formed using .
［作 用］
プラズマジェット中に膜材料の硝酸塩あるいは酢酸塩等
の水溶液を霧状にして吹き付けると、硝酸塩あるいは酢
酸塩等の水溶液のミストは高温のプラズマによって熱分
解して酸化物原子状となり、この原子状となる時に一部
は励起され、あるいはさらに活性化されて電離する。こ
のような状態となって基板上に堆積するため、膜の緻密
化が可能になり、かつ成膜速度は相当に大きい。[Function] When an aqueous solution of membrane material such as nitrate or acetate is sprayed in the form of a mist during a plasma jet, the mist of the aqueous solution of nitrate or acetate is thermally decomposed by the high temperature plasma and becomes atomic oxide. When it becomes atomic, a part of it is excited or further activated and ionized. Since the film is deposited on the substrate in such a state, the film can be made denser and the film formation rate is considerably high.
なお、本発明は大気圧下で行うこともできるが、上記の
成膜を数＋ｔｏｒｒの低圧雰囲気下で行うと、プラズマ
ジェットの速度が上がるため、酸化物原子の微粒子の飛
行速度が大となり、膜の緻密性はさらに向上する。Although the present invention can be carried out under atmospheric pressure, if the above film formation is carried out in a low pressure atmosphere of several + torr, the speed of the plasma jet increases, so the flight speed of fine particles of oxide atoms increases, The denseness of the film is further improved.
［実施例］ 以下、本発明の一実施例を図により説明する。[Example] Hereinafter, one embodiment of the present invention will be described with reference to the drawings.
ただ１つの図面は本発明の被膜形成方法の説明図である
。図に示すように、溶射トーチ１の前方に被膜２を形成
すべき基板３を、ヒーター４を内蔵した支持台５上に取
り付ける。ヒーター４は被膜の接着性向上のために基板
３を予熱するのに用いられる。The only drawing is an illustration of the coating forming method of the present invention. As shown in the figure, a substrate 3 on which a coating 2 is to be formed is mounted in front of a thermal spraying torch 1 on a support 5 having a built-in heater 4. The heater 4 is used to preheat the substrate 3 to improve the adhesion of the coating.
硝酸塩あるいは酢酸塩等の水溶液は溶射トーチ１のノズ
ル近辺に配設された噴霧ノズル６よりプラズマジェット
７の方向に対してほぼ直角方向に噴霧するようになって
いる。The aqueous solution of nitrate or acetate is sprayed from a spray nozzle 6 disposed near the nozzle of the thermal spray torch 1 in a direction substantially perpendicular to the direction of the plasma jet 7.
上記のように構成された被膜形成装置において、溶射ト
ーチ１にアルゴンガスあるいはヘリウムガス等を供給し
プラズマガスをつくってプラズマジェット７を噴出させ
る。このプラズマジェット７中に噴霧ノズル６より酸化
物水溶液を霧状にして吹き付けると、酸化物水溶液の微
粒子が前述のようにプラズマ熱によって分解し、原子状
となって基［３の表面上に堆積し被膜２を形成すること
になる。In the film forming apparatus configured as described above, argon gas, helium gas, or the like is supplied to the thermal spraying torch 1 to generate plasma gas, and the plasma jet 7 is ejected. When the atomized oxide aqueous solution is sprayed into the plasma jet 7 from the spray nozzle 6, the fine particles of the oxide aqueous solution are decomposed by the plasma heat as described above, become atomic, and deposit on the surface of the group [3]. Then, a coating 2 is formed.
例えば、ＡＢＯという多元系酸化物の披ｘ ｙ
ｚ
膜２をつくる場合、モル比が
Ａ（Ｎｏ ） ：Ｂ（ＮＯａ）ｂ＝ｘ：ｙａ
となるように水溶液をつくり、これを霧状にしてプラズ
マジェット７中に入れる。For example, a multi-component oxide called ABO
When forming the z film 2, an aqueous solution is prepared such that the molar ratio is A(No):B(NOa)b=x:ya, and this is atomized and introduced into the plasma jet 7.
具体的に説明する。I will explain in detail.
ＹＢａＣｕＯ系超電導膜を形成するにあたり、成膜条件
を次のように設定した。In forming a YBaCuO-based superconducting film, film forming conditions were set as follows.
■硝酸塩水溶液のモル比と濃度
Ｙ（Ｎｏ ） ：Ｂａ （Ｎｏ３）２ ：Ｃｕ
（Ｎｏ３）２”１：２：３
■プラズマ電流・電圧
６００Ａ−５０ｖ（アルゴンガス使用）■基板 ＭｇＯ
■基板−溶射トーチ間間隔 ８０ ｍｍ■チャンバ内圧
力 ２０ ｔｏｒｒ
なお、成膜速度は５００人／ｓｅｅ、膜厚は８μｍであ
った。また、成膜後、酸素ガス中で９００℃、１時間の
アニールを行った。この結果、膜の超電導特性；臨界温
度ＴＣ−８８に膜組成；Ｙ： Ｂａ ： Ｃｕ＝ １
： ２．０５ ： ３．０２が得られた。■Molar ratio and concentration of nitrate aqueous solution Y(No):Ba(No3)2:Cu
(No. 3) 2” 1:2:3 ■Plasma current/voltage 600A-50V (using argon gas) ■Substrate MgO ■Substrate-to-spray torch spacing 80 mm ■Chamber internal pressure 20 torr The film-forming rate was 500 people/ See, the film thickness was 8 μm.After the film was formed, it was annealed at 900°C for 1 hour in oxygen gas.As a result, the superconducting properties of the film; Ba: Cu=1
: 2.05 : 3.02 were obtained.
このように膜組成において、理論値にきわめて近いもの
が得られ、従来のスパッタリング法やイオンブレーティ
ング法では、
Ｙ：Ｂａ：Ｃｕ −１： １．８： ３．５程度の
ものしか得られないのに比べ、緻密性が著しく向上して
いることがわかる。また、ＢＬ−Ｓ ｒ−Ｃａ−Ｃｕ−
０系の超電導膜を形成する場合にももちろん可能であっ
た。In this way, a film composition very close to the theoretical value can be obtained, and conventional sputtering methods and ion blating methods can only obtain a film composition of approximately Y:Ba:Cu -1: 1.8: 3.5. It can be seen that the density is significantly improved compared to the previous one. Also, BL-S r-Ca-Cu-
Of course, this was also possible when forming a 0-based superconducting film.
なお、膜材料の酸化物は単元系のものであっても良いこ
とはいうまでもなく、また、本発明は大気圧下でも行う
ことができる。しかし、適当な低圧雰囲気下で行った場
合には成膜速度は１０００人／ｓｅｃにも達する。Note that it goes without saying that the oxide of the film material may be a monomer type, and the present invention can also be carried out under atmospheric pressure. However, when carried out under an appropriate low pressure atmosphere, the film formation rate reaches as high as 1000 people/sec.
［発明の効果］
以上のように本発明によれば、プラズマジェット中に硝
酸塩あるいは酢酸塩等の水溶液を霧状にして吹き付ける
ことにより、硝酸塩あるいは酢酸塩等の水溶液の微粒子
が原子状となって被膜を形成することができるため、成
膜速度が大であり、膜の化学組成の制御性も容易で、か
つその緻密性が著しく向上するという効果が得られる。[Effects of the Invention] As described above, according to the present invention, by spraying an aqueous solution of nitrate or acetate in the form of a mist into a plasma jet, fine particles of the aqueous solution of nitrate or acetate become atomic. Since a film can be formed, the film formation rate is high, the chemical composition of the film can be easily controlled, and the denseness of the film is significantly improved.
したがって、本発明は、膜組成の特に厳密な条件が要求
される超電導部材や固体燃料電池の電極等に利用して効
果を発揮する。Therefore, the present invention can be effectively applied to superconducting members, electrodes of solid fuel cells, etc., which require particularly strict conditions for membrane composition.
図面は本発明の被膜形成方法を実施する装置の概念図で
ある。
１・・・溶射トーチ
２・・・被膜
３・・・基板
６・・・噴霧ノズル
７・・・プラズマジェットThe drawing is a conceptual diagram of an apparatus for carrying out the film forming method of the present invention. 1...Thermal spray torch 2...Coating 3...Substrate 6...Spray nozzle 7...Plasma jet
Claims (1)
を霧状にしてプラズマジェット中に吹き付けることによ
り基板面上に被膜を形成することを特徴とする酸化物被
膜の形成方法。1. A method for forming an oxide film, which comprises forming a film on a substrate surface by spraying a mono- or multi-component aqueous solution of nitrate, acetate, etc. in the form of a mist into a plasma jet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1093225A JPH02277759A (en) | 1989-04-14 | 1989-04-14 | Formation of oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1093225A JPH02277759A (en) | 1989-04-14 | 1989-04-14 | Formation of oxide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02277759A true JPH02277759A (en) | 1990-11-14 |
Family
ID=14076606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1093225A Pending JPH02277759A (en) | 1989-04-14 | 1989-04-14 | Formation of oxide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02277759A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015145515A (en) * | 2014-01-31 | 2015-08-13 | 三菱重工業株式会社 | Film deposition apparatus, film deposition method, high-temperature part, and gas turbine |
-
1989
- 1989-04-14 JP JP1093225A patent/JPH02277759A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015145515A (en) * | 2014-01-31 | 2015-08-13 | 三菱重工業株式会社 | Film deposition apparatus, film deposition method, high-temperature part, and gas turbine |
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