JP2019039068A - Film formation method and metallic material - Google Patents
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Abstract
Description
本発明は、金属の表面に対して、プラズマ電解酸化処理により皮膜を形成する方法、及び金属材料に関する。 The present invention relates to a method for forming a film on a metal surface by plasma electrolytic oxidation, and a metal material.
従来、金属の表面に皮膜を形成する方法として、陽極酸化処理を使用する方法が提案されており、例えば、アルカリ性水溶液において、連続パルス電源または交直重畳電源を用いて２つ以上の電位で繰り返し印加する陽極酸化を行うことにより、アルミニウム系マグネシウム合金の表面に、アルミニウム含有量が富化された陽極酸化皮膜を形成する方法が開示されている。そして、このような方法により、アルミニウムを含むマグネシウム合金の耐食性を向上させることができると記載されている（特許文献１参照）。 Conventionally, as a method for forming a film on the surface of a metal, a method using an anodizing treatment has been proposed. For example, an alkaline aqueous solution is repeatedly applied at two or more potentials using a continuous pulse power supply or an AC / DC power supply. A method of forming an anodic oxide film enriched in aluminum content on the surface of an aluminum-based magnesium alloy by performing anodic oxidation is disclosed. It is described that the corrosion resistance of a magnesium alloy containing aluminum can be improved by such a method (see Patent Document 1).
また、プラズマ電解酸化（Plasma Electrolytic Oxidation、以下「ＰＥＯ」とも称する）処理を使用して金属の表面に皮膜を形成する方法が提案されている。 In addition, a method of forming a film on the surface of a metal using plasma electrolytic oxidation (hereinafter also referred to as “PEO”) treatment has been proposed.
このＰＥＯ処理は、金属を電解液に浸漬させた状態で、金属に対して高電圧を印加することにより、金属と電解液との間にプラズマ放電を発生させて、金属の表面に酸化皮膜を形成する処理方法である。 In this PEO treatment, a high voltage is applied to the metal in a state where the metal is immersed in the electrolytic solution, thereby generating a plasma discharge between the metal and the electrolytic solution to form an oxide film on the surface of the metal. It is the processing method to form.
そして、このＰＥＯ処理を使用した皮膜形成方法としては、例えば、窒素原子含有カチオンとアルミニウムに対する安定度定数が９以上のアミノカルボン酸アニオンとを含有する水性電解浴中で、ＰＥＯ処理によりアルミニウム又はアルミニウム合金の表面に、酸化アルミニウムを含有するセラミックス皮膜を形成する方法が開示されている。そして、このような方法により、アルミニウム及びその合金の表面にアルカリ金属を含有しない酸化アルミニウムの平滑性に優れる皮膜が形成された金属材料を提供することができると記載されている（例えば、特許文献２参照）。 As a film forming method using this PEO treatment, for example, in an aqueous electrolytic bath containing a nitrogen atom-containing cation and an aminocarboxylic acid anion having a stability constant for aluminum of 9 or more, aluminum or aluminum is obtained by PEO treatment. A method of forming a ceramic film containing aluminum oxide on the surface of an alloy is disclosed. And it is described by such a method that the metal material by which the film | membrane excellent in the smoothness of the aluminum oxide which does not contain an alkali metal was formed in the surface of aluminum and its alloy can be provided (for example, patent document) 2).
また、ジルコニウム化合物を含有する電解液中で金属を陽極としてＰＥＯ処理を行うことにより、金属の表面にセラミック皮膜を形成する方法が開示されている。そして、このような方法により、耐摩耗性及び摺動特性に優れた金属材料を提供することができると記載されている（例えば、特許文献３参照）。 Also disclosed is a method for forming a ceramic film on the surface of a metal by performing a PEO treatment with the metal as an anode in an electrolytic solution containing a zirconium compound. And it is described that the metal material excellent in abrasion resistance and sliding characteristics can be provided by such a method (for example, refer patent document 3).
ここで、上記特許文献１に記載のプラズマ放電を伴わない陽極酸化処理においては、得られる皮膜が多孔質であるため、腐食の原因となる塩分等の成分が当該多孔質を浸透してしまい、例えば、マグネシウムやマグネシウム合金等の耐食性に乏しい金属において、耐食性を十分に向上することができないという問題があった。 Here, in the anodizing treatment without plasma discharge described in Patent Document 1, since the obtained film is porous, components such as salt that cause corrosion penetrate the porous material, For example, there has been a problem that corrosion resistance cannot be sufficiently improved in metals having poor corrosion resistance such as magnesium and magnesium alloys.
また、上記特許文献２，３に記載の方法では、金属の平滑性や耐摩耗性等を向上することはできるものの、金属の耐食性について検討が不十分であり、上述の耐食性に乏しい金属において、耐食性及び素地との密着性を十分に向上することができないという問題があった。 In addition, in the methods described in Patent Documents 2 and 3, although the smoothness and wear resistance of the metal can be improved, the examination of the corrosion resistance of the metal is insufficient, and in the above-described metal having poor corrosion resistance, There was a problem that the corrosion resistance and the adhesion to the substrate could not be sufficiently improved.
そこで、本発明は、上述の問題に鑑みてなされたものであり、金属の表面に耐食性及び素地との密着性の高い皮膜を形成して、耐食性に優れた金属材料を得ることができるプラズマ電解酸化による皮膜形成方法、及び金属材料を提供することを目的とする。 Accordingly, the present invention has been made in view of the above-described problems, and plasma electrolysis that can form a metal material having excellent corrosion resistance by forming a coating having high corrosion resistance and adhesion to the substrate on the surface of the metal. An object is to provide a film forming method by oxidation and a metal material.
上記目的を達成するために、本発明の皮膜形成方法は、第１水溶性化合物を含有する第１電解液に金属を浸漬させた状態で、プラズマ放電を伴わない陽極酸化処理を施すことにより、金属の表面に第１皮膜を形成する第１皮膜形成工程と、第２水溶性化合物を含有し、第１電解液とは組成の異なる第２電解液に金属を浸漬させた状態で、金属と第２電解液との間にプラズマ放電を発生させてプラズマ電解酸化処理を施すことにより、金属表面と第１皮膜の間に第１皮膜とは異なる組成を有する第２皮膜を形成する第２皮膜形成工程とを備えることを特徴とする。 In order to achieve the above-mentioned object, the film forming method of the present invention performs an anodic oxidation treatment without plasma discharge in a state in which a metal is immersed in the first electrolytic solution containing the first water-soluble compound. A first film forming step of forming a first film on the surface of the metal; and a second water-soluble compound, the metal being immersed in a second electrolytic solution having a composition different from that of the first electrolytic solution, A second coating that forms a second coating having a composition different from that of the first coating between the metal surface and the first coating by performing plasma electrolytic oxidation treatment by generating plasma discharge with the second electrolytic solution. And a forming step.
同構成によれば、金属の表面に、組成の異なる複数の皮膜を積層させて形成するため、耐食性及び密着性の高い皮膜を形成することが可能になる。従って、耐食性並びに金属と第２皮膜との密着性に優れた金属材料を得ることができる。 According to this configuration, a plurality of coatings having different compositions are laminated on the surface of the metal, so that a coating having high corrosion resistance and high adhesion can be formed. Therefore, a metal material excellent in corrosion resistance and adhesion between the metal and the second film can be obtained.
本発明の皮膜形成方法においては、第２水溶性化合物が、リン酸塩、ケイ酸塩、硝酸塩、アルミン酸塩、タングステン酸塩、ホウ酸塩、ジルコニウム酸塩、モリブデン酸塩、炭酸塩、重炭酸塩、及び水酸化物からなる群より選ばれる少なくとも１種であってもよい。 In the film forming method of the present invention, the second water-soluble compound is phosphate, silicate, nitrate, aluminate, tungstate, borate, zirconate, molybdate, carbonate, heavy salt. It may be at least one selected from the group consisting of carbonates and hydroxides.
本発明の皮膜形成方法においては、第２電解液中の第２水溶性化合物の濃度が０．００１Ｍ〜５Ｍであってもよい。 In the film forming method of the present invention, the concentration of the second water-soluble compound in the second electrolytic solution may be 0.001M to 5M.
同構成によれば、皮膜の密着性及び成膜性を向上させることができる。 According to this configuration, the adhesion and film-forming property of the film can be improved.
本発明の皮膜形成方法においては、金属として、マグネシウムまたはマグネシウム合金を使用してもよい。 In the film forming method of the present invention, magnesium or a magnesium alloy may be used as the metal.
同構成によれば、特に、耐食性の乏しいマグネシウムまたはマグネシウム合金の表面に耐食性の高い皮膜を形成することが可能になるため、耐食性に優れたマグネシウム材料またはマグネシウム合金材料を得ることができる。 According to this configuration, it is possible to form a highly corrosion-resistant film on the surface of magnesium or a magnesium alloy having particularly poor corrosion resistance, so that a magnesium material or a magnesium alloy material having excellent corrosion resistance can be obtained.
本発明の金属材料は、金属基板と、金属基板の表面に形成された皮膜とを備えた金属材料であって、皮膜は、金属基板の表面において金属基板を覆うように形成された第２皮膜と、第２皮膜の表面において第２皮膜を覆うように形成された第１皮膜により構成され、第１皮膜は、少なくとも水酸化物を含有し、第２皮膜は、リン酸塩、ケイ酸塩、硝酸塩、アルミン酸塩、タングステン酸塩、ホウ酸塩、ジルコニウム酸塩、モリブデン酸塩、炭酸塩、重炭酸塩、水酸化物及び金属酸化物からなる群より選ばれる少なくとも１種を含有することを特徴とする。 The metal material of the present invention is a metal material including a metal substrate and a film formed on the surface of the metal substrate, and the film is a second film formed so as to cover the metal substrate on the surface of the metal substrate. And a first film formed so as to cover the second film on the surface of the second film, the first film contains at least a hydroxide, and the second film includes phosphate and silicate. Containing at least one selected from the group consisting of nitrate, aluminate, tungstate, borate, zirconate, molybdate, carbonate, bicarbonate, hydroxide and metal oxide It is characterized by.
同構成によれば、金属の表面に、組成の異なる複数の皮膜が積層するため、耐食性及び密着性の高い皮膜を形成することが可能になる。従って、耐食性並びに金属と第２皮膜との密着性に優れた金属材料を提供することができる。 According to this configuration, since a plurality of coatings having different compositions are laminated on the metal surface, it is possible to form a coating with high corrosion resistance and adhesion. Therefore, it is possible to provide a metal material excellent in corrosion resistance and adhesion between the metal and the second film.
本発明の金属材料においては、第２皮膜が、金属基板の表面上に形成された第１緻密層と、第１緻密層の表面上に形成された第２緻密層により構成されていてもよい。 In the metal material of the present invention, the second film may be composed of a first dense layer formed on the surface of the metal substrate and a second dense layer formed on the surface of the first dense layer. .
本発明によれば、金属の表面に、耐食性及び金属との密着性に優れた皮膜を形成することが可能になり、耐食性に優れた金属材料を得ることができる。 ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to form the membrane | film | coat excellent in corrosion resistance and the adhesiveness with a metal on the surface of a metal, and can obtain the metal material excellent in corrosion resistance.
以下、本発明の実施形態を図面に基づいて詳細に説明する。尚、本発明は、以下の実施形態に限定されるものではない。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The present invention is not limited to the following embodiment.
図１は、本発明の実施形態に係る皮膜が形成された金属材料を示す断面図である。 FIG. 1 is a cross-sectional view showing a metal material on which a film according to an embodiment of the present invention is formed.
図１に示すように、本実施形態の金属材料１は、金属基板２と金属基板２の表面に形成された皮膜（複合皮膜）３とを備えている。 As shown in FIG. 1, the metal material 1 of this embodiment includes a metal substrate 2 and a film (composite film) 3 formed on the surface of the metal substrate 2.
金属基板２を形成する金属としては、ＰＥＯ処理において電流を流すことができるものであれば特に限定されず、例えば、マグネシウム、アルミニウム、亜鉛、マンガン、カルシウム、イットリウム、シリコン、チタン、鉄及びこれらの合金を使用することができる。 The metal forming the metal substrate 2 is not particularly limited as long as a current can flow in the PEO process. For example, magnesium, aluminum, zinc, manganese, calcium, yttrium, silicon, titanium, iron, and these Alloys can be used.
また、本実施形態の金属材料１においては、金属基板２の表面に、組成の異なる複数の皮膜を積層させることにより皮膜３が形成されている。 Moreover, in the metal material 1 of this embodiment, the film 3 is formed on the surface of the metal substrate 2 by laminating a plurality of films having different compositions.
より具体的には、図１に示すように、皮膜３は、金属基板２の表面において該金属基板２を覆うように形成された第２皮膜５と、第２皮膜５の表面において第２皮膜５を覆うように形成された第１皮膜４とにより構成されている。また、第１皮膜４は第２皮膜５とは異なる組成及び構造を有している。 More specifically, as shown in FIG. 1, the coating 3 includes a second coating 5 formed so as to cover the metal substrate 2 on the surface of the metal substrate 2, and a second coating on the surface of the second coating 5. And a first film 4 formed so as to cover 5. The first film 4 has a composition and structure different from those of the second film 5.
第１皮膜４は、第１水溶性化合物を含有する第１電解液に金属材料１を陽極として浸漬させた状態で、プラズマ放電を伴わない陽極酸化処理を施すことにより形成され、少なくとも水酸化物（例えば、水酸化マグネシウム等）を含有している。 The first film 4 is formed by performing anodization without plasma discharge in a state where the metal material 1 is immersed as an anode in a first electrolytic solution containing a first water-soluble compound. (For example, magnesium hydroxide).
第１電解液は、水を主成分とし、第１皮膜４の原料となる第１水溶性化合物（水溶性塩）とを含有するものが使用される。 As the first electrolytic solution, one containing water as a main component and containing a first water-soluble compound (water-soluble salt) that is a raw material of the first coating 4 is used.
第１水溶性化合物としては、低電圧で陽極酸化処理できるアルカリ溶液であれば特に限定はされず、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム及び水酸化バリウム等の水酸化物を使用することができる。 The first water-soluble compound is not particularly limited as long as it is an alkaline solution that can be anodized at a low voltage. For example, hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and barium hydroxide are used. can do.
また、マグネシウム及びその合金はアルカリ性において安定であるとの観点から、第１電解液のｐＨは１３以上が好ましく、本実施形態においては、電解液のｐＨが上記範囲内となるように、第１電解液にＫＯＨ等のｐＨ調整剤を添加してもよい。 In addition, from the viewpoint that magnesium and its alloys are stable in alkalinity, the pH of the first electrolytic solution is preferably 13 or more. In the present embodiment, the first electrolytic solution has a pH within the above range. You may add pH adjusters, such as KOH, to electrolyte solution.
第２皮膜５は、第２水溶性化合物を含有し、第１電解液とは組成の異なる第２電解液に第１皮膜４が形成された金属基板２を浸漬させた状態で、金属基板２に対して電流を流すことにより、金属基板２と第２電解液との間にプラズマ放電を発生させて、ＰＥＯ処理を施すことにより、金属基板２の表面と第１皮膜４の間に形成される。 The second coating 5 contains the second water-soluble compound, and the metal substrate 2 is immersed in the second electrolytic solution having a composition different from that of the first electrolytic solution. Is formed between the surface of the metal substrate 2 and the first coating 4 by applying a PEO treatment by generating a plasma discharge between the metal substrate 2 and the second electrolyte. The
第２皮膜５は、リン酸塩、ケイ酸塩、硝酸塩、アルミン酸塩、タングステン酸塩、ホウ酸塩、ジルコニウム酸塩、モリブデン酸塩、炭酸塩、重炭酸塩、水酸化物及び金属酸化物からなる群より選ばれる少なくとも１種を含有している。 The second film 5 is composed of phosphate, silicate, nitrate, aluminate, tungstate, borate, zirconate, molybdate, carbonate, bicarbonate, hydroxide and metal oxide. At least one selected from the group consisting of:
この第２皮膜５は、図１に示すように、金属基板２の表面上に形成された第１緻密層５ａと、第１緻密層５ａの表面上に形成された第２緻密層５ｂにより構成されている。 As shown in FIG. 1, the second film 5 is composed of a first dense layer 5a formed on the surface of the metal substrate 2 and a second dense layer 5b formed on the surface of the first dense layer 5a. Has been.
そして、第１緻密層５ａは、ボイドが少なく通常のセラミック皮膜（厚み：約１０ｎｍ）と比較して非常に厚い（数〜数十μｍ）という特異な構造を有しているため、金属基材２と第２緻密層５ｂとの密着性を高め、金属材料２の耐食性を向上させることが出来る。また、第２緻密層５ｂは第１皮膜４の孔を埋めるように緻密な酸化物が生成しているため、第１皮膜４との密着性を向上させることが可能になる。 And since the 1st dense layer 5a has a peculiar structure that there are few voids and it is very thick (several to several tens of μm) compared with a normal ceramic film (thickness: about 10 nm), the metal substrate 2 and the second dense layer 5b can be improved, and the corrosion resistance of the metal material 2 can be improved. In addition, since the dense oxide is generated in the second dense layer 5 b so as to fill the holes of the first coating 4, it is possible to improve the adhesion with the first coating 4.
ＰＥＯ処理において使用する第２電解液は、水を主成分とし、第２皮膜５の原料となる水溶性化合物（水溶性塩）とを含有するものが使用される。 As the second electrolytic solution used in the PEO treatment, one containing water as a main component and containing a water-soluble compound (water-soluble salt) that is a raw material for the second coating 5 is used.
第２水溶性化合物としては、特に限定はされず、例えば、リン酸三ナトリウム等のリン酸塩、メタケイ酸ナトリウム等のケイ酸塩、硝酸ナトリウム等の硝酸塩、アルミン酸ナトリウム等のアルミン酸塩、タングステン酸ナトリウム等のタングステン酸塩、六フッ化ジルコン酸カリウム等のジルコニウム酸塩、モリブテン酸ナトリウム等のモリブデン酸塩、炭酸ナトリウム等の炭酸塩、炭酸水素ナトリウム等の重炭酸塩、ホウ砂、ホウ酸ナトリウム等のホウ酸塩及び水酸化ナトリウムや水酸化カリウム等の水酸化物を使用することができる。 The second water-soluble compound is not particularly limited, for example, phosphates such as trisodium phosphate, silicates such as sodium metasilicate, nitrates such as sodium nitrate, aluminates such as sodium aluminate, Tungstates such as sodium tungstate, zirconates such as potassium hexafluorozirconate, molybdates such as sodium molybdate, carbonates such as sodium carbonate, bicarbonates such as sodium bicarbonate, borax, borax Borates such as sodium acid and hydroxides such as sodium hydroxide and potassium hydroxide can be used.
また、第２電解液には、水酸化カリウムや水酸化ナトリウム等をｐＨ調整剤として含有させてもよい。また、プラズマ放電の安定化のため、第２電解液に、エチレングリコール等のアルコール性水酸基を有する溶剤を加えてもよい。 Further, the second electrolytic solution may contain potassium hydroxide, sodium hydroxide or the like as a pH adjuster. In order to stabilize the plasma discharge, a solvent having an alcoholic hydroxyl group such as ethylene glycol may be added to the second electrolytic solution.
また、金属基板２の表面を安定化させるとの観点から、電解液のｐＨは７〜１４の範囲が好ましく、本実施形態においては、電解液のｐＨが上記範囲内となるように、電解液に上記ｐＨ調整剤が添加できる。 Further, from the viewpoint of stabilizing the surface of the metal substrate 2, the pH of the electrolytic solution is preferably in the range of 7 to 14, and in this embodiment, the electrolytic solution is adjusted so that the pH of the electrolytic solution is within the above range. The above pH adjuster can be added.
次に、本発明の実施形態に係るプラズマ電解酸化による皮膜形成方法について説明する。図２は、本発明の実施形態に係るプラズマ電解酸化による皮膜形成方法を説明するための図である。 Next, a film forming method by plasma electrolytic oxidation according to an embodiment of the present invention will be described. FIG. 2 is a view for explaining a film formation method by plasma electrolytic oxidation according to an embodiment of the present invention.
＜第１皮膜形成工程＞
まず、溶媒である水に、例えば、第１皮膜４の原料でありｐＨ調整剤としても機能する水酸化カリウムを加え、均一となるように攪拌して混合することにより、第１水溶性化合物を含有する第１電解液を作製する。なお、必要に応じて、ＥＤＴＡ等のキレート剤を加えてもよい（ステップＳ１）。
<First film forming step>
First, for example, potassium hydroxide that is a raw material of the first film 4 and also functions as a pH adjuster is added to water as a solvent, and the first water-soluble compound is obtained by stirring and mixing so as to be uniform. The 1st electrolyte solution to contain is produced. In addition, you may add chelating agents, such as EDTA, as needed (step S1).
なお、第１皮膜４の密着性及び成膜性を向上させるとの観点から、第１電解液中の第１水溶性化合物の濃度は０．００１Ｍ〜５Ｍが好ましく、０．１Ｍ〜２Ｍがより好ましい。 The concentration of the first water-soluble compound in the first electrolytic solution is preferably 0.001M to 5M, more preferably 0.1M to 2M, from the viewpoint of improving the adhesion and film-forming properties of the first film 4. preferable.
次に、例えば、マグネシウムからなる金属基板２を第１電解液に浸漬させ（ステップＳ２）、金属基板２を第１電解液に浸漬させた状態で、プラズマ放電を伴わない陽極酸化処理を施すことにより、図３に示すように、金属基板２の表面に第１皮膜４を形成する（ステップＳ３）。 Next, for example, a metal substrate 2 made of magnesium is immersed in the first electrolyte solution (step S2), and an anodizing process without plasma discharge is performed in a state where the metal substrate 2 is immersed in the first electrolyte solution. Thus, as shown in FIG. 3, the first film 4 is formed on the surface of the metal substrate 2 (step S3).
この際、金属基板２を構成する金属（例えば、マグネシウム）と第１電解液に含有された水酸化物（例えば、水酸化カリウム）が反応するため、第１皮膜４は、少なくとも水酸化物（例えば、水酸化マグネシウム等）を含有することになる。 At this time, since the metal (for example, magnesium) constituting the metal substrate 2 and the hydroxide (for example, potassium hydroxide) contained in the first electrolyte solution react, the first coating 4 has at least a hydroxide (for example, For example, magnesium hydroxide is contained.
ここで、本実施形態における「プラズマ放電を伴わない陽極酸化処理」とは、電気化学反応のみで反応が進行する処理をいう。なお、この処理においては、後述のＰＥＯ反応時のような発光現象は観察されない。 Here, the “anodic oxidation process without plasma discharge” in the present embodiment refers to a process in which the reaction proceeds only by an electrochemical reaction. In this process, no light emission phenomenon is observed as in the PEO reaction described later.
また、陽極酸化の処理法としては、金属基板２を陽極として用いた、パルス電解法、直流電解法、定電圧電解法及び定電流電解法等が使用できるが、均一に皮膜を形成するとの観点から、本実施形態においては、直流の定電流電解法を使用することが好ましい。 In addition, as an anodic oxidation treatment method, a pulse electrolysis method, a direct current electrolysis method, a constant voltage electrolysis method, a constant current electrolysis method and the like using the metal substrate 2 as an anode can be used, but from the viewpoint of forming a film uniformly. In this embodiment, it is preferable to use a DC constant current electrolysis method.
また、電解電流としては、最大電流が放電（アーク放電）電流未満であればよいが、陽極酸化処理の安定性を向上させるとの観点から、２０〜６００Ａ／ｍ２が好ましく、１００〜２００Ａ／ｍ２がより好ましい。 Moreover, as electrolysis current, the maximum current may be less than the discharge (arc discharge) current, but from the viewpoint of improving the stability of the anodizing treatment, 20 to 600 A / m 2 is preferable, and 100 to 200 A / m 2 is preferable. m 2 is more preferable.
また、陽極酸化処理の時間は、第１皮膜４の耐食性の確保とエネルギー効率の観点から適宜変更することができ、例えば、１〜１００分、好ましくは２０〜５０分に設定することができる。 Moreover, the time of an anodizing process can be suitably changed from a viewpoint of ensuring corrosion resistance of the 1st membrane | film | coat 4, and energy efficiency, for example, can be set to 1 to 100 minutes, Preferably it is 20 to 50 minutes.
また、陽極酸化処理を行う際の対極を形成する材料としては、例えば、ステンレス、黒鉛、銅、チタン及び白金等を使用することができる。 Moreover, as a material which forms the counter electrode at the time of performing an anodizing process, stainless steel, graphite, copper, titanium, platinum, etc. can be used, for example.
＜第２皮膜形成工程＞
まず、溶媒である水に、例えば、第２皮膜５の原料となるリン酸三ナトリウムと水酸化カリウム等のｐＨ調整剤とを加え、均一となるように攪拌して混合することにより、第２水溶性化合物を含有する第２電解液を作製する。なお、必要に応じて、ＥＤＴＡ等のキレート剤を加えてもよい（ステップＳ４）。
<Second film forming step>
First, for example, trisodium phosphate as a raw material of the second film 5 and a pH adjuster such as potassium hydroxide are added to water as a solvent, and the mixture is stirred and mixed to be uniform. A second electrolytic solution containing a water-soluble compound is prepared. In addition, you may add chelating agents, such as EDTA, as needed (step S4).
なお、第２皮膜５の密着性及び成膜性を向上させるとの観点から、第２電解液中の第２水溶性化合物の濃度は０．００１Ｍ〜５Ｍが好ましく、０．０１M〜１Mがより好ましい。 The concentration of the second water-soluble compound in the second electrolytic solution is preferably 0.001M to 5M, more preferably 0.01M to 1M from the viewpoint of improving the adhesion and film-forming properties of the second film 5. preferable.
次に、例えば、図３に示す第１皮膜４が形成されたマグネシウムからなる金属基板２を第２電解液に浸漬させ（ステップＳ５）、金属基板２を第２電解液に浸漬させた状態で、金属基板２に対して定電流を流すことにより、金属基板２と電解液との間にプラズマ放電を発生させて、ＰＥＯ処理を施すことにより、図１に示すように、金属基板２の表面と第１皮膜４の間に、第１皮膜４とは異なる組成を有する第２皮膜５を形成する（ステップＳ６）。 Next, for example, the metal substrate 2 made of magnesium on which the first film 4 shown in FIG. 3 is formed is immersed in the second electrolytic solution (step S5), and the metal substrate 2 is immersed in the second electrolytic solution. By applying a constant current to the metal substrate 2, a plasma discharge is generated between the metal substrate 2 and the electrolytic solution, and a PEO treatment is performed, as shown in FIG. A second film 5 having a composition different from that of the first film 4 is formed between the first film 4 and the first film 4 (step S6).
なお、ここで言う「ＰＥＯ処理」とは、発光を伴う陽極酸化処理のことを言う。 The “PEO treatment” here refers to an anodizing treatment with light emission.
より具体的には、ＰＥＯ処理を開始すると、図４〜図５に示すように、第２電解液中に含まれる酸素を含む化学種（即ち、リン酸ナトリウム等の水溶性化合物）６が第１皮膜４に浸透するとともに当該第１皮膜４を通過して、陽極である金属基板２の表面に移動する。そして、金属基板２において電解反応が発生して発光が生じ、金属基板２を形成する金属と水中の酸素を含む化学種６とが反応して、第１皮膜４に形成された孔を金属基材２に接している側から埋めるように緻密な酸化物が生成し、第２緻密層５ｂ（例えば、水酸化マグネシウムとリン酸マグネシウム，および酸化マグネシウムによる複合皮膜）が形成される。更に電解を継続すると、金属基板２の表面に第１緻密層（例えば、酸化マグネシウムとリン酸マグネシウム（いずれも非晶質）から成るボイドやポアを含まない、またはボイドやポアが少ないバリア型の酸化物層）５ａが形成される。 More specifically, when the PEO treatment is started, as shown in FIGS. 4 to 5, the chemical species (that is, a water-soluble compound such as sodium phosphate) 6 containing oxygen contained in the second electrolyte solution is changed to the first. It penetrates into one coating 4 and passes through the first coating 4 to move to the surface of the metal substrate 2 that is an anode. Then, an electrolytic reaction occurs in the metal substrate 2 to generate light emission, and the metal forming the metal substrate 2 reacts with the chemical species 6 containing oxygen in water, so that the holes formed in the first coating 4 are formed on the metal substrate. A dense oxide is generated so as to be buried from the side in contact with the material 2, and a second dense layer 5b (for example, a composite film made of magnesium hydroxide, magnesium phosphate, and magnesium oxide) is formed. If the electrolysis is further continued, the surface of the metal substrate 2 does not contain a first dense layer (for example, voids or pores made of magnesium oxide and magnesium phosphate (both amorphous), or a barrier type with few voids and pores). Oxide layer) 5a is formed.
なお、第２緻密層５ｂが形成される際に、第１緻密層５ａが同時に形成される場合もある。 In addition, when the 2nd dense layer 5b is formed, the 1st dense layer 5a may be formed simultaneously.
以上により、図１に示すように、金属基板２の表面上に数μｍ〜数十μｍの厚みを有する多孔質のセラミック膜（即ち、例えば、リン酸マグネシウムを含有する第２皮膜５）が形成される。 Thus, as shown in FIG. 1, a porous ceramic film having a thickness of several μm to several tens of μm (that is, for example, the second film 5 containing magnesium phosphate) is formed on the surface of the metal substrate 2. Is done.
なお、ＰＥＯ処理法として、金属基板２を陽極として用いたパルス電解法、直流電解法、定電圧電解法及び定電流電解法等が使用できるが、均一に第２皮膜５を形成するとの観点から、本実施形態においては、直流の定電流電解法を使用することが好ましい。 In addition, as a PEO treatment method, a pulse electrolysis method using a metal substrate 2 as an anode, a direct current electrolysis method, a constant voltage electrolysis method, a constant current electrolysis method, and the like can be used. From the viewpoint of uniformly forming the second film 5, In the present embodiment, it is preferable to use a DC constant current electrolysis method.
また、電解電流としては、最大電流が放電（アーク放電）電流以上であればよいが、ＰＥＯ処理の安定性を向上させるとの観点から、２０〜６００Ａ／ｍ２が好ましく、１００〜２００Ａ／ｍ２がより好ましい。 Moreover, as an electrolysis current, although the maximum current should just be more than a discharge (arc discharge) current, 20-600 A / m < 2 > is preferable from a viewpoint of improving the stability of PEO process, and 100-200 A / m. 2 is more preferable.
また、ＰＥＯ処理の時間は、第２皮膜５の耐食性の確保とエネルギー効率の観点から適宜変更することができ、例えば、２０秒〜５分、好ましくは３０〜６０分に設定することができる。 Moreover, the time of PEO process can be suitably changed from a viewpoint of ensuring corrosion resistance of the 2nd membrane | film | coat 5, and energy efficiency, for example, can be set to 20 second-5 minutes, Preferably it is 30-60 minutes.
また、ＰＥＯ処理を行う際の対極を形成する材料としては、上述のステンレス、黒鉛、銅、チタン及び白金等を使用することができる。 Moreover, as a material which forms the counter electrode at the time of performing a PEO process, the above-mentioned stainless steel, graphite, copper, titanium, platinum, etc. can be used.
以上のように、本実施形態においては、陽極酸化処理により第１皮膜４を形成した後にＰＥＯ処理を行うことにより、金属基板２の表面と第１皮膜４との間に第１皮膜４とは異なる組成を有する第２皮膜５を形成することが可能になる。その結果、単一皮膜（即ち、第１皮膜４）の欠陥を減少し補完することができるため、耐食性の高い皮膜３を形成することが可能になる。 As described above, in the present embodiment, the first film 4 is formed between the surface of the metal substrate 2 and the first film 4 by performing the PEO process after the first film 4 is formed by the anodic oxidation process. It becomes possible to form the 2nd membrane | film | coat 5 which has a different composition. As a result, defects in the single film (that is, the first film 4) can be reduced and supplemented, and thus the film 3 having high corrosion resistance can be formed.
以上のようにして、図１に示す、金属基板２の表面上に皮膜３が形成された、耐食性に優れた金属材料１を作製することができる。 As described above, the metal material 1 having excellent corrosion resistance in which the film 3 is formed on the surface of the metal substrate 2 shown in FIG. 1 can be produced.
なお、第１皮膜形成工程において、本発明のプラズマ放電を伴わない陽極酸化処理を行う代わりに、例えば、金属基板に熱可塑性樹脂または熱硬化性樹脂を塗布することにより金属基板の表面に第１皮膜を形成する方法も考えられるが、この皮膜は陽極酸化処理により得られる皮膜とは異なり多孔質ではないため、第２電解液中に含まれる第２水溶性化合物が第１皮膜４を浸透することができないものと考えられる。従って、樹脂の塗布により第１皮膜を形成した後にＰＥＯ処理を行った場合では、金属基板の表面と第１皮膜との間に第１皮膜とは異なる組成を有する第２皮膜を形成することが困難になるため、耐食性の高い皮膜を形成することが困難になるものと考えられる。 In the first film forming step, instead of performing the anodizing treatment without plasma discharge of the present invention, for example, a first resin is applied to the surface of the metal substrate by applying a thermoplastic resin or a thermosetting resin to the metal substrate. Although a method of forming a film is also conceivable, unlike the film obtained by anodic oxidation, this film is not porous, so that the second water-soluble compound contained in the second electrolytic solution penetrates the first film 4. It is considered impossible. Therefore, when the PEO treatment is performed after the first film is formed by applying the resin, a second film having a composition different from that of the first film may be formed between the surface of the metal substrate and the first film. It becomes difficult to form a highly corrosion-resistant film.
また、上記実施形態においては第１緻密層５ａと第２緻密層５ｂにより構成された第２皮膜５を説明したが、本発明の第２皮膜５は、第１緻密層５ａ及び第２緻密層５ｂの少なくとも一方により構成されていればよい。例えば、第２皮膜５が、第２緻密層５ｂのみにより構成されていてもよい。 Moreover, in the said embodiment, although the 2nd membrane | film | coat 5 comprised by the 1st dense layer 5a and the 2nd dense layer 5b was demonstrated, the 2nd membrane | film | coat 5 of this invention is the 1st dense layer 5a and the 2nd dense layer. What is necessary is just to be comprised by at least one of 5b. For example, the 2nd membrane | film | coat 5 may be comprised only by the 2nd dense layer 5b.
以下に、本発明を実施例に基づいて説明する。なお、本発明は、これらの実施例に限定されるものではなく、これらの実施例を本発明の趣旨に基づいて変形、変更することが可能であり、それらを本発明の範囲から除外するものではない。 Hereinafter, the present invention will be described based on examples. In addition, this invention is not limited to these Examples, These Examples can be changed and changed based on the meaning of this invention, and they are excluded from the scope of the present invention. is not.
（実施例１）
（第１電解液の作製）
溶媒である水に、水酸化カリウム（和光純薬工業（株）製）を加え、均一となるように攪拌して、第１電解液を作製した。
Example 1
(Preparation of first electrolyte)
Potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added to water as a solvent, and the mixture was stirred uniformly to produce a first electrolytic solution.
なお、第１電解液中の水酸化カリウムの濃度が１．０Ｍとなるように調整した。また、電解液のｐＨは１３．６５であった。 In addition, it adjusted so that the density | concentration of the potassium hydroxide in a 1st electrolyte solution might be 1.0M. The pH of the electrolytic solution was 13.65.
（第１皮膜用の陽極酸化処理）
次に、アルミニウムを３％、亜鉛を１％添加したマグネシウム合金（ＡＺ３１）からなり、厚みが１ｍｍ、表面積が１０ｃｍ２であるマグネシウム合金板を陽極として使用するとともに炭素棒を対極として使用し、マグネシウム合金板を第１皮膜用の電解液に浸漬させた状態で、３０分間、直流の定電流電解法（電解電流：２００Ａ／ｍ２）により、マグネシウム合金板と電解液との間にプラズマ放電を伴わない陽極酸化処理を行い、マグネシウム合金板の表面に、約１２μｍの厚みを有する第１皮膜を形成した。
(Anodizing treatment for the first film)
Next, a magnesium alloy plate (AZ31) containing 3% aluminum and 1% zinc and having a thickness of 1 mm and a surface area of 10 cm 2 is used as an anode and a carbon rod is used as a counter electrode. With the alloy plate immersed in the electrolytic solution for the first film, plasma discharge was performed between the magnesium alloy plate and the electrolytic solution by a direct current constant current electrolytic method (electrolytic current: 200 A / m 2 ) for 30 minutes. An anodic oxidation treatment was performed, and a first film having a thickness of about 12 μm was formed on the surface of the magnesium alloy plate.
なお、この第１皮膜を、Ｘ線回折装置（Bruker製、商品名：XRD，MXP-18AHF22）を利用してＸ線回折法によって確認したところ、第１皮膜は水酸化マグネシウムを含有していた。 In addition, when this 1st membrane | film | coat was confirmed by the X-ray-diffraction method using the X-ray-diffraction apparatus (The product made from Bruker, brand name: XRD, MXP-18AHF22), the 1st membrane | film | coat contained magnesium hydroxide. .
（第２電解液の作製）
次いで、溶媒である水にリン酸三ナトリウム（和光純薬工業（株）製）を加え、均一となるように攪拌して、第２電解液を作製した。
(Preparation of second electrolyte)
Subsequently, trisodium phosphate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to water as a solvent, and the mixture was stirred uniformly to prepare a second electrolytic solution.
なお、電解液中のリン酸三ナトリウムの濃度が０．５Ｍとなるように調整した。また、電解液のｐＨは１２．６３であった。 In addition, it adjusted so that the density | concentration of the trisodium phosphate in electrolyte solution might be set to 0.5M. The pH of the electrolytic solution was 12.63.
（第２皮膜用のＰＥＯ処理）
次に、上述の第１皮膜が形成されたマグネシウム合金板を陽極として使用するとともに炭素棒を対極として使用し、第１皮膜が形成されたマグネシウム合金板を第２皮膜用の第２電解液に浸漬させた状態で、１分間、直流の定電流電解法（電解電流：２００Ａ／ｍ２）により、第１皮膜が形成されたマグネシウム合金板と第２皮膜用の電解液との間に微少なプラズマ放電を発生させて、マグネシウム合金板の表面と第１皮膜との間に、約２μｍの厚みを有する第２皮膜を形成し、本実施例の金属材料を作製した。
(PEO treatment for second coating)
Next, the magnesium alloy plate on which the first film is formed is used as an anode and a carbon rod is used as a counter electrode, and the magnesium alloy plate on which the first film is formed is used as the second electrolytic solution for the second film. In the soaked state, a minute amount is applied between the magnesium alloy plate on which the first film is formed and the electrolyte solution for the second film by a direct current electrolysis method (electrolytic current: 200 A / m 2 ) for 1 minute. A plasma discharge was generated to form a second film having a thickness of about 2 μm between the surface of the magnesium alloy plate and the first film, and a metal material of this example was produced.
なお、この第２皮膜をエネルギー分散型Ｘ線分析装置（日本電子（株）製、商品名：ＥＤＸ，ＥＸ−５４１７５ＪＭＵ）によって確認したところ、第２皮膜は酸化マグネシウムに加えて電解液由来のリンを含有していた。 The second film was confirmed by an energy dispersive X-ray analyzer (manufactured by JEOL Ltd., trade name: EDX, EX-54175JMU). As a result, the second film was a phosphorous derived from an electrolyte in addition to magnesium oxide. Contained.
（比較例１）
上述の第２電解液を用いた第２皮膜用のＰＥＯ処理を行わず、上述の第１電解液を用いた第１皮膜用の酸化処理のみを行い、マグネシウム合金板の表面に第１皮膜のみを形成して、本比較例の金属材料を作製した。
(Comparative Example 1)
Without performing the PEO treatment for the second coating using the second electrolytic solution described above, only the oxidation treatment for the first coating using the first electrolytic solution described above is performed, and only the first coating is applied to the surface of the magnesium alloy plate. The metal material of this comparative example was produced.
（比較例２）
上述の第１電解液を用いた第１皮膜用の酸化処理を行わず、上述の第２電解液を用いた第２皮膜用のＰＥＯ処理のみを行い、マグネシウム合金板の表面に第２皮膜のみを形成して、本比較例の金属材料を作製した。
(Comparative Example 2)
Without performing the oxidation treatment for the first coating using the first electrolytic solution described above, only the PEO treatment for the second coating using the second electrolytic solution described above is performed, and only the second coating is applied to the surface of the magnesium alloy plate. The metal material of this comparative example was produced.
（耐食性評価）
実施例１及び比較例１〜２で作製した各金属材料を０．１Ｍの塩化ナトリウム水溶液（マナック（株））に、１００時間、浸漬させた後、金属材料を観察し、錆及び孔食の発生（即ち、腐食の発生）の有無を観察した。
(Corrosion resistance evaluation)
After immersing each metal material produced in Example 1 and Comparative Examples 1 and 2 in a 0.1 M aqueous sodium chloride solution (Manac Co., Ltd.) for 100 hours, the metal material was observed, and rust and pitting corrosion were observed. The presence or absence of occurrence (that is, occurrence of corrosion) was observed.
なお、目視により、腐食面積の割合が各金属材料の表面積の１０％未満の場合を耐食性が良好とした。以上の結果を表１に示す。 In addition, when the ratio of the corroded area was less than 10% of the surface area of each metal material, the corrosion resistance was considered good. The results are shown in Table 1.
（皮膜の密着性試験）
実施例１及び比較例１〜２で作製した各金属材料について、ＪＩＳ Ｋ５４００に準拠して、皮膜の密着性試験を行った。より具体的には、試験面にカッターナイフを用いて素地に達する１１本の切り傷を１ｍｍ間隔で付け１００個の碁盤目を作り、碁盤目部分に粘着テープを強く圧着させ、テープの端を４５°の角度で一気に引き剥がし、剥がしたテープの粘着面をＳＥＭで観察し、付着してきた皮膜の面積を比較することで評価した。以上の結果を表１に示す。
(Film adhesion test)
About each metal material produced in Example 1 and Comparative Examples 1-2, the adhesiveness test of the film | membrane was done based on JISK5400. More specifically, 11 cuts reaching the substrate using a cutter knife are applied to the test surface at intervals of 1 mm to form 100 grids, and an adhesive tape is strongly pressed on the grid, and the end of the tape is 45 The tape was peeled off at an angle of 0 °, and the adhesive surface of the peeled tape was observed with an SEM and evaluated by comparing the areas of the adhered films. The results are shown in Table 1.
表１に示すように、マグネシウム合金板の表面にプラズマ放電を伴わない陽極酸化処理を施すことにより第１皮膜を形成した後マグネシウム合金板と第２電解液との間にプラズマ放電を発生させてＰＥＯ処理を施すことにより、マグネシウム合金板の表面と第１皮膜の間に第１皮膜とは異なる組成を有する第２皮膜を形成した実施例１においては、金属材料に錆及び孔食が発生している割合が小さく、耐食性が良好であることが確認できた。 As shown in Table 1, after the first coating is formed on the surface of the magnesium alloy plate by anodizing without plasma discharge, plasma discharge is generated between the magnesium alloy plate and the second electrolytic solution. In Example 1 in which the second film having a composition different from that of the first film was formed between the surface of the magnesium alloy plate and the first film by performing the PEO treatment, rust and pitting corrosion occurred in the metal material. It was confirmed that the ratio of corrosion resistance was small and the corrosion resistance was good.
一方、第１電解液を用いた第１皮膜用の酸化処理のみを行った比較例１及び第２電解液を用いた第２皮膜用の酸化処理のみを行った比較例２においては、金属材料に錆及び孔食が発生している割合が大きく、耐食性に乏しいことが確認できた。 On the other hand, in Comparative Example 1 in which only the oxidation treatment for the first film using the first electrolytic solution was performed and in Comparative Example 2 in which only the oxidation treatment for the second film using the second electrolytic solution was performed, the metal material The ratio of occurrence of rust and pitting was large, and it was confirmed that the corrosion resistance was poor.
また、比較例１及び比較例２の金属材料に比し、実施例１の金属材料は、粘着テープへの皮膜の付着量（付着面積）が少なく、耐食性に優れていることが分かった。 Moreover, compared with the metal material of the comparative example 1 and the comparative example 2, it turned out that the metal material of Example 1 has few adhesion amounts (attachment area) of the film | membrane to an adhesive tape, and is excellent in corrosion resistance.
以上より、実施例１の方法により、耐食性に優れた金属材料を得ることができることが分かる。 From the above, it can be seen that a metal material having excellent corrosion resistance can be obtained by the method of Example 1.
また、表１に示すように、実施例１においては、第１皮膜４と金属基材２との間に両者との接合性に優れた第２皮膜５が存在し、更に第２皮膜５自身はボイドが少なく緻密であるため、マグネシウム合金板との密着性に優れた皮膜を得ることができることが分かる。 Moreover, as shown in Table 1, in Example 1, the 2nd membrane | film | coat 5 excellent in the adhesiveness of both exists between the 1st membrane | film | coat 4 and the metal base material 2, and also 2nd membrane | film | coat 5 itself It can be seen that a film having excellent adhesion to the magnesium alloy plate can be obtained because it is dense with few voids.
（皮膜の断面構造）
実施例１の金属材料における第１及び第２皮膜の断面構造を走査型電子顕微鏡（ＳＥＭ）により観察した。得られた電子顕微鏡写真（ＳＥＭ写真）を図６に示す。
(Cross-sectional structure of the film)
The cross-sectional structures of the first and second films in the metal material of Example 1 were observed with a scanning electron microscope (SEM). The obtained electron micrograph (SEM photograph) is shown in FIG.
（エネルギー分散型Ｘ線分析）
実施例１の金属材料に対して、エネルギー分散型Ｘ線分析（ＥＤＸ分析）を行い、第１及び第２皮膜の組成を確認した。
(Energy dispersive X-ray analysis)
The metal material of Example 1 was subjected to energy dispersive X-ray analysis (EDX analysis) to confirm the compositions of the first and second films.
より具体的には、エネルギー分散型Ｘ線分析装置（日本電子（株）製、商品名：ＥＤＸ，ＥＸ−５４１７５ＪＭＵ）を使用して、実施例１において作製した金属材料の第１及び第２皮膜の各々について、ＳＥＭ−ＥＤＸ分析（加速電圧：１５ｋＶ）を行い、マグネシウム、アルミニウム及びリンの含有率を確認した。以上の結果を、図７に示す。 More specifically, using the energy dispersive X-ray analyzer (manufactured by JEOL Ltd., trade name: EDX, EX-54175JMU), the first and second coatings of the metal material produced in Example 1 About each of these, SEM-EDX analysis (acceleration voltage: 15 kV) was performed, and the content rate of magnesium, aluminum, and phosphorus was confirmed. The above results are shown in FIG.
図７に示すように、第１皮膜に比し第２皮膜はリンを多く含むことから、上述のＰＥＯ処理を開始すると、第２電解液中に含まれる酸素を含む化学種（即ち、リン酸アニオン）が第１皮膜を通過して陽極であるマグネシウム合金の表面に移動し、リンを多く含む耐食性に優れた第２皮膜が形成されていることが確認された。 As shown in FIG. 7, since the second film contains more phosphorus than the first film, when the above PEO treatment is started, a chemical species containing oxygen contained in the second electrolytic solution (that is, phosphoric acid). It was confirmed that the anion) passed through the first film and moved to the surface of the magnesium alloy as the anode, and a second film excellent in corrosion resistance containing a large amount of phosphorus was formed.
以上説明したように、本発明は、金属の表面に対して、プラズマ電解酸化処理により皮膜を形成する方法に適している。 As described above, the present invention is suitable for a method of forming a film on a metal surface by plasma electrolytic oxidation.
１ 金属材料
２ 金属基板
３ 皮膜
４ 第１皮膜
５ 第２皮膜
６ 酸素を含む化学種
1 Metal material
2 Metal substrate
3 Coating 4 First Coating 5 Second Coating 6 Chemical Species Containing Oxygen
Claims (6)
第２水溶性化合物を含有し、前記第１電解液とは組成の異なる第２電解液に前記金属を浸漬させた状態で、前記金属と前記第２電解液との間にプラズマ放電を発生させてプラズマ電解酸化処理を施すことにより、前記金属の表面と前記第１皮膜の間に該第１皮膜とは異なる組成を有する第２皮膜を形成する第２皮膜形成工程と
を備えることを特徴とする皮膜形成方法。 A first film forming step of forming a first film on the surface of the metal by performing anodization without plasma discharge in a state where the metal is immersed in the first electrolytic solution containing the first water-soluble compound. When,
A plasma discharge is generated between the metal and the second electrolyte in a state where the metal is immersed in a second electrolyte containing a second water-soluble compound and having a composition different from that of the first electrolyte. And a second film forming step of forming a second film having a composition different from that of the first film between the surface of the metal and the first film by performing plasma electrolytic oxidation treatment. Film forming method.
前記金属基板の表面に形成された皮膜と
を備えた金属材料であって、
前記皮膜は、前記金属基板の表面において該金属基板を覆うように形成された第２皮膜と、前記第２皮膜の表面において該第２皮膜を覆うように形成された第１皮膜により構成され、
前記第１皮膜は、少なくとも水酸化物を含有し、
前記第２皮膜は、リン酸塩、ケイ酸塩、硝酸塩、アルミン酸塩、タングステン酸塩、ホウ酸塩、ジルコニウム酸塩、モリブデン酸塩、炭酸塩、重炭酸塩、水酸化物及び金属酸化物からなる群より選ばれる少なくとも１種を含有する
ことを特徴とする金属材料。 A metal substrate;
A metal material provided with a film formed on the surface of the metal substrate,
The coating is composed of a second coating formed so as to cover the metal substrate on the surface of the metal substrate, and a first coating formed so as to cover the second coating on the surface of the second coating,
The first film contains at least a hydroxide,
The second coating is composed of phosphate, silicate, nitrate, aluminate, tungstate, borate, zirconate, molybdate, carbonate, bicarbonate, hydroxide and metal oxide. A metal material comprising at least one selected from the group consisting of:
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