JP2014136832A - Anodic oxide film and method for manufacturing the same - Google Patents
Anodic oxide film and method for manufacturing the same Download PDFInfo
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- JP2014136832A JP2014136832A JP2013007377A JP2013007377A JP2014136832A JP 2014136832 A JP2014136832 A JP 2014136832A JP 2013007377 A JP2013007377 A JP 2013007377A JP 2013007377 A JP2013007377 A JP 2013007377A JP 2014136832 A JP2014136832 A JP 2014136832A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
- C25D11/246—Chemical after-treatment for sealing layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
Abstract
Description
本発明は、アルミニウム又はアルミニウム合金の表面に施した陽極酸化皮膜及びその製造方法に関する。 The present invention relates to an anodized film formed on the surface of aluminum or an aluminum alloy and a method for producing the same.
アルミニウムやアルミ展伸材、アルミ鋳造材、アルミダイカスト材などのアルミニウム合金の耐食性を向上させる方法として、従来から陽極酸化処理が行われている。陽極酸化処理は、アルミニウムを酸化することによってその表面に酸化皮膜を作製する方法である。しかし、この酸化皮膜は多孔質皮膜であり、耐食性低下の一因となっているため、更なる耐食性の向上を目的として、陽極酸化処理後に孔を塞ぐ封孔処理が行われている。 As a method for improving the corrosion resistance of aluminum alloys such as aluminum, aluminum wrought material, aluminum cast material, and aluminum die-cast material, anodizing treatment has been conventionally performed. Anodizing is a method of producing an oxide film on the surface of aluminum by oxidizing it. However, since this oxide film is a porous film and contributes to a decrease in corrosion resistance, a sealing process for closing the holes after the anodizing process is performed for the purpose of further improving the corrosion resistance.
従来から知られている封孔処理の一つである水和封孔処理には、蒸気によって陽極酸化皮膜を封孔する蒸気封孔型と、封孔助剤を添加した３０〜５０℃の温水にアルミニウムを浸漬する低温水和型と、金属塩等の封孔助剤を添加した８０〜１００℃の熱水にアルミニウム材を１０分以上浸漬する高温水和型とがある。船外機などの高い耐食性が必要とされるアルミニウム部品では、高温水和型の封孔処理が施されている。しかし、高温水和型の封孔処理は、封孔処理液を８０〜１００℃まで加熱、維持する必要があり、また、処理時間が１０分以上と長いため、大量のエネルギーを消費してしまう。 Hydration sealing treatment, one of the conventionally known sealing treatments, includes a steam sealing mold that seals the anodized film with steam, and hot water at 30 to 50 ° C. to which a sealing aid is added. There are a low temperature hydration type in which aluminum is immersed in and a high temperature hydration type in which an aluminum material is immersed in hot water at 80 to 100 ° C. to which a sealing aid such as a metal salt is added. Aluminum parts that require high corrosion resistance such as outboard motors are subjected to high-temperature hydration-type sealing treatment. However, the high-temperature hydration type sealing treatment needs to heat and maintain the sealing treatment solution up to 80 to 100 ° C., and the treatment time is as long as 10 minutes or more, which consumes a large amount of energy. .
一方、近年、省エネルギー型の封孔処理として、例えば特許文献１のような技術が開発されている。 On the other hand, in recent years, for example, a technique as disclosed in Patent Document 1 has been developed as an energy-saving sealing process.
本発明は前記事情に鑑みてなされたものであって、高い耐食性を維持することができる陽極酸化皮膜及びその製造方法を提供することを目的とする。 This invention is made | formed in view of the said situation, Comprising: It aims at providing the anodic oxide film which can maintain high corrosion resistance, and its manufacturing method.
前記課題を解決するため、本発明に係る陽極酸化皮膜の製造方法は、アルミニウム又はアルミニウム合金部材の表面に陽極酸化皮膜を作製する工程と、前記陽極酸化皮膜の表面を、リチウムイオンを含む封孔処理液を用いて処理する工程と、前記封孔処理された陽極酸化皮膜を加熱する工程とを含む。
前記加熱する工程は、１６０〜４００℃の範囲内で行われることが好適である。
前記封孔処理液のリチウムイオン濃度は０．０２〜２０ｇ／Ｌであり、前記封孔処理液のｐＨ値は１０．５以上であり、前記封孔処理液の温度は１０〜６５℃であることが好適である。
In order to solve the above problems, the method for producing an anodized film according to the present invention includes a step of producing an anodized film on the surface of an aluminum or aluminum alloy member, and the surface of the anodized film is sealed with lithium ions. A step of treating with the treatment liquid and a step of heating the anodized film subjected to the sealing treatment.
The heating step is preferably performed within a range of 160 to 400 ° C.
The concentration of lithium ions in the sealing treatment liquid is 0.02 to 20 g / L, the pH value of the sealing treatment liquid is 10.5 or more, and the temperature of the sealing treatment liquid is 10 to 65 ° C. Is preferred.
また、本発明は他の側面で陽極酸化皮膜であり、アルミニウム又はアルミニウム合金部材の表面に形成された陽極酸化皮膜であって、前記陽極酸化皮膜の表面に細孔を備えており、前記細孔内に少なくともリチウム金属又はリチウムを主成分とする合金もしくは化合物を備えており、前記陽極酸化皮膜の表面にマイクロクラックをさらに備える。
前記マイクロクラックの数は、５０〜２００個／ｍｍであることが好適である。
前記マイクロクラックは、前記アルミニウム又はアルミニウム合金部材にまで達していることが好適である。
前記リチウム金属又はリチウムを主成分とする合金もしくは化合物は、前記アルミニウム又はアルミニウム合金部材側よりも前記陽極酸化皮膜の表面側に多く存在することが好適である。
In another aspect, the present invention is an anodized film, which is an anodized film formed on the surface of an aluminum or aluminum alloy member, and has pores on the surface of the anodized film. It contains at least lithium metal or an alloy or compound containing lithium as a main component, and further has a microcrack on the surface of the anodized film.
The number of microcracks is preferably 50 to 200 / mm.
It is preferable that the micro crack reaches the aluminum or aluminum alloy member.
It is preferable that the lithium metal or the alloy or compound containing lithium as a main component is present more on the surface side of the anodized film than on the aluminum or aluminum alloy member side.
本発明の陽極酸化皮膜及びその製造方法によれば、高い耐食性を維持することができる。 According to the anodized film and the method for producing the same of the present invention, high corrosion resistance can be maintained.
以下、本発明の実施の形態について説明する。
（被処理物）
本発明において、陽極酸化処理の処理対象物は、アルミニウム又は、シリコンや銅等の合金成分を含むアルミニウム合金部材である。アルミニウム合金部材としては、特に限定されるものではなく、例えばアルミ展伸材、アルミ鋳造材、アルミダイカスト材等を用いることができる。
Embodiments of the present invention will be described below.
(Processed object)
In the present invention, the object to be anodized is aluminum or an aluminum alloy member containing an alloy component such as silicon or copper. The aluminum alloy member is not particularly limited, and for example, an aluminum wrought material, an aluminum cast material, an aluminum die cast material, or the like can be used.
（陽極酸化処理）
陽極酸化皮膜は、アルミニウム又はアルミニウム合金部材の表面に作製される。陽極酸化皮膜は、陽極酸化処理液中にアルミニウム又はアルミニウム合金を陽極として、チタンやステンレス板等を陰極としてそれぞれ配置し、処理液を電気分解することによって得られる。陽極酸化処理液としては、硫酸、シュウ酸、リン酸、クロム酸等の酸性水溶液、水酸化ナトリウム、リン酸ナトリウム、フッ化ナトリウム等の塩基性水溶液のいずれを用いてもよく、本発明において陽極酸化処理の対象となるアルミニウム又はアルミニウム合金部材は、特定の陽極酸化処理液を使用したものには限定されない。陽極酸化皮膜の膜厚も特に限定されないが、通常３〜４０μｍがよい。電気分解の方法としては、特に限定されるものではなく、例えば直流電解、交流電解、交直重畳電解、Ｄｕｔｙ電解等、いずれの電解方法を用いてもよい。
(Anodizing treatment)
An anodized film is produced on the surface of aluminum or an aluminum alloy member. The anodized film is obtained by disposing aluminum or an aluminum alloy in the anodizing treatment liquid as an anode and titanium or stainless steel plate as a cathode and electrolyzing the treatment liquid. As the anodizing treatment liquid, any of acidic aqueous solutions such as sulfuric acid, oxalic acid, phosphoric acid and chromic acid, and basic aqueous solutions such as sodium hydroxide, sodium phosphate and sodium fluoride may be used. The aluminum or aluminum alloy member to be oxidized is not limited to one using a specific anodizing solution. The thickness of the anodic oxide film is not particularly limited, but is usually 3 to 40 μm. The electrolysis method is not particularly limited, and any electrolysis method such as direct current electrolysis, alternating current electrolysis, AC / DC superposition electrolysis, duty electrolysis, or the like may be used.
（封孔処理）
陽極酸化皮膜を作製した処理対象物に対し、リチウムイオンを含む封孔処理液を用いて封孔処理を施す。具体的には、陽極酸化皮膜を作製した処理対象物を封孔処理液に浸漬し、又は処理対象物に封孔処理液を塗布やスプレーする等、封孔処理液を陽極酸化皮膜の表面に付着させることにより封孔処理を行う。
(Sealing treatment)
The object to be processed on which the anodized film has been prepared is subjected to sealing treatment using a sealing treatment liquid containing lithium ions. Specifically, the sealing treatment liquid is applied to the surface of the anodized film by immersing the treatment object on which the anodized film is prepared in the sealing treatment liquid, or by applying or spraying the sealing treatment liquid on the treatment object. Sealing treatment is performed by adhering.
陽極酸化皮膜を作製した処理対象物を封孔処理液に浸漬し、又は処理対象物に封孔処理液を塗布やスプレーした後、乾燥することが好ましい。乾燥温度は、好ましくは１００〜１５０℃の範囲内である。また、陽極酸化皮膜を作製した処理対象物を封孔処理液に浸漬し、５分以下で封孔処理液から取り出し、水洗、乾燥することが好ましい。塗布やスプレーによる封孔処理方法は、部分的に封孔処理することができ、大型部品でも浸漬する必要がないため、大型の槽を必要としない。 It is preferable that the object to be processed on which the anodized film has been produced is dipped in the sealing treatment liquid, or the sealing treatment liquid is applied or sprayed on the treatment object and then dried. The drying temperature is preferably in the range of 100 to 150 ° C. Moreover, it is preferable to immerse the processing object which produced the anodic oxide film in the sealing treatment liquid, take out from a sealing treatment liquid in 5 minutes or less, wash with water, and dry. The sealing treatment method by coating or spraying can partially seal and does not need to immerse even a large component, and therefore does not require a large tank.
封孔処理液はリチウムイオンを含む水溶液であり、リチウムイオン源となる薬品としては、硫酸リチウム、塩化リチウム、ケイ酸リチウム、硝酸リチウム、炭酸リチウム、リン酸リチウム、水酸化リチウム、及びそれらの水和物などを使用することができる。そのうち、水溶液が塩基性を示すものとして水酸化リチウム、炭酸リチウム、ケイ酸リチウムが好ましい。但し、ケイ酸リチウムは毒性が強く、水に溶けにくいため、実用的ではない。よって、炭酸リチウムと水酸化リチウムがより好適である。 The sealing treatment liquid is an aqueous solution containing lithium ions, and the chemicals used as the lithium ion source include lithium sulfate, lithium chloride, lithium silicate, lithium nitrate, lithium carbonate, lithium phosphate, lithium hydroxide, and water thereof. Japanese products can be used. Of these, lithium hydroxide, lithium carbonate, and lithium silicate are preferred as the aqueous solution exhibits basicity. However, lithium silicate is not practical because it is highly toxic and hardly soluble in water. Therefore, lithium carbonate and lithium hydroxide are more preferable.
封孔処理液のリチウムイオン濃度は、０．０２〜２０ｇ／Ｌにする必要がある。０．０２ｇ／Ｌ以上の濃度のリチウムイオンで封孔処理の反応が促進される。下限は、好ましくは０．０８ｇ／Ｌであり、より好ましくは２ｇ／Ｌである。上限は、より好ましくは１０ｇ／Ｌである。リチウムイオン濃度が１０ｇ／Ｌを超えた封孔処理液では、急速に反応が進み、陽極酸化皮膜のないアルミニウム素地の溶解が起こる場合がある。 The lithium ion concentration of the sealing treatment liquid needs to be 0.02 to 20 g / L. The reaction of the sealing treatment is promoted by lithium ions having a concentration of 0.02 g / L or more. The lower limit is preferably 0.08 g / L, and more preferably 2 g / L. The upper limit is more preferably 10 g / L. In the sealing treatment liquid having a lithium ion concentration exceeding 10 g / L, the reaction proceeds rapidly, and dissolution of the aluminum base without the anodized film may occur.
封孔処理液のｐＨ値は、１０．５以上にする必要がある。好ましくは１１以上であり、さらに好ましくは１２以上である。また、ｐＨ値の上限は１４が好ましい。封孔処理液が塩基性のため、酸性水溶液で処理した皮膜と反応しやすく、後述するリチウム化合物を速やかに生成する。また、ｐＨ値１２以上では、リチウム化合物をより速やかに生成する。ｐＨ値が１０．５未満の封孔処理液では、腐食率が高く、耐食性を向上させる効果が低くなる場合がある。また、リチウムイオン源によってｐＨ値は異なるので、硫酸、シュウ酸、リン酸、クロム酸等の酸や、水酸化ナトリウム、リン酸ナトリウム、フッ化ナトリウム等の塩基を用いてｐＨを調整することができる。 The pH value of the sealing treatment liquid needs to be 10.5 or more. Preferably it is 11 or more, More preferably, it is 12 or more. Further, the upper limit of the pH value is preferably 14. Since the sealing treatment liquid is basic, it easily reacts with a film treated with an acidic aqueous solution, and a lithium compound described later is rapidly formed. Further, when the pH value is 12 or more, the lithium compound is generated more rapidly. In a sealing treatment liquid having a pH value of less than 10.5, the corrosion rate is high, and the effect of improving the corrosion resistance may be low. Since the pH value varies depending on the lithium ion source, it is possible to adjust the pH using an acid such as sulfuric acid, oxalic acid, phosphoric acid or chromic acid, or a base such as sodium hydroxide, sodium phosphate or sodium fluoride. it can.
封孔処理液の温度は、６５℃以下にする必要がある。下限は１０℃以上が好ましい。より好ましくは２５〜５０℃である。２５℃よりも低い温度で処理を施すと、活性が低く、反応が弱くなるが、ある程度の耐食性は期待できる。逆に、６５℃を超える温度では、陽極酸化皮膜表面からの皮膜の溶解が急速に進み、皮膜が消失して高い耐食性は得られなくなる場合がある。 The temperature of the sealing treatment liquid needs to be 65 ° C. or lower. The lower limit is preferably 10 ° C. or higher. More preferably, it is 25-50 degreeC. When the treatment is performed at a temperature lower than 25 ° C., the activity is low and the reaction becomes weak, but a certain degree of corrosion resistance can be expected. On the other hand, at a temperature exceeding 65 ° C., dissolution of the film from the surface of the anodized film proceeds rapidly, and the film disappears and high corrosion resistance may not be obtained.
封孔処理液の処理時間（浸漬時間）は、少なくとも０．５分あれば、高い耐食性が発揮される。上限は好ましくは５分以下である。５分を超える処理時間では、皮膜の溶解が急速に進み、耐食性が低下する場合がある。 When the treatment time (immersion time) of the sealing treatment liquid is at least 0.5 minutes, high corrosion resistance is exhibited. The upper limit is preferably 5 minutes or less. When the treatment time exceeds 5 minutes, dissolution of the film proceeds rapidly, and the corrosion resistance may decrease.
陽極酸化皮膜を作製したアルミニウム又はアルミニウム合金部材は、封孔処理液に浸漬、又は、封孔処理液を塗布する前に、水洗浄等の前処理を行うことが好ましい。陽極酸化皮膜に付着した陽極酸化処理液が封孔処理液に混入することを防止し、また孔内の陽極酸化処理液を除去するためである。 The aluminum or aluminum alloy member on which the anodized film is produced is preferably subjected to a pretreatment such as water washing before being immersed in the sealing treatment liquid or before the sealing treatment liquid is applied. This is to prevent the anodizing solution adhering to the anodized film from being mixed into the sealing treatment solution and to remove the anodizing solution in the holes.
リチウムは非常に小さい元素であり、皮膜の隙間に入って反応しやすいため、好適である。リチウムと同族の元素であるナトリウムやカリウムは、皮膜の封孔処理回数に対して敏感であり、処理回数の増加に伴い、耐食性は顕著に低下する。また、薬液管理に関してコスト高を招くため、生産を考慮すると望ましくない。これに対して、リチウムは処理回数に鈍感で、安定した耐食性を有する。 Lithium is a very small element and is suitable because it easily enters a gap in the film and reacts. Sodium and potassium, which are elements of the same family as lithium, are sensitive to the number of sealing treatments of the film, and the corrosion resistance decreases significantly with the increase in the number of treatments. In addition, the cost associated with chemical solution management is undesirable, and this is not desirable in consideration of production. On the other hand, lithium is insensitive to the number of treatments and has stable corrosion resistance.
（加熱処理）
封孔処理された陽極酸化皮膜を加熱する。加熱温度は、好ましくは１６０〜４００℃の範囲内である。１６０℃に満たない温度では、後述するように、封孔処理時に生成する微細なマイクロクラックに変化が見られない場合があり、４００℃を超える温度では、アルミニウム合金の種類によってはアルミニウム合金部材の溶解が始まってしまう場合があるからである。加熱時間については、部品の大きさや形状によって部品が均一に加熱されるまでの時間が異なるため、使用する部品ごとに最適な加熱時間を設定することが好ましい。
(Heat treatment)
The anodized film that has been sealed is heated. The heating temperature is preferably in the range of 160 to 400 ° C. At temperatures below 160 ° C., as will be described later, there may be no change in fine microcracks generated during the sealing treatment. At temperatures above 400 ° C., depending on the type of aluminum alloy, This is because dissolution may start. As for the heating time, it is preferable to set an optimum heating time for each component to be used because the time until the component is uniformly heated varies depending on the size and shape of the component.
加熱処理は、上述したような封孔処理後の乾燥工程と一体化させることも、別々に行うことも可能である。乾燥工程の乾燥温度を上げることによって、加熱処理と乾燥工程を一体化することができ、工程の簡略化が可能になる。また、使用する部品によって求められる耐食性能が異なることもあり、そのような部品複数種を同時に陽極酸化処理を施す場合も頻繁にあるため、まず上述したような通常の乾燥を行い、その後高い耐食性を必要とする部品のみに対して加熱処理を行うことも可能である。 The heat treatment can be integrated with the drying step after the sealing treatment as described above, or can be performed separately. By raising the drying temperature in the drying process, the heat treatment and the drying process can be integrated, and the process can be simplified. In addition, the corrosion resistance required may vary depending on the parts used, and since there are frequent cases where multiple types of such parts are subjected to anodizing simultaneously, first perform normal drying as described above, and then have high corrosion resistance. It is also possible to perform the heat treatment only on the parts that require the heat treatment.
（陽極酸化皮膜）
アルミダイカスト材、例えばＡＤＣ１２材等のシリコンを多く含むアルミニウム合金部材に陽極酸化皮膜を作製した場合、シリコン量が少なくアルミニウム量が多い部分には厚い皮膜が生成し、シリコン量が多くアルミニウム量が少ない部分には薄い皮膜が生成するため、全体的に不均一な膜厚の皮膜が得られる。本発明者らは、このような陽極酸化皮膜の耐食性について鋭意検討を行った。このような部品を、例えば過酷な腐食環境下である海で使用した場合、海水中に含まれる塩分が皮膜を攻撃（溶解）し、皮膜に海水が徐々に浸透していく。そして、海水がアルミニウム合金部材に達することによって、アルミニウム合金部材の腐食が始まる。膜厚の薄い部分は海水がアルミニウム合金部材に達するまでの時間が短いため、膜厚の薄い部分から腐食していくことになる。海水中では、陰極がアルミニウム合金部材、陽極が皮膜、電解液が海水とみなされる局部電池が形成され、２種類の金属と水との間で起こる電気化学反応によって腐食電流が発生する。この腐食電流を小さくすることによって、陽極酸化皮膜の耐食性を向上させることができると考えられる。しかしながら、封孔処理はあくまで陽極酸化皮膜の孔を塞ぐ処理であるため、封孔処理のみによって腐食電流を小さくすることは困難である。
(Anodized film)
When an anodized film is formed on an aluminum alloy member containing a large amount of silicon such as an aluminum die cast material, for example, ADC12 material, a thick film is formed in a portion where the amount of silicon is small and the amount of aluminum is large, and the amount of silicon is large and the amount of aluminum is small. Since a thin film is formed on the portion, a film having a non-uniform film thickness can be obtained as a whole. The present inventors have intensively studied the corrosion resistance of such an anodized film. When such a component is used in, for example, a sea under a severe corrosive environment, salt contained in seawater attacks (dissolves) the film, and the seawater gradually permeates the film. And when seawater reaches an aluminum alloy member, corrosion of an aluminum alloy member begins. Since the time until the seawater reaches the aluminum alloy member is short in the thin film portion, the thin film portion is corroded from the thin film portion. In seawater, a local battery is formed in which the cathode is an aluminum alloy member, the anode is a film, and the electrolyte is seawater, and a corrosion current is generated by an electrochemical reaction between two kinds of metals and water. It is considered that the corrosion resistance of the anodized film can be improved by reducing the corrosion current. However, since the sealing process is a process for closing the holes of the anodic oxide film, it is difficult to reduce the corrosion current only by the sealing process.
一方、ＡＤＣ１２材等のシリコンを多く含むアルミニウム合金部材に限らず、アルミニウム合金部材には様々な合金成分が含まれている。陽極酸化皮膜はアルミニウムを酸化させて体積を膨張させたものであるため、皮膜中の合金成分の周囲には隙間が生じ、または、合金成分がなくなって空洞になる。これにより、皮膜には欠陥が存在することとなる。上述した海での使用例で考えると、このような欠陥のある部分は海水が浸透しやすいため、膜厚の薄い部分と同様に腐食しやすい。したがって、腐食電流が集中しやすい膜厚の薄い部分や皮膜欠陥部において最初に腐食が発生し、その後、腐食が拡がっていくことによって、耐食性が悪化する。よって、皮膜の耐食性を向上させるためには、発生する腐食電流を如何に小さくするかが重要である。 On the other hand, the aluminum alloy member is not limited to an aluminum alloy member containing a large amount of silicon such as the ADC12 material, and the aluminum alloy member contains various alloy components. Since the anodized film is obtained by oxidizing aluminum to expand the volume, a gap is formed around the alloy component in the film, or the alloy component disappears and becomes a cavity. Thereby, a defect exists in the film. Considering the above-described use example in the sea, seawater is likely to permeate such a defective part, so that it is likely to corrode similarly to a thin part. Accordingly, corrosion occurs first in a thin film portion or a film defect portion where corrosion current tends to concentrate, and then the corrosion spreads, thereby deteriorating the corrosion resistance. Therefore, in order to improve the corrosion resistance of the film, it is important how to reduce the generated corrosion current.
そこで、本発明者らは、上述したように、リチウムイオンを含む封孔処理液を用いて封孔処理を行った陽極酸化皮膜について加熱処理を行うことを見出した。加熱処理を行うことによって、陽極酸化皮膜の表面にマイクロクラックを作製する。発生する腐食電流を、作製したマイクロクラックの数だけ分散させることにより小さくし、陽極酸化皮膜の耐食性を向上させることができる。 Therefore, the present inventors have found that, as described above, the anodic oxide film subjected to the sealing treatment using the sealing treatment liquid containing lithium ions is subjected to the heat treatment. By performing heat treatment, microcracks are formed on the surface of the anodized film. The generated corrosion current can be reduced by dispersing the number of produced microcracks, and the corrosion resistance of the anodized film can be improved.
本発明の陽極酸化皮膜は、アルミニウム又はアルミニウム合金部材の表面に形成された陽極酸化皮膜であって、陽極酸化皮膜の表面に細孔を備えており、細孔内に少なくともリチウム金属又はリチウムを主成分とする合金もしくは化合物を備えており、陽極酸化皮膜の表面にマイクロクラックをさらに備える。リチウム化合物としては、詳細は後述するが、ＬｉＨ（ＡｌＯ２）２・５Ｈ２Ｏ等を挙げることができる。また、このリチウム化合物は、後述するように、アルミニウム又はアルミニウム合金部材側よりも陽極酸化皮膜の表面側に多く存在することが好ましい。 The anodized film of the present invention is an anodized film formed on the surface of aluminum or an aluminum alloy member, and has pores on the surface of the anodized film, and at least lithium metal or lithium is mainly contained in the pores. An alloy or compound as a component is provided, and a microcrack is further provided on the surface of the anodized film. Examples of the lithium compound include LiH (AlO 2 ) 2 .5H 2 O, which will be described later in detail. Further, as will be described later, it is preferable that the lithium compound is present more on the surface side of the anodized film than on the aluminum or aluminum alloy member side.
作製したマイクロクラックは、アルミニウム又はアルミニウム合金部材にまで達していることが好ましい。これにより、陽極酸化皮膜の膜厚の薄い部分よりも、マイクロクラックが存在する部分の方が腐食しやすい状態となる。マイクロクラックが陽極酸化皮膜の表面に１個存在する場合と複数個存在する場合において、発生するトータルの腐食電流は同じであるから、マイクロクラックが複数個存在する場合の方がマイクロクラック1個当たりで生じる腐食電流は小さくなり、腐食はゆっくりと進行する。マイクロクラックを皮膜の全体に均一に作製することによって、部品全体がゆっくりと腐食していくことになるが、その腐食速度はかなり遅くなると推定され、長期的に見ると皮膜の耐食性は加熱処理を行わない場合と比較して２倍以上に向上すると考えられる。 It is preferable that the produced microcracks reach aluminum or an aluminum alloy member. Thereby, the part where the micro crack exists is more likely to corrode than the part where the film thickness of the anodized film is thin. When one microcrack is present on the surface of the anodized film and when there are multiple microcracks, the total corrosion current generated is the same. Corrosion current generated in the process becomes smaller and the corrosion proceeds slowly. By creating microcracks uniformly throughout the coating, the entire part will slowly corrode, but the corrosion rate is estimated to be considerably slow. It is thought that it is improved more than twice as compared with the case where it is not performed.
本発明の加熱処理における加熱温度は、上述したように、１６０〜４００℃の範囲内である。このような加熱処理を行うことにより、陽極酸化皮膜全体に均一にマイクロクラックを好ましくは５０〜２００個／ｍｍ、より好ましくは７０〜１７５個／ｍｍ、さらに好ましくは１１０〜１４５個／ｍｍ作製することができる。５０個／ｍｍ未満である場合には、加熱処理を行わない場合と比べて腐食面積率があまり変わらない場合があり、２００個／ｍｍを超える場合には、マイクロクラックが本来生成しやすい膜厚の薄い部分に発生する割合が高くなり、マイクロクラックの分布が不均一になるため、耐食性が悪化するおそれがある。 As described above, the heating temperature in the heat treatment of the present invention is in the range of 160 to 400 ° C. By performing such a heat treatment, it is preferable to produce 50 to 200 pieces / mm, more preferably 70 to 175 pieces / mm, and more preferably 110 to 145 pieces / mm uniformly in the entire anodized film. be able to. If it is less than 50 pieces / mm, the corrosion area ratio may not change much compared to the case where heat treatment is not performed. If it exceeds 200 pieces / mm, the film thickness is likely to generate microcracks. The rate of occurrence in thin portions increases, and the distribution of microcracks becomes non-uniform, which may deteriorate the corrosion resistance.
なお、本明細書において、マイクロクラックの数（個／ｍｍ）は次の方法により算出した。電界放射型走査電子顕微鏡（ＦＥ−ＳＥＭ）を用いて陽極酸化皮膜の表面を拡大して撮影した写真（幅６０μｍ）に、６０μｍの長さの直線を引き、当該直線とマイクロクラックが交わる数を測定した。この測定を１０回行い、１０回の平均値を１ｍｍ単位に換算した値をマイクロクラックの数として採用した。 In the present specification, the number of microcracks (pieces / mm) was calculated by the following method. A photograph (width 60 μm) taken by enlarging the surface of the anodized film using a field emission scanning electron microscope (FE-SEM) is drawn with a straight line having a length of 60 μm, and the number of intersections of the straight line and the microcracks is shown. It was measured. This measurement was performed 10 times, and a value obtained by converting the average value of 10 times into units of 1 mm was adopted as the number of microcracks.
本発明はリチウムイオンを含む封孔処理液を用いた封孔処理でのみ可能な方法であり、その理由は次のように考えられる。図１に本発明による耐食性向上のメカニズムを示す。図１（ａ）に示すように、アルミニウム合金部材１１の表面に作製した陽極酸化皮膜１２は封孔処理によって化学反応を起こすため、孔１３と孔１３の間の陽極酸化皮膜部分の強度が低下する。リチウムイオンを含む封孔処理液を用いた封孔処理では、リチウム化合物１４（ＬｉＨ（ＡｌＯ２）２・５Ｈ２Ｏ）とジアスポア１５（ＡｌＯ・ＯＨ）が生成しており、陽極酸化皮膜１２の最表面にはそれらの化合物が薄片状となっている（図１（ｂ））。処理対象物がシリコンを含むアルミニウム合金部材１１である場合、薄片状の下にはもともと陽極酸化皮膜１２の表面に内包されていたシリコン１６が、封孔処理時の皮膜の溶解により析出している（図１（ｂ））。陽極酸化皮膜１２の表層は多くのリチウム化合物１４が緻密に存在しており、このリチウム化合物１４は陽極酸化皮膜１２の奥深くまで生成している（図１（ｂ））。また、陽極酸化皮膜１２の表層部近傍の孔１３内には、リチウム化合物１４が特に密集して生成するため、陽極酸化皮膜１２の表層部では、孔１３内から陽極酸化皮膜１２側への圧力Ｐが発生する（図１（ｂ））。この圧力Ｐによって、陽極酸化皮膜１２にナノレベルの大きさのマイクロクラック１７が発生し、その結果、孔１３と孔１３が繋がる（図１（ｃ））。孔１３と孔１３が繋がった際の衝撃等により、孔１３内の化合物にもマイクロクラック１７が発生する（図１（ｃ））。なお、孔１３内の生成物は、極小の化合物が集まったものであるため、強度は高くない。多数のマイクロクラック１７が繋がることにより、陽極酸化皮膜１２の表層部にて、マイクロクラック１７は大きく成長する（図１（ｄ））。つまり、リチウム化合物１４が特に密集して生成している表層部（深さ約１μｍ）のみ、マイクロクラック１７が生成される。その後、図１（ｅ）に示すように、１６０〜４００℃の加熱処理によって、微細なマイクロクラック１７が伸展して大きくなり、また、新たなマイクロクラックが生成しやすくなり、アルミニウム合金部材１１にまで達したマイクロクラック１８が作製される。このアルミニウム合金部材１１にまで達したマイクロクラック１８により、腐食電流がアルミニウム合金部材１１に分散して流れるため、アルミニウム合金部材の腐食の進行速度を抑制することができ、耐食性が向上すると考えられる。 The present invention is a method that is possible only by a sealing treatment using a sealing treatment liquid containing lithium ions, and the reason is considered as follows. FIG. 1 shows a mechanism for improving corrosion resistance according to the present invention. As shown in FIG. 1 (a), the anodized film 12 produced on the surface of the aluminum alloy member 11 causes a chemical reaction by the sealing treatment, so that the strength of the anodized film portion between the holes 13 and 13 decreases. To do. In the sealing treatment using the sealing treatment liquid containing lithium ions, lithium compound 14 (LiH (AlO 2 ) 2 .5H 2 O) and diaspore 15 (AlO.OH) are generated. Those compounds are flaky on the outermost surface (FIG. 1 (b)). When the object to be treated is the aluminum alloy member 11 containing silicon, the silicon 16 originally contained in the surface of the anodized film 12 is deposited under the flake shape due to dissolution of the film during the sealing treatment. (FIG. 1 (b)). Many lithium compounds 14 are densely present on the surface layer of the anodic oxide film 12, and the lithium compounds 14 are generated deep in the anodic oxide film 12 (FIG. 1B). Further, since the lithium compound 14 is particularly densely formed in the holes 13 in the vicinity of the surface layer portion of the anodic oxide film 12, the pressure from the inside of the holes 13 to the anodic oxide film 12 side is generated in the surface layer portion of the anodic oxide film 12. P is generated (FIG. 1B). With this pressure P, micro cracks 17 having a nano level size are generated in the anodic oxide film 12, and as a result, the holes 13 and 13 are connected (FIG. 1C). Microcracks 17 are also generated in the compound in the hole 13 due to an impact or the like when the hole 13 and the hole 13 are connected (FIG. 1C). In addition, since the product in the hole 13 is a collection of extremely small compounds, the strength is not high. By connecting a large number of microcracks 17, the microcracks 17 grow greatly in the surface layer portion of the anodic oxide film 12 (FIG. 1D). That is, the microcrack 17 is generated only in the surface layer portion (depth of about 1 μm) where the lithium compound 14 is particularly densely formed. Thereafter, as shown in FIG. 1 (e), the heat treatment at 160 to 400 ° C. causes the fine microcracks 17 to expand and become large, and new microcracks are easily generated. A microcrack 18 reaching the maximum is produced. The microcracks 18 reaching the aluminum alloy member 11 cause the corrosion current to be dispersed and flow in the aluminum alloy member 11, so that the progress rate of corrosion of the aluminum alloy member can be suppressed, and the corrosion resistance is considered to be improved.
以上説明したように、本発明の陽極酸化皮膜及びその製造方法によれば、陽極酸化皮膜の表面に作製されたマイクロクラックによって腐食電流が分散されるため、耐食性を向上させることができる。 As described above, according to the anodized film of the present invention and the method for producing the same, the corrosion current is dispersed by the microcracks produced on the surface of the anodized film, so that the corrosion resistance can be improved.
以下、実施例等を示して本発明を具体的に説明するが、本発明はこれらに限定されるものではない。
（実施例１）
アルミニウム合金ダイカスト材ＡＤＣ１２を試験片として用いた。２００ｇ／Ｌの硫酸浴に試験片を陽極として浸漬し、電流密度１．５Ａ／ｄｍ２で直流を１０分間通電することにより、膜厚が３μｍの陽極酸化皮膜を作製した。陽極酸化処理後の試験片を、０．８ｇ／Ｌのリチウムイオンを含み、ｐＨを１２、温度を４０℃とした封孔処理液に1分間浸漬して封孔処理を行い、その後オーブンで１２０℃、３０ｍｉｎの乾燥を行った。乾燥後の試験片を、再びオーブンで１２０〜４００℃、３０〜３００ｍｉｎの加熱処理を行った。得られた試験片について、陽極酸化皮膜表面のマイクロクラック数を測定した。また、塩水噴霧試験（ＪＩＳ Ｚ ２３７１）を２４０ｈ行い、耐食性評価を行った。耐食性評価については、下式（１）に従って、腐食面積率を算出した。
腐食面積率（％）＝評価面における腐食した面積／評価面の全面積 ・・・式（１）
腐食面積率が低いほど腐食している部分が少なく、耐食性が高いことを示す。なお、評価面における腐食した面積については、画像処理により算出した。
EXAMPLES Hereinafter, although an Example etc. are shown and this invention is demonstrated concretely, this invention is not limited to these.
Example 1
Aluminum alloy die-cast material ADC12 was used as a test piece. The test piece was immersed as an anode in a 200 g / L sulfuric acid bath, and a direct current was applied for 10 minutes at a current density of 1.5 A / dm 2 to produce an anodized film having a thickness of 3 μm. The test piece after the anodization treatment was immersed in a sealing treatment solution containing 0.8 g / L lithium ion, pH 12 and temperature 40 ° C. for 1 minute, and then sealed in an oven. Drying was performed at ° C for 30 minutes. The test piece after drying was again heat-treated in an oven at 120 to 400 ° C. for 30 to 300 minutes. About the obtained test piece, the number of microcracks on the anodized film surface was measured. Further, a salt spray test (JIS Z 2371) was performed for 240 hours to evaluate corrosion resistance. For the corrosion resistance evaluation, the corrosion area ratio was calculated according to the following formula (1).
Corrosion area ratio (%) = Corroded area on the evaluation surface / Total area of the evaluation surface (1)
The lower the corrosion area ratio, the fewer parts are corroded and the higher the corrosion resistance. The corroded area on the evaluation surface was calculated by image processing.
（比較例１）
１２０〜４００℃、３０〜３００ｍｉｎの加熱処理を行わなかったこと以外は、実施例１と同様に行った。
(Comparative Example 1)
It carried out similarly to Example 1 except not having performed 120-400 degreeC and the heat processing for 30-300 min.
実施例１及び比較例１におけるマイクロクラック数と腐食面積率の関係を図２と表１に示す。また、実施例１において４００℃加熱処理を行った試験片のＦＥ−ＳＥＭによる表面写真を図３に、比較例１についての試験片のＦＥ−ＳＥＭによる表面写真を図４に、それぞれ示す。 The relationship between the number of microcracks and the corrosion area ratio in Example 1 and Comparative Example 1 is shown in FIG. Moreover, the surface photograph by FE-SEM of the test piece which performed 400 degreeC heat processing in Example 1 is shown in FIG. 3, The surface photograph by FE-SEM of the test piece about Comparative Example 1 is shown in FIG. 4, respectively.
表１より、比較例１の場合、マイクロクラック数は３８個／ｍｍ、腐食面積率は２．１％であった。また、乾燥後に、乾燥と同条件で加熱処理を行っても、マイクロクラック数と腐食面積率に大きな変化は見られなかった。一方、実施例１の１６０℃以上の加熱処理を行った場合、マイクロクラック数は５２〜１９４個／ｍｍと増加し、腐食面積率は比較例１と比べて半分以下である０．２〜１．０％となった。これは、マイクロクラックが皮膜全体に均一に生成することによって、腐食電流が膜厚の薄い部分に集中することなく分散されたためである。また、マイクロクラック数が２００個／ｍｍまでは均一にクラックが作製されるが、２００個／ｍｍを超えると、マイクロクラックが本来生成しやすい膜厚の薄い部分におけるマイクロクラックの割合が高まり、マイクロクラックの分布が不均一になるため、耐食性は悪化すると考えられる。
図２より、マイクロクラック数は、腐食面積率が比較例１と比べて半分以下となる５０〜２００個／ｍｍが好ましく、７０〜１７５個／ｍｍがさらに好ましいと考えられる。
図３より、皮膜表面には多数の大きなマイクロクラックが均一に生成していることが確認された。一方、図４より、比較例１の皮膜表面には小さなクラックが点在していることが確認された。
From Table 1, in the case of the comparative example 1, the number of microcracks was 38 pieces / mm and the corrosion area rate was 2.1%. Moreover, even if it heat-processed on the same conditions as drying after drying, the big change was not seen by the number of microcracks and the corrosion area rate. On the other hand, when heat treatment at 160 ° C. or higher in Example 1 was performed, the number of microcracks increased to 52 to 194 pieces / mm, and the corrosion area rate was 0.2 to 1 that is less than half that of Comparative Example 1. 0.0%. This is because the corrosion currents are dispersed without concentrating on the thin part because the microcracks are uniformly generated in the entire film. Moreover, although the number of microcracks is uniform up to 200 / mm, the cracks are uniformly formed. However, when the number exceeds 200 / mm, the ratio of microcracks increases in the thin portion where the microcracks are likely to be generated. It is considered that the corrosion resistance deteriorates because the distribution of cracks becomes uneven.
From FIG. 2, it is considered that the number of microcracks is preferably 50 to 200 / mm, and more preferably 70 to 175 / mm, in which the corrosion area rate is less than half that of Comparative Example 1.
From FIG. 3, it was confirmed that a large number of large microcracks were uniformly generated on the coating surface. On the other hand, it was confirmed from FIG. 4 that small cracks were scattered on the surface of the film of Comparative Example 1.
（実施例２）
実施例１と同様に行った。
（比較例２）
アルミニウム合金ダイカスト材ＡＤＣ１２を試験片として用いた。２００ｇ／Ｌの硫酸浴に試験片を陽極として浸漬し、電流密度１．５Ａ／ｄｍ２で直流を１０分間通電することにより、膜厚が３μｍの陽極酸化皮膜を作製した。陽極酸化処理後の試験片について、酢酸ニッケル水溶液（トップシールＨ−２９８）を用いた高温水和型の封孔処理を行い、その後オーブンで１２０℃、３０ｍｉｎの乾燥を行った。乾燥後の試験片を、再びオーブンで２００〜４００℃、３０ｍｉｎの加熱処理を行った。
(Example 2)
The same operation as in Example 1 was performed.
(Comparative Example 2)
Aluminum alloy die-cast material ADC12 was used as a test piece. The test piece was immersed as an anode in a 200 g / L sulfuric acid bath, and a direct current was applied for 10 minutes at a current density of 1.5 A / dm 2 to produce an anodized film having a thickness of 3 μm. The test piece after the anodizing treatment was subjected to a high temperature hydration type sealing treatment using an aqueous nickel acetate solution (Top Seal H-298), and then dried in an oven at 120 ° C. for 30 minutes. The test piece after drying was again subjected to a heat treatment at 200 to 400 ° C. for 30 minutes in an oven.
実施例２及び比較例２で得られた試験片について、実施例１と同様に、陽極酸化皮膜表面のマイクロクラック数を測定した。また、実施例１と同様に、塩水噴霧試験（ＪＩＳ Ｚ ２３７１）を２４０ｈ行い、耐食性評価を行った。加熱温度とマイクロクラック数の関係を図５に、マイクロクラック数と腐食面積率の関係を図６に、図５及び図６のプロットデータを表２に、それぞれ示す。 For the test pieces obtained in Example 2 and Comparative Example 2, the number of microcracks on the anodized film surface was measured in the same manner as in Example 1. Moreover, similarly to Example 1, the salt spray test (JIS Z 2371) was performed for 240 hours, and corrosion resistance evaluation was performed. FIG. 5 shows the relationship between the heating temperature and the number of microcracks, FIG. 6 shows the relationship between the number of microcracks and the corrosion area ratio, and Table 2 shows the plot data of FIGS.
図５及び図６より、比較例２では、加熱処理を行ってもマイクロクラック数はほとんど増加せず、腐食面積率が増加した。つまり、耐食性が悪化することが確認された。このことから、高温水和型の封孔処理を用いた場合、加熱処理を行ってもマイクロクラックは作製されにくいことが示された。図６より、比較例２では、少量生成するマイクロクラックは、膜厚が薄い部分に集中する傾向があるため、腐食電流を分散させることができず、もともと耐食性の低い膜厚が薄い部分にマイクロクラックが作製されることにより、さらに耐食性が低下することが示された。これらのことから、本発明はリチウムイオンを含む封孔処理液を用いた封孔処理でのみ可能な方法であることが示された。 5 and 6, in Comparative Example 2, the number of microcracks hardly increased even when heat treatment was performed, and the corrosion area ratio increased. That is, it was confirmed that the corrosion resistance deteriorates. From this, it was shown that when a high temperature hydration type sealing treatment is used, microcracks are hardly produced even if heat treatment is performed. From FIG. 6, in Comparