JP6594209B2 - Preparation method of metal spray coating - Google Patents
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本発明は、亜酸化銅を含有する金属溶射皮膜の作製方法に関する。 The present invention relates to a method for manufacturing a metal spray coating containing cuprous oxide.
亜酸化銅（Ｃｕ２Ｏ）はフジツボなどの海洋生物の忌避成分であるため、亜酸化銅を含有する塗料は、いわゆる防汚塗料として船底などに広く適用されている（例えば特許文献１及び非特許文献１参照）。 Since cuprous oxide (Cu 2 O) is a repellent component of marine organisms such as barnacles, paints containing cuprous oxide are widely applied to ship bottoms as so-called antifouling paints (for example, Patent Document 1 and Non-Patent Document 1). Patent Document 1).
しかし、亜酸化銅を含有する塗料により形成される塗膜は、塗膜形成要素として樹脂を含有するため、金属皮膜に比べるとどうしても耐傷付き性に劣り、耐紫外線性などの耐候性にも劣る。また、塗膜は、基材に対して単に塗布することにより形成するため、基材に対する密着性（接着性）も十分とはいえない。 However, since the coating film formed with a paint containing cuprous oxide contains a resin as a coating film forming element, it is inferior in scratch resistance and inferior in weather resistance such as ultraviolet resistance compared to a metal film. . Further, since the coating film is formed by simply applying to the substrate, it cannot be said that the adhesion (adhesiveness) to the substrate is sufficient.
本発明が解決しようとする課題は、従来の塗膜に比べ、耐傷付き性、耐候性及び基材に対する密着性を向上させ得る、亜酸化銅を含有する新たな皮膜の作製方法を提供することにある。 An object of the present invention is to provide, compared to the conventional coating film, scratch resistance, can improve adhesion to weathering and substrate, to provide a manufacturing method of a new coating containing cuprous oxide It is in.
上記課題を解決するため、本発明者らは、溶射技術の適用により亜酸化銅を含有する金属溶射皮膜を作製しようという発想のもと、その作製方法について鋭意検討した。その結果、溶射材料に酸化銅を添加すると溶射により酸化銅が亜酸化銅に還元され、これにより亜酸化銅を含有する金属溶射皮膜を作製できるという知見を得た。 In order to solve the above-mentioned problems, the present inventors diligently studied a production method based on the idea of producing a metal spray coating containing cuprous oxide by applying a spraying technique. As a result, when copper oxide was added to the thermal spray material, the copper oxide was reduced to cuprous oxide by thermal spraying, thereby obtaining a knowledge that a metal spray coating containing cuprous oxide could be produced.
すなわち、本発明の一観点によれば、「溶射により、溶射材料中の酸化銅を亜酸化銅に還元して基材上に亜酸化銅を含有する金属溶射皮膜を作製する、金属溶射皮膜の作製方法」が提供される。この本発明の作製方法において、溶射材料としては、Ａｌ合金、Ｚｎ合金、Ｎｉ合金、Ｆｅ合金、Ｎｉ基アモルファス合金又はＦｅ基アモルファス合金の粉末に酸化銅の粉末を添加したものを使用することができる。また、溶射は、溶融した溶射材料の噴流（溶射火炎（フレーム））を囲むように冷却ガスを噴射しながら実施することができる。このとき冷却ガスとしては、窒素ガス又は不活性ガスを使用することができる。 That is, according to one aspect of the present invention, “a metal sprayed coating that produces a metal sprayed coating containing cuprous oxide on a substrate by reducing the copper oxide in the sprayed material to cuprous oxide by thermal spraying” A production method "is provided. In this production method of the present invention, as the thermal spray material, an Al alloy, Zn alloy, Ni alloy, Fe alloy , Ni-based amorphous alloy or Fe-based amorphous alloy powder added with copper oxide powder may be used. it can. Further, the thermal spraying can be performed while injecting a cooling gas so as to surround a jet of the molten thermal spray material (thermal spray flame (frame)). At this time, nitrogen gas or inert gas can be used as the cooling gas.
