JP2004300500A - Member with film deposited thereon, and method for depositing film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film of excellent corrosion resistance and oxidation resistance on pipes for a boiler or the like. <P>SOLUTION: Gas of vaporized organic metallic material containing Al (aluminum) element is mixed with gas containing oxygen or oxygen atoms, and the gas mixture is subjected to vapor-phase reaction in a vicinity of a surface of a member 2 to deposit a metal oxide film on the surface of the member 2. Since the metal oxide film is deposited on the surface of the member 2 by the reaction of gas molecules of very small size with each other, least air enters the metal oxide film and the dense metal oxide film of the porosity below 1% is deposited. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００６８】
表１に示すように、成膜時間が１０分、３０分、６０分のときの金属酸化皮膜（酸化アルミニウム膜）３のそれぞれの厚みは約１２０ｎｍ、約３００ｎｍ、約５５０ｎｍであった。
【００６９】
気孔率は、光学顕微鏡を用いて測定した結果であり、全ての金属酸化皮膜３において１％未満であった。
【００７０】
耐酸化性は、図４に示す耐酸化性評価装置を用いて行った。耐酸化性評価装置２００では、濃硫酸を二酸化マンガンとともに加熱して塩素ガスを発生させる。この塩素ガスを水中を通してガスに含まれるＨＣｌを除き、さらに硫酸中を通して乾燥させて、窒素ガスと混合する。窒素ガスの濃度は約３％とし、流量は毎分１０００ｃｃとした。
【００７１】
このガスをセラミックヒータ２０１にて３００℃〜９００℃に加熱し、加熱直後にそのガスを皮膜付部材１の金属酸化皮膜３へ接触させた。これにより、金属酸化皮膜３の耐酸化能力を評価した。なお、この皮膜付部材１は、銅製の水冷ジャケット２０２に接触固定されており、これにより、放熱が効果的に行われる。
【００７２】
このようにして調べた全ての金属酸化皮膜３の耐酸化性は、実用に問題なく耐えられる酸化性に優れたものであった。
【００７３】
【発明の効果】
請求項１ないし４の発明によれば、金属酸化皮膜の気孔率が１％未満であるので従来の皮膜よりも耐食耐酸化性が優れている。
【００７４】
請求項５ないし９の発明によれば、非常に小さいサイズのガス分子同士が反応しあって部材の表面上に皮膜が形成されるので、皮膜に空気の入り込む余地がほとんど無く、気孔率が１％未満の緻密な皮膜を形成することができ、これにより、耐食耐酸化性に優れた皮膜を得ることができる。また、皮膜は気相成長によって形成されるので、温度条件・圧力条件・形成時間などを制御することによって複雑な３次元形状の部材であってもその表面全体にその加工公差以内の厚さに皮膜を均一に形成することができる。また、酸化アルミニウム主体の強固な皮膜を形成することができる。
【００７５】
請求項８記載の発明によれば、請求項５又は７記載の皮膜形成方法において、有機金属材料として常温常圧では固体である材料を用いることにより、皮膜の形成の容易化を図ることができる。
【００７６】
請求項９記載の発明によれば、請求項５，６，７又は８記載の皮膜形成方法において、混合した前記ガスを気相反応させる際に、プラズマ状態を発生させることにより、金属の酸化物を通常の化学反応で必要な温度よりも低い温度で形成することができる。
【００７７】
請求項１０又は１１記載の発明の皮膜付部材によれば、金属酸化皮膜は気孔率が１％未満の緻密な皮膜であり、これにより、従来の皮膜よりも耐食耐酸化性が優れている。
【図面の簡単な説明】
【図１】本発明の第一の実施の形態の皮膜付部材を模式的に示す縦断正面図である。
【図２】皮膜形成装置を示す模式図である。
【図３】本発明の第二の実施の形態の皮膜付部材を模式的に示す縦断正面図である。
【図４】本発明の実施例の耐酸化性評価装置を示す模式図である。
【符号の説明】
１ 皮膜付部材
２ 部材
３ 金属酸化皮膜
３ａ 第一の金属酸化皮膜
３ｂ 第二の金属酸化皮膜
４ 積層皮膜[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a member with a film and a method for forming a film.
[0002]
[Prior art]
BACKGROUND ART Conventionally, in a device such as a boiler for burning a mixture of heavy oil and coal, there is a metal heat transfer tube used for its piping and the like. Such metal heat transfer tubes are often eroded by components such as chlorine contained in heavy oil and coal ash. Such an erosion phenomenon is not only a problem unique to a heat transfer tube such as a boiler, but also occurs in various other devices, and a countermeasure for the problem has been required.
[0003]
In order to solve such a problem, there has been proposed a method for preventing the above-mentioned erosion by forming a metal oxide film having few pores on a member surface (for example, see Patent Document 1).
[0004]
In the method of Patent Document 1, (1) a film of aluminum or an aluminum alloy is formed on the surface of a member, and (2) an oxide powder such as aluminum oxide, zirconium oxide, titanium oxide, or chromium oxide is coated on the film with aluminum or aluminum. This is a procedure in which a coating is further formed by mixing with an aluminum alloy, and (3) the coating is oxidized at 600 ° C. for 5 hours.
[0005]
[Patent Document 1]
Japanese Patent Publication No. 7-830
[0006]
[Problems to be solved by the invention]
However, the method of Patent Document 1 requires a long time of 10 hours or more to form an oxide film or a corrosion-resistant film, and requires a processing temperature of 900 ° C. to 600 ° C. and requires a very high temperature. There's a problem. Further, the formed film becomes a very thick film of about 500 μm. In addition, there is a problem that the porosity of the coating, which is an index of the denseness, is as large as 1% to 3%, and the coating is only porous (porous), and sufficient corrosion resistance and oxidation resistance in practical use of the coating cannot be obtained. .
[0007]
An object of the present invention is to obtain a film having excellent corrosion resistance and oxidation resistance.
[0008]
[Means for Solving the Problems]
The member with a film according to the first aspect of the present invention includes a member and a metal oxide film containing Al (aluminum) and O (oxygen) and formed on the surface of the member and having a porosity of less than 1%.
[0009]
Therefore, since the porosity is less than 1%, the corrosion resistance and the oxidation resistance are superior to the conventional coating.
[0010]
Here, in the member with a film according to claim 1, the metal oxide film may include at least one or more elements other than Al (aluminum) and O (oxygen) (claim 2).
[0011]
According to a third aspect of the present invention, there is provided a member with a film, a first metal oxide film containing Al (aluminum) and O (oxygen), and at least one or more of Al (aluminum) and O (oxygen) and others. A laminated film having a porosity of less than 1% in which at least one second metal oxide film containing an element is alternately formed, and a member having the laminated film formed on the surface.
[0012]
Therefore, since the porosity is less than 1%, the corrosion resistance and the oxidation resistance are superior to the conventional coating.
[0013]
Here, in the member with a film according to claim 2 or 3, the element is Li (lithium), Be (beryllium), B (boron), N (nitrogen), F (fluorine), Na (sodium), Mg (Magnesium), Si (silicon), P (phosphorus), Cl (chlorine), K (potassium), Ca (calcium), Ti (titanium), Cr (chromium), Mn (manganese), Fe (iron), Co (Cobalt), Ni (nickel), Cu (copper), Zn (zinc), Ge (germanium), As (arsenic), Rb (rubidium), Sr (strontium), Y (yttrium), Zr (zircon), Nb (Niobium), Sn (tin), Sb (antimony), Ba (barium), La (lanthanum), Ta (tantalum), Tl (thallium), Bi (bismuth), Ce (cerium), Nd ( Ojimu), Sm (thorium), Gd (gadolinium), Tb (terbium), Yb (ytterbium), Th (it is desirable to include at least one or more of the group consisting of thorium) (claim 4).
[0014]
According to a fifth aspect of the present invention, there is provided a film forming method comprising mixing a gas in which an organometallic material containing an Al (aluminum) element is vaporized and a gas containing oxygen or an oxygen atom, and mixing the mixed gas near the surface of the member. To form a metal oxide film on the surface of the member.
[0015]
Accordingly, since gas molecules having extremely small sizes react with each other to form a film on the surface of the member, there is almost no room for air to enter the film, and the film becomes a dense film having a porosity of less than 1%. This results in a film having better corrosion resistance and oxidation resistance than conventional films. In addition, since the film is formed by vapor phase growth, even if the member has a complicated three-dimensional shape by controlling the temperature conditions, pressure conditions, formation time, etc., the entire surface of the member has a thickness within the processing tolerance. It is possible to form a film uniformly.
[0016]
Here, in the film forming method according to claim 5, the organometallic material may include at least one or more metal elements other than the Al (aluminum) element (claim 6).
[0017]
According to a seventh aspect of the present invention, there is provided a film forming method, wherein a gas in which an organometallic material containing an Al (aluminum) element is vaporized and a gas containing oxygen or an oxygen atom are mixed, and the mixed gas is mixed on the surface of the member. First step of forming a first metal oxide film by performing a gas phase reaction with an organic metal material containing an Al (aluminum) element and at least one metal element other than the Al (aluminum) element And a gas containing oxygen or an oxygen atom, and a second step of forming a second metal oxide film by causing a gas phase reaction of the mixed gases near the surface of the member, The first step and the second step are alternately performed, and at least one first metal film and at least one second metal film are alternately formed on the surface of the member.
[0018]
Accordingly, since gas molecules having extremely small sizes react with each other to form a film on the surface of the member, there is almost no room for air to enter the film, and the film becomes a dense film having a porosity of less than 1%. This results in a film having better corrosion resistance and oxidation resistance than conventional films. In addition, since the film is formed by vapor phase growth, even if the member has a complicated three-dimensional shape by controlling the temperature conditions, pressure conditions, formation time, etc., the entire surface of the member has a thickness within the processing tolerance. It is possible to form a film uniformly.
[0019]
According to an eighth aspect of the present invention, in the film forming method according to the fifth or seventh aspect, the organometallic material containing an Al (aluminum) element is Al (i-OC). ₃ H ₇ ) ₃ [Triisopropoxyaluminum: triisopropoxyaluminum], Al (OCH ₃ ) ₃ [Trimethyoxyluminum: trimethoxyaluminum], Al (n-OC ₄ H ₉ ) ₃ [Trinormalbutoxyaluminum: Trinormal butoxyaluminum], Al (n-OC ₃ H ₇ ) ₃ [Trinormalpropoxyaluminum: Trinormal propoxyaluminum], Al (C ₅ H ₇ O ₂ ) ₃ [Triacetylacetonatoaluminum: aluminum triacetylacetonate], Al (C ₁₁ H ₁₉ O ₂ ) ₃ [Trisipivaloylmethanatoaluminum: aluminum tripipivaloylmethanate], Al (C ₅ HFO ₂ ) ₃ [Trishexafluoroacetylacetonatoaluminum: trihexafluoroacetylacetonatoaluminum], Al (OC ₂ H ₅ ) ₃ [Triethoxyaluminum: triethoxyaluminum], Al (i-OC ₄ H ₉ ) ₃ [Triisobutoxyaluminum: triisobutoxyaluminum].
[0020]
Therefore, all of these materials are solid at room temperature and pressure and are easy to handle, so that the formation of a film is facilitated.
[0021]
According to a ninth aspect of the present invention, in the film forming method of the fifth, sixth, seventh or eighth aspect, a plasma state is generated when the mixed gas is subjected to a gas phase reaction.
[0022]
Therefore, it becomes possible to form the metal oxide at a temperature lower than the temperature required for a normal chemical reaction. In addition, a dense film can be formed.
[0023]
In the film-coated member according to the tenth aspect, a metal oxide film is formed on the surface of the member by the film-forming method according to the fifth or sixth aspect.
[0024]
Therefore, the metal oxide film is a dense film having a porosity of less than 1%, and thus has higher corrosion resistance and oxidation resistance than conventional films.
[0025]
In the film-coated member according to the eleventh aspect, at least one first metal oxide film and the second metal oxide film are alternately formed on the surface of the member by the film forming method according to the seventh aspect.
[0026]
Therefore, the metal oxide film is a dense film having a porosity of less than 1%, and thus has higher corrosion resistance and oxidation resistance than conventional films.
[0027]
BEST MODE FOR CARRYING OUT THE INVENTION
A first embodiment of the present invention will be described with reference to FIGS. Here, FIG. 1 is a vertical sectional front view schematically showing the member with a coating of the present embodiment.
[0028]
As shown in FIG. 1, the member with a film 1 is configured by forming a metal oxide film 3 on a member 2.
[0029]
The metal oxide film 3 is formed from Al (aluminum) and O (oxygen). The thickness of the metal oxide film 3 is 10 μm or less, and the porosity of the metal oxide film 3 is less than 1%.
[0030]
Here, the metal oxide film 3 is not limited to this. The metal oxide film 3 contains one or more types of elements M (M1, M2,...) Other than Al (aluminum) and O (oxygen). May be included.
[0031]
As the element M, Li (lithium), Be (beryllium), B (boron), N (nitrogen), F (fluorine), Na (sodium), Mg (magnesium), Si (silicon), P (phosphorus), Cl (chlorine), K (potassium), Ca (calcium), Ti (titanium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Ge (germanium), As (arsenic), Rb (rubidium), Sr (strontium), Y (yttrium), Zr (zircon), Nb (niobium), Sn (tin), Sb (antimony), Ba (barium), La (lanthanum), Ta (tantalum), Tl (thallium), Bi (bismuth), Ce (cerium), Nd (neodymium), Sm (thorium), Gd (gadolini) Arm), Tb (terbium), Yb (ytterbium), and the like can be exemplified Th (thorium).
[0032]
Next, a method of forming the metal oxide film 3 on the member 2 will be described with reference to FIG. Here, FIG. 2 is a schematic diagram showing a film forming apparatus.
[0033]
First, the film forming apparatus 100 will be described. As shown in FIG. 2, the film forming apparatus 100 includes a vacuum container 101 for accommodating the member 2. Generally, various gaseous materials are fed into the vacuum container 101, and the member 2 is placed in the vacuum container 101. The metal oxide film 3 is formed on the substrate.
[0034]
The film forming apparatus 100 includes an aluminum supply unit 102 for supplying Al (aluminum) to the vacuum container 101, an element supply unit 103 for supplying the element M to the vacuum container 101, and an oxygen gas for supplying oxygen gas to the vacuum container 101. A supply unit 104, an infrared lamp heater 105 provided in the vacuum vessel 101, and parallel plate electrodes 106a and 106b provided in the vacuum vessel 101 and generating plasma for the member 2 in the vacuum vessel 101 are provided. . A vacuum pump 108 is connected to an exhaust port 107 of the vacuum vessel 101, and an exhaust control valve 109 is provided in the exhaust port 107. Hereinafter, these units will be briefly described.
[0035]
The aluminum supply unit 102 heats the organic metal material for aluminum supply including the aluminum element placed on the zirconia ceramic dish 111a in the heating chamber 110 by the heater 111b to generate a vaporized gas, and opens the opening / closing valve 112. By the way, N ₂ A carrier gas, which is an inert gas such as (nitrogen gas) or Ar, is introduced into the heating chamber 110, the opening and closing valve 113 is opened, and the vaporized gas of the organometallic material is introduced into the vacuum vessel 101 together with the carrier gas.
[0036]
Here, as the organometallic material containing an aluminum element, Al (i-OC ₃ H ₇ ) ₃ [Triisopropoxyaluminum: triisopropoxyaluminum], Al (OCH ₃ ) ₃ [Trimethyoxyluminum: trimethoxyaluminum], Al (n-OC ₄ H ₉ ) ₃ [Trinormalbutoxyaluminum: Trinormal butoxyaluminum], Al (n-OC ₃ H ₇ ) ₃ [Trinormalpropoxyaluminum: Trinormal propoxyaluminum], Al (C ₅ H ₇ O ₂ ) ₃ [Triacetylacetonatoaluminum: aluminum triacetylacetonate], Al (C ₁₁ H ₁₉ O ₂ ) ₃ [Trisipivaloylmethanatoaluminum: aluminum tripipivaloylmethanate], Al (C ₅ HFO ₂ ) ₃ [Trishexafluoroacetylacetonatoaluminum: trihexafluoroacetylacetonatoaluminum], Al (OC ₂ H ₅ ) ₃ [Triethoxyaluminum: triethoxyaluminum], Al (i-OC ₄ H ₉ ) ₃ [Triisobutoxyaluminum: triisobutoxyaluminum] and the like. All of these materials are solid at room temperature and pressure and are easy to handle, so that the formation of a film is facilitated. Further, these materials are vaporized and gasified by adjusting temperature conditions (120 ° C. to 270 ° C.) and pressure conditions (760 Torr to 0.01 Torr).
[0037]
The element supply unit 103 includes a plurality of single element supply units 103a and 103b. The basic structure of the single element supply units 103a and 103b is the same as that of the aluminum supply unit 102. Organometallic materials for supplying different elements M are set in the heating chambers 110 of the single element supply units 103a and 103b. In addition, the number of the single element supply units 103a and 103b may be one or plural.
[0038]
The oxygen gas supply unit 104 is provided with an oxygen cylinder 114. The supply amount of oxygen from the oxygen cylinder 114 is adjusted by an on-off valve 115.
[0039]
Among the parallel plate electrodes 106a and 106b, one of the parallel plate electrodes 106a is connected to the high frequency power supply 119, and the other parallel plate electrode 106b is connected to the high frequency matching box 120. These parallel plate electrodes 106a and 106b are brought into a plasma state by applying an electric field to the atmosphere near the member 2. As a result, the mixed gas charged and mixed into the vacuum vessel 101 becomes a plasma state, and a chemical reaction that occurs only at a temperature of several hundred degrees or more in a normal state other than the plasma state proceeds at room temperature (normal temperature). Here, as the electric field, for example, in the case of an AC electric field, 13.56 MHz, 5 W / cm ² And in the case of a DC electric field, 10 kV / cm ² It is.
[0040]
Next, a method of forming the metal oxide film 3 on the member 2 using such a film forming apparatus 100 will be described. Here, as the metal oxide film 3, a film formed from Al (aluminum) and O (oxygen) will be described as an example.
[0041]
First, as a pre-process, the surface of the member 2 is irradiated with infrared light from the infrared lamp heater 105 to heat the member 2.
[0042]
Next, as a gas mixing step, an organic metal gas for supplying aluminum is supplied into the vacuum vessel 101 from the aluminum supply section 102 together with the carrier gas, and oxygen gas is supplied from the oxygen gas supply section 104 into the vacuum vessel 101. The supply of these gases is performed simultaneously. Thereby, those gases are mixed in the vacuum vessel 101 (hereinafter, such a gas is referred to as a mixed gas).
[0043]
Then, as a film forming step, the pressure in the vacuum vessel 101 is adjusted according to the growth conditions of the metal oxide film 3. This is performed by adjusting the amount of gas to be supplied and the amount of exhaust by the vacuum pump 108. In addition, plasma is generated by the parallel plate electrodes 106a and 106b. As a result, the mixed gas undergoes a gas phase reaction near the surface of the member 2, and the metal oxide film 3 is formed on the surface of the member 2. Thus, the member 1 with a film is completed.
[0044]
At this time, if the member 2 has a complicated structure, the thickness of the metal oxide film 3 to be formed may vary greatly depending on the relationship with the gas flow. It is important to form a film while uniformly flowing the gas into the vacuum vessel 101 and rotating the member 2 by rotating means (not shown) so as to change the portion of the member 2 that contacts the gas flow.
[0045]
When the metal oxide film 3 is formed from Al (aluminum), O (oxygen), and the element M, a vacuum is supplied from the element supply unit 103 together with the organic metal gas for supplying aluminum and the oxygen gas in the gas mixing step. By supplying an organic metal gas for supplying the element M together with the carrier gas into the container 101, the gases are mixed.
[0046]
By forming the metal oxide film 3 on the surface of the member 2 by the method described above, gases of very small sizes react with each other to form the metal oxide film 3, so that the metal oxide film 3 There is almost no room for entry, and the dense metal oxide film 3 having a porosity of less than 1% is obtained. Here, even if a volatile gas is generated when the mixed gas undergoes a chemical reaction, such a gas can hardly stay on the surface of the member 2 in the process of forming the film (in the metal oxide film 3). Therefore, it is pushed out of the metal oxide film 3 and the porosity is less than 1%. Thereby, the metal oxide film 3 having more excellent corrosion resistance and oxidation resistance than the conventional film is obtained. Here, in the conventional method, since the film is formed using the powder material, it is considered that air enters between the powders and many pores are formed.
[0047]
In addition, since gas molecules having extremely small sizes react with each other to form the metal oxide film 3 on the surface of the member 2, a thin metal oxide film 3 having a thickness of 10 μm or less is formed on the surface of the member 2. It becomes possible.
[0048]
Further, since the metal oxide film 3 is formed by vapor phase growth, even if the member has a complicated three-dimensional shape by controlling the temperature condition, the pressure condition, the formation time, and the like, the entire surface thereof is within the processing tolerance. The metal oxide film 3 can be formed uniformly to a thickness.
[0049]
In the present embodiment, a method of applying an electric field to the atmosphere near the member 2 has been described as an example of a method of generating plasma. However, the present invention is not limited to this. For example, a microwave may be applied to a mixed gas. Thus, a plasma state may be generated. At this time, the microwave energy is desirably 0.2 W or more.
[0050]
Next, a second embodiment of the present invention will be described with reference to FIG. Here, FIG. 3 is a longitudinal sectional front view schematically showing the member with a film of the present embodiment.
[0051]
The member 1 with a film according to the present embodiment is formed by laminating a first metal oxide film 3a and a second metal oxide film 3b on a member 2.
[0052]
The first metal oxide film 3a is formed from Al (aluminum) and O (oxygen). The second metal oxide film 3b is formed of Al (aluminum), O (oxygen), and at least one other element M. The first metal oxide film 3a and the second metal oxide film 3b constitute a laminated film 4 having a thickness of 10 μm or less. The porosity of the laminated film 4 is less than 1%.
[0053]
Next, a method of forming the laminated film 4 on the member 2 using the film forming apparatus 100 will be described.
[0054]
First, as a first step, a first metal oxide film 3a composed of Al (aluminum) and O (oxygen) is formed based on the method of forming the metal oxide film 3 described in the first embodiment. Form.
[0055]
Next, as a second step, a second metal oxide film 3b is formed on the first metal oxide film 3a based on the method for forming the metal oxide film 3 described in the first embodiment. Thereby, the laminated film 4 is formed on the surface of the member 2.
[0056]
By forming the laminated film 4 on the surface of the member 2 by the method described above, the same function and effect as in the first embodiment can be obtained.
[0057]
In the present embodiment, the laminated film 4 has been described by way of example in which the first metal oxide film 3a and the second metal oxide film 3b are laminated one by one, but the present invention is not limited to this. In the laminated film 4, a plurality of first metal oxide films 3a and a plurality of second metal oxide films 3b may be alternately laminated.
[0058]
【Example】
Next, an embodiment of the present invention will be described with reference to FIG.
[0059]
In the present embodiment, as the member 2,
・ Pure aluminum (1000 series) 1080
・ Aluminum-copper alloy system (2000 system) 2014
・ Aluminum-manganese alloy (3000 series) 3105
・ Aluminum-silicon alloy (4000 series) 4032
・ Aluminum-magnesium alloy (5000 series) 5052
・ Aluminum-magnesium-silicon alloy (6000 series) 6061
・ Aluminum-zinc-magnesium alloy (7000 series) 7075
The metal oxide film 3 was formed on the member 2 by the method of forming the metal oxide film 3 described in the first embodiment described above.
[0060]
Specifically, as an organometallic material containing an aluminum element, Al (C ₁₁ H ₁₉ O ₂ ) ₃ 5 g of [Trispivaloylmethanatoaluminum: aluminum tripipalloyl methanate] was placed on a zirconia ceramic dish 111a in the heating chamber 110 of the aluminum supply unit 102, and the temperature in the heating chamber 110 was set to 253 ° C. More specifically, the organometallic material is placed on the plate 111a in the heating chamber 110 at room temperature (22 ° C.), and argon gas is introduced as a carrier gas into the heating chamber 110 to change the inside of the heating chamber 110 from the atmospheric state. The heater was turned on with 100% argon gas. At this time, the time from the start of the operation until the inside of the heating chamber 110 reached 253 ° C. and became stable was 18 minutes.
[0061]
At the same time, after the member 2 was set in the vacuum vessel 101, the pressure in the vacuum vessel 101 was set to a vacuum state of 3 × 10E-3 Torr. The time required for this operation was 19 minutes. That is, the work time up to this point is 19 minutes. Then, the member 2 was irradiated with infrared light by the infrared lamp heater 105 to set the temperature of the surface of the member 2 to 150 ° C. At this time, it took 20 minutes.
[0062]
Then, in the aluminum supply unit 102, argon gas was supplied to the heating chamber 110 at a rate of 36 cc / min, and was sent into the vacuum vessel 101 together with the vaporized trippialloylmethanate aluminum that had been overheated and vaporized (sublimated). At the same time, 24 cc of oxygen gas was fed into the vacuum vessel 101 per minute. Thereby, the gas containing the organic metal material and the oxygen gas are mixed and reach the surface of the member 2. The time required for this operation was one minute.
[0063]
Then, the pressure in the vacuum vessel 101 is adjusted to 0.1 Torr by exhaust adjustment, and 7 W / cm is supplied by a 13.56 MHz high frequency power supply 119. ² The state of the atmosphere near the member 2 was changed to the plasma state by the power of. The metal oxide film 3 was formed on the member 2 by selecting the film formation time from 10 minutes, 30 minutes, and 60 minutes. Thereby, the member 1 with a film was completed.
[0064]
After the film formation is completed, the pressure in the vacuum vessel 101 is returned from 0.1 Torr to the atmospheric pressure over 25 minutes while slowly lowering the temperature of the member 2, and the member 1 with the film is removed from the vacuum vessel 101. I took it out.
[0065]
The total time required for forming the metal oxide film 3 was 19 minutes + 20 minutes + 1 minute + 60 minutes (the longest time) +25 minutes = 2 hours 5 minutes. As described above, according to the film forming method of the present invention, the formation time of the metal oxide film 3 can be significantly reduced as compared with the conventional method.
[0066]
The thickness, porosity, and oxidation resistance of the metal oxide film 3 thus formed were examined. Table 1 shows the results.
[0067]
[Table 1]

[0068]
As shown in Table 1, the thicknesses of the metal oxide film (aluminum oxide film) 3 when the film formation time was 10 minutes, 30 minutes, and 60 minutes were about 120 nm, about 300 nm, and about 550 nm.
[0069]
The porosity was measured using an optical microscope, and was less than 1% in all the metal oxide films 3.
[0070]
The oxidation resistance was measured using an oxidation resistance evaluation device shown in FIG. In the oxidation resistance evaluation apparatus 200, concentrated sulfuric acid is heated together with manganese dioxide to generate chlorine gas. This chlorine gas is passed through water to remove HCl contained in the gas, and further dried through sulfuric acid, and mixed with nitrogen gas. The nitrogen gas concentration was about 3%, and the flow rate was 1000 cc / min.
[0071]
This gas was heated to 300 ° C. to 900 ° C. by the ceramic heater 201, and immediately after heating, the gas was brought into contact with the metal oxide film 3 of the member 1 with a film. Thereby, the oxidation resistance of the metal oxide film 3 was evaluated. In addition, the member 1 with a film is fixed in contact with a water cooling jacket 202 made of copper, so that heat radiation is effectively performed.
[0072]
The oxidation resistance of all the metal oxide films 3 examined in this way was excellent in oxidization that could be endured without practical problems.
[0073]
【The invention's effect】
According to the invention of claims 1 to 4, the porosity of the metal oxide film is less than 1%, so that the metal oxide film has better corrosion resistance and oxidation resistance than the conventional film.
[0074]
According to the fifth to ninth aspects of the present invention, since gas molecules having extremely small sizes react with each other to form a film on the surface of the member, there is almost no room for air to enter the film, and the porosity is 1%. % Can be formed, whereby a film having excellent corrosion resistance and oxidation resistance can be obtained. In addition, since the film is formed by vapor phase growth, even if the member has a complicated three-dimensional shape by controlling the temperature conditions, pressure conditions, formation time, etc., the entire surface of the member has a thickness within the processing tolerance. A film can be formed uniformly. Further, a strong film mainly composed of aluminum oxide can be formed.
[0075]
According to the eighth aspect of the present invention, in the film forming method according to the fifth or seventh aspect, by using a material that is solid at normal temperature and normal pressure as the organometallic material, the formation of the film can be facilitated. .
[0076]
According to the ninth aspect of the present invention, in the method of forming a film according to the fifth, sixth, seventh, or eighth aspect, when the mixed gas is subjected to a gas phase reaction, a plasma state is generated, whereby a metal oxide is generated. Can be formed at temperatures lower than required by normal chemical reactions.
[0077]
According to the member with a film according to the tenth or eleventh aspect of the invention, the metal oxide film is a dense film having a porosity of less than 1%, and thus has higher corrosion resistance and oxidation resistance than a conventional film.
[Brief description of the drawings]
FIG. 1 is a longitudinal sectional front view schematically showing a member with a film according to a first embodiment of the present invention.
FIG. 2 is a schematic view showing a film forming apparatus.
FIG. 3 is a longitudinal sectional front view schematically showing a member with a film according to a second embodiment of the present invention.
FIG. 4 is a schematic diagram showing an oxidation resistance evaluation device according to an example of the present invention.
[Explanation of symbols]
1 Coated material
2 members
3 Metal oxide film
3a First metal oxide film
3b Second metal oxide film
4 Laminated film

Claims (11)

Components,
A metal oxide film containing Al (aluminum) and O (oxygen) and formed on the surface of the member and having a porosity of less than 1%;
A member with a film comprising: The member with a film according to claim 1, wherein the metal oxide film includes at least one or more elements other than Al (aluminum) and O (oxygen). A first metal oxide film containing Al (aluminum) and O (oxygen), and a second metal oxide film containing Al (aluminum), O (oxygen), and at least one other element are included. A laminated film having a porosity of less than 1% alternately formed at least one layer at a time,
A member having the laminated film formed on a surface thereof,
A member with a film comprising: The elements are Li (lithium), Be (beryllium), B (boron), N (nitrogen), F (fluorine), Na (sodium), Mg (magnesium), Si (silicon), P (phosphorus), Cl (Chlorine), K (potassium), Ca (calcium), Ti (titanium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (Zinc), Ge (germanium), As (arsenic), Rb (rubidium), Sr (strontium), Y (yttrium), Zr (zircon), Nb (niobium), Sn (tin), Sb (antimony), Ba (Barium), La (lanthanum), Ta (tantalum), Tl (thallium), Bi (bismuth), Ce (cerium), Nd (neodymium), Sm (thorium), Gd (gadolinium) , Tb (terbium), Yb (ytterbium), according to claim 2 or 3 coating with member according comprises at least one or more of the group consisting of Th (thorium). A gas in which an organometallic material containing an Al (aluminum) element is vaporized and a gas containing oxygen or an oxygen atom are mixed, and the mixed gas is subjected to a gas phase reaction near the surface of the member to form a gas phase reaction on the surface of the member. Film forming method for forming a metal oxide film on the surface. The method according to claim 5, wherein the organometallic material includes at least one or more metal elements other than the Al (aluminum) element. A first metal oxide film formed by mixing a gas obtained by vaporizing an organic metal material containing an Al (aluminum) element and a gas containing oxygen or an oxygen atom, and subjecting the mixed gas to a gas phase reaction near the surface of the member; A first step of forming
A gas in which an organometallic material containing at least one or more metal elements other than the Al (aluminum) element and the Al (aluminum) element is vaporized, and a gas containing oxygen or an oxygen atom are mixed, and the mixed gases are mixed. A second step of forming a second metal oxide film by performing a gas phase reaction near the surface of the member,
Including
A film forming method in which the first step and the second step are alternately performed to form at least one first metal film and at least one second metal film alternately on the surface of the member. The organometallic material containing an Al (aluminum) element,
_{Al (i-OC 3 H 7} ) 3 [Triisopropoxyaluminum: triisopropoxyaluminum,
Al (OCH ₃ ) ₃ [Trimethoxyaluminum: trimethoxyaluminum],
Al (n-OC ₄ H ₉ ) ₃ [Trinormalbutoxyaluminum: trinormal butoxyaluminum],
_{Al (n-OC 3 H 7} ) 3 [Trinormalpropoxyaluminum: tri-n-propoxy aluminum,
Al (C ₅ H ₇ O ₂ ) ₃ [Triacetylacetonatoaluminum: aluminum triacetylacetonate],
Al (C ₁₁ H ₁₉ O ₂ ) ₃ [Tris dipivaloylmethanatoaluminum: aluminum tripipalloyl methanate],
Al (C ₅ HFO ₂ ) ₃ [Trihexafluoroacetylacetonatoaluminum: aluminum trihexafluoroacetylacetonato],
Al (OC ₂ H ₅ ) ₃ [Triethoxyaluminum: triethoxyaluminum],
_{Al (i-OC 4 H 9} ) 3 [Triisobutoxyaluminum: tri isobutoxy aluminum,
The film forming method according to claim 5, comprising at least one of the following. 9. The film forming method according to claim 5, wherein a plasma state is generated when the mixed gas is subjected to a gas phase reaction. A member with a film, wherein a metal oxide film is formed on the surface of the member by the film forming method according to claim 5. A member with a film, wherein at least one first metal oxide film and a second metal oxide film are alternately formed on the surface of the member by the film forming method according to claim 7.

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