本発明の金属溶射皮膜は、皮膜のマトリックスが金属であるので、従来の塗膜に比べ、耐傷付き性及び耐候性を向上させ得る。また、溶射により基材と密着するので、基材に対する密着性も向上させ得る。さらに、亜酸化銅を含有するので、海洋生物の忌避効果（防汚性）を発揮し得る。そして、皮膜のマトリックスにＡｌ合金、Ｚｎ合金、Ｎｉ合金、Ｆｅ合金、Ｎｉ基アモルファス合金、Ｆｅ基アモルファス合金といった防食性又は耐食性材料を適用することで、防汚性と防食性又は耐食性を兼ね備えた皮膜の提供が可能となる。 The metal spray coating of the present invention can improve scratch resistance and weather resistance compared to conventional coating films because the coating matrix is metal. Moreover, since it adheres with a base material by thermal spraying, the adhesiveness with respect to a base material can also be improved. Furthermore, since it contains cuprous oxide, it can exhibit the repellent effect (antifouling property) of marine organisms. And by applying anti-corrosion or anti-corrosion material such as Al alloy, Zn alloy, Ni alloy, Fe alloy, Ni-base amorphous alloy, Fe-base amorphous alloy to the matrix of the film, it has both anti-stain property and anti-corrosion property or corrosion resistance A coating can be provided.
さらに、従来、亜酸化銅を含有する金属溶射皮膜の作製方法は確立されていなかったところ、本発明によれば、溶射材料に酸化銅を添加して溶射するという簡単な方法によって亜酸化銅を含有する金属溶射皮膜の作製が可能となる。 Furthermore, conventionally, a method for producing a metal spray coating containing cuprous oxide has not been established. According to the present invention, cuprous oxide can be applied by a simple method of adding copper oxide to a thermal spray material and spraying. It becomes possible to produce a metal sprayed coating.
本発明の亜酸化銅含有溶射皮膜は、図１に示す溶射装置によって作製可能である。 The cuprous oxide-containing thermal spray coating of the present invention can be produced by the thermal spraying apparatus shown in FIG.
同図に示す溶射装置は、公知の粉末式フレーム溶射ガンの先端に２重筒構造のシリンダーノズルを取り付けてある。この溶射装置では、粉末式フレーム溶射ガンに溶射材料とともに燃焼ガスが供給され、粉末式フレーム溶射ガンの先端から、溶融した溶射材料（以下「溶射粒子」という。）を含む溶射火炎（フレーム）が噴流として噴射される。この溶射粒子の噴流は、２重筒構造のシリンダーノズルの内筒内を進行する。一方、２重筒構造のシリンダーノズルの内筒と外筒の間に冷却ガスを供給する。これにより、冷却ガスが溶射粒子の噴流を囲むように噴射される。この冷却ガスにより溶射粒子が急冷されるとともに、溶射粒子と大気との接触が抑えられ、溶射粒子の酸化が抑制される。 In the thermal spraying apparatus shown in the figure, a cylinder nozzle having a double cylinder structure is attached to the tip of a known powder type flame spray gun. In this thermal spraying apparatus, a combustion gas is supplied to a powder flame spray gun together with a thermal spray material, and a thermal spray flame (frame) containing a molten thermal spray material (hereinafter referred to as “thermal spray particles”) is provided from the tip of the powder flame spray gun. It is injected as a jet. The jet of spray particles travels in the inner cylinder of a cylinder nozzle having a double cylinder structure. On the other hand, a cooling gas is supplied between the inner cylinder and the outer cylinder of the cylinder nozzle having a double cylinder structure. Thereby, cooling gas is injected so that the jet of a thermal spray particle may be enclosed. While the sprayed particles are rapidly cooled by this cooling gas, contact between the sprayed particles and the atmosphere is suppressed, and oxidation of the sprayed particles is suppressed.
本発明では溶射材料として酸化銅の粉末を添加したものを使用する。そうすると、この溶射材料中の酸化銅が溶射中に還元されて亜酸化銅に変化し、これにより亜酸化銅含有溶射皮膜が得られる。溶射材料中の酸化銅の添加量（含有量）は４〜３５ｍｏｌ％であることが好ましい。また、図１に示したように冷却ガスを噴射しながら溶射を実施すると、この冷却ガスによる急冷効果及び大気遮断効果により、酸化銅の還元が進み過ぎて銅になるのを抑制できるとともに、皮膜組織を微細化することができ皮膜特性が向上する。冷却ガスとしては、窒素ガス又は不活性ガスを使用することが好ましい。 In the present invention, a thermal spray material to which copper oxide powder is added is used. If it does so, the copper oxide in this thermal spray material will be reduce | restored during thermal spraying, and changes to a cuprous oxide, and, thereby, a cuprous oxide containing thermal spray coating is obtained. The addition amount (content) of copper oxide in the thermal spray material is preferably 4 to 35 mol%. In addition, when spraying is performed while injecting a cooling gas as shown in FIG. 1, the rapid cooling effect and the air blocking effect by the cooling gas can suppress the reduction of the copper oxide so that copper is reduced, and the coating film The structure can be refined and the film properties are improved. Nitrogen gas or inert gas is preferably used as the cooling gas.
本発明の亜酸化銅含有溶射皮膜のマトリックスは、Ａｌ合金、Ｚｎ合金、Ｎｉ合金、Ｆｅ合金、Ｎｉ基アモルファス合金又はＦｅ基アモルファス合金とすることができる。すなわち、溶射材料として、Ａｌ合金、Ｚｎ合金、Ｎｉ合金、Ｆｅ合金、Ｎｉ基アモルファス合金又はＦｅ基アモルファス合金の粉末に酸化銅の粉末を添加したものを使用することで、これらをマトリックスとする亜酸化銅含有溶射皮膜が得られる。 The matrix of the cuprous oxide-containing thermal spray coating of the present invention can be an Al alloy, Zn alloy, Ni alloy, Fe alloy , Ni-based amorphous alloy or Fe-based amorphous alloy . In other words, as a thermal spray material, an Al alloy, Zn alloy, Ni alloy, Fe alloy , Ni-based amorphous alloy or Fe-based amorphous alloy powder added with copper oxide powder is used as a matrix. A copper oxide-containing thermal spray coating is obtained.
Ａｌ合金及びＺｎ合金は犠牲防食作用により亜酸化銅含有溶射皮膜の防食性を向上させる。また、Ｎｉ合金、Ｆｅ合金、Ｎｉ基アモルファス合金及びＦｅ基アモルファス合金は、亜酸化銅含有溶射皮膜の表面に不働態皮膜などを形成するので、亜酸化銅含有溶射皮膜の耐食性を向上させる。すなわち、亜酸化銅含有溶射皮膜のマトリックスをＡｌ合金、Ｚｎ合金、Ｎｉ合金、Ｆｅ合金、Ｎｉ基アモルファス合金又はＦｅ基アモルファス合金とすることで、亜酸化銅による防汚性とマトリックスによる防食性又は耐食性を兼ね備えた亜酸化銅含有溶射皮膜を得ることができる。 Al alloy and Zn alloy improve the corrosion resistance of the sprayed coating containing cuprous oxide by sacrificial corrosion protection. In addition, Ni alloys, Fe alloys , Ni-based amorphous alloys, and Fe-based amorphous alloys form a passive film on the surface of the cuprous oxide-containing thermal spray coating, thereby improving the corrosion resistance of the cuprous oxide-containing thermal spray coating. That is, by making the matrix of the cuprous oxide-containing spray coating Al alloy, Zn alloy, Ni alloy, Fe alloy , Ni-based amorphous alloy or Fe-based amorphous alloy , antifouling property by cuprous oxide and anticorrosion property by matrix or A cuprous oxide-containing thermal spray coating having corrosion resistance can be obtained.
防汚性を向上させる点から、亜酸化銅含有溶射皮膜中の亜酸化銅の含有量は０．２ｍｏｌ％以上であることが好ましく、亜酸化銅含有溶射皮膜中の銅成分のうち亜酸化銅の割合は５ｍｏｌ％以上であることが好ましい。また、亜酸化銅含有溶射皮膜を塩水（５質量％塩化ナトリウム水溶液）に浸漬したときの銅成分の溶出量は０．００５μｇ／ｃｍ２／ｄａｙ（０．０２ｍｇ／Ｌ）以上であることが好ましい。 From the viewpoint of improving the antifouling property, the content of cuprous oxide in the cuprous oxide-containing thermal spray coating is preferably 0.2 mol% or more, and among the copper components in the cuprous oxide-containing thermal spray coating, cuprous oxide The ratio is preferably 5 mol% or more. In addition, the elution amount of the copper component when the cuprous oxide-containing thermal spray coating is immersed in salt water (5% by mass sodium chloride aqueous solution) is preferably 0.005 μg / cm 2 / day (0.02 mg / L) or more. .
図１の溶射装置を用いて、マトリックス用材料に酸化銅を添加した溶射材料を基材に対して溶射し、亜酸化銅含有溶射皮膜を作製した。具体的な溶射条件は、以下のとおりである。 Using the thermal spraying apparatus shown in FIG. 1, a thermal spray material obtained by adding copper oxide to a matrix material was sprayed on a base material to prepare a cuprous oxide-containing thermal spray coating. Specific spraying conditions are as follows.
マトリックス用材料としては、Ａｌ−５質量％Ｍｇ合金（Ａｌ合金）、Ｚｎ−４質量％Ｍｇ合金（Ｚｎ合金）、ＳＵＳ３１６（Ｆｅ合金）、Ｎｉ−１５質量％Ａｌ合金（Ｎｉ合金）、Ｎｉ基アモルファス合金及びＦｅ基アモルファス合金の粉末を使用した。このマトリックス用材料に酸化銅の粉末（Ｄ５０＝３０μｍ）を添加して溶射材料とした。溶射材料中の酸化銅の含有量は４０質量％（１８〜３７ｍｏｌ％）となるようにした。 As matrix materials, Al-5 mass% Mg alloy (Al alloy), Zn-4 mass% Mg alloy (Zn alloy), SUS316 (Fe alloy), Ni-15 mass% Al alloy (Ni alloy), Ni base Amorphous alloy and Fe-based amorphous alloy powders were used. Copper oxide powder (D50 = 30 μm) was added to the matrix material to obtain a thermal spray material. The content of copper oxide in the thermal spray material was set to 40% by mass (18 to 37 mol%).
燃焼ガスとしてはアセチレンガスと酸素ガスを使用し、その体積比（アセチレンガス：酸素ガス）は、６：５とした。冷却ガスとして窒素ガスを使用し、その流量は４００〜６００Ｌ／ｍｉｎとした。 As the combustion gas, acetylene gas and oxygen gas were used, and the volume ratio (acetylene gas: oxygen gas) was 6: 5. Nitrogen gas was used as the cooling gas, and the flow rate was 400 to 600 L / min.
基材はＳＳ４００とし、ブラスト処理を行い、表面粗度をＲａ：３．５〜４．５μｍ程度とした。アモルファス合金を含む溶射材料を溶射する際には、基材を２５０〜３００℃に予熱したのち溶射を行った。 The base material was SS400, blasting was performed, and the surface roughness was Ra: about 3.5 to 4.5 μm. When spraying a thermal spray material containing an amorphous alloy, the base material was preheated to 250 to 300 ° C. and then sprayed.
溶射中の溶射材料の供給量は１０〜１５ｇ／ｍｉｎとし、基材上の亜酸化銅含有溶射皮膜の膜厚は２００〜２５０μｍとした。 The supply amount of the thermal spray material during thermal spraying was 10 to 15 g / min, and the film thickness of the cuprous oxide-containing thermal spray coating on the substrate was 200 to 250 μm.
得られたそれぞれの亜酸化銅含有溶射皮膜について、ＳＥＭによる断面観察、エネルギー分散型Ｘ線分析（ＥＤＳ）及びＸ線回折測定（ＸＲＤ）を実施した。また、防食性の評価として、塩水浸漬試験（条件：５質量％塩化ナトリウム水溶液）を実施した。そして、塩水浸漬試験を行った溶液について誘導結合プラズマ質量分析（ＩＣＰ−ＭＳ）を行い、溶液中の銅成分の含有量、すなわち銅成分の溶出量を評価した。 About each obtained cuprous oxide containing thermal spray coating, cross-sectional observation by SEM, energy dispersive X-ray analysis (EDS), and X-ray diffraction measurement (XRD) were implemented. Moreover, the salt water immersion test (condition: 5 mass% sodium chloride aqueous solution) was implemented as evaluation of corrosion resistance. And the inductively coupled plasma mass spectrometry (ICP-MS) was performed about the solution which performed the salt water immersion test, and the content of the copper component in a solution, ie, the elution amount of a copper component, was evaluated.
これらの評価結果を表１にまとめて示す。また図２〜５には、ＳＥＭ観察結果、ＸＲＤ結果、ＥＤＳ結果及び塩水浸漬試験結果の生データ例として、マトリックスがＡｌ−Ｍｇ合金である亜酸化銅含有溶射皮膜のものを示す。さらに図６には、マトリックスがＡｌ−Ｍｇ合金である亜酸化銅含有溶射皮膜を実際の海洋に浸漬した結果を示す。 These evaluation results are summarized in Table 1. Moreover, in FIG. 2-5, the thing of the cuprous oxide containing sprayed coating whose matrix is an Al-Mg alloy is shown as an example of raw data of a SEM observation result, a XRD result, an EDS result, and a salt water immersion test result. Further, FIG. 6 shows a result of immersing a cuprous oxide-containing sprayed coating whose matrix is an Al—Mg alloy in an actual ocean.
表１に示すように、全ての溶射皮膜について亜酸化銅の存在が確認され、亜酸化銅含有溶射皮膜が得られていることが確認された。本実施例において、亜酸化銅含有溶射皮膜中の亜酸化銅含有量はＸ線回折ピークのピーク比により定量したが、マトリックスがＳＵＳ３１６の場合は亜酸化銅とＳＵＳ３１６のＸ線回折ピークが分離できなかったため、マトリックスがアモルファス合金の場合はハローピークが存在していたため、亜酸化銅含有量は定量できなかった。 As shown in Table 1, the presence of cuprous oxide was confirmed for all sprayed coatings, and it was confirmed that a cuprous oxide-containing sprayed coating was obtained. In this example, the cuprous oxide content in the sprayed coating containing cuprous oxide was quantified by the peak ratio of the X-ray diffraction peaks. However, when the matrix is SUS316, the X-ray diffraction peaks of cuprous oxide and SUS316 can be separated. Since there was no halo peak when the matrix was an amorphous alloy, the cuprous oxide content could not be quantified.
また、今回得られた亜酸化銅含有溶射皮膜からは銅成分の溶出が確認されたので、本発明の亜酸化銅含有溶射皮膜は海洋生物の忌避効果（防汚性）を発揮し得ると考えられる。 Moreover, since elution of copper components was confirmed from the cuprous oxide-containing thermal spray coating obtained this time, it is considered that the cuprous oxide-containing thermal spray coating of the present invention can exhibit the repellent effect (antifouling property) of marine organisms. It is done.
さらに、図２のＳＥＭ観察結果及び図３のＥＤＳ結果に示すように、亜酸化銅含有溶射皮膜中の亜酸化銅は皮膜中にほぼ均一に分散しており、基材に沿うような偏平状の形状を有している。溶射に伴う基材との衝突により偏平状に変形したものと考えられる。このように、皮膜中で亜酸化銅が偏平状になると表面積が増大するので、皮膜からの銅成分の溶出量が増大して、海洋生物の忌避効果（防汚性）の増大につながると考えられる。 Furthermore, as shown in the SEM observation result of FIG. 2 and the EDS result of FIG. 3, the cuprous oxide in the cuprous oxide-containing thermal spray coating is almost uniformly dispersed in the coating, and is flat like the base material. It has the shape of It is thought that it deform | transformed into flat shape by the collision with the base material accompanying spraying. In this way, when cuprous oxide is flattened in the film, the surface area increases, so the elution amount of the copper component from the film increases, which leads to an increase in the repellent effect (antifouling property) of marine organisms. It is done.
図５及び図６に示すように、マトリックスがＡｌ−Ｍｇ合金である亜酸化銅含有溶射皮膜は、塩水浸漬試験及び海洋浸漬試験の結果、基材の腐食による赤さびの発生が抑制されることが確認された。すなわち、マトリックスを防食性を有する金属とすることで防食性を発揮でき、しかもこのマトリックス中に亜酸化銅を含有することで、海洋生物の忌避効果（防汚性）も発揮できるといえる。 As shown in FIGS. 5 and 6, the cuprous oxide-containing thermal spray coating whose matrix is an Al—Mg alloy can suppress the occurrence of red rust due to corrosion of the substrate as a result of the salt water immersion test and the marine immersion test. confirmed. That is, it can be said that the anti-corrosion property can be exhibited by making the matrix a metal having an anti-corrosion property, and that the marine organism repellent effect (anti-fouling property) can be exhibited by containing cuprous oxide in the matrix.
なお、比較のため、酸化銅に替えて亜酸化銅を添加した溶射材料を使用して図１の溶射装置により溶射を行ったところ、亜酸化銅が銅に還元され亜酸化銅を含む皮膜は得られなかった。 For comparison, when the thermal spraying material shown in FIG. 1 was sprayed using a thermal spray material in which cuprous oxide was added instead of copper oxide, the coating containing cuprous oxide was reduced to copper. It was not obtained.
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| CN109652755A (en) * | 2019-02-12 | 2019-04-19 | 南昌航空大学 | A kind of preparation method of Mg alloy surface corrosion-inhibiting coating |
| CN109778105A (en) * | 2019-03-07 | 2019-05-21 | 上海海洋大学 | A kind of amorphous composite coating and preparation method thereof |
| US11802330B1 (en) * | 2022-08-22 | 2023-10-31 | The Royal Institution for the Advancement of Learning/McGill Concordia University | Gas turbine engine component with copper oxide coating |
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| JPS60131875A (en) * | 1983-12-20 | 1985-07-13 | 三菱重工業株式会社 | Method of bonding ceramic and metal |
| JPH0340936A (en) * | 1989-07-06 | 1991-02-21 | Shinagawa Refract Co Ltd | Thermal spray material for preventing sticking of shellfish and algae and its using method |
| JP2004083964A (en) * | 2002-08-26 | 2004-03-18 | Hitachi Ltd | Copper-based heat sink and method of manufacturing the same |
| JP2007056327A (en) * | 2005-08-25 | 2007-03-08 | Miyoshi Nakagawa | Arc type metal thermal spraying method |
| JP6367567B2 (en) * | 2014-01-31 | 2018-08-01 | 吉川工業株式会社 | Corrosion-resistant thermal spray coating, method for forming the same, and thermal spraying apparatus for forming the same |
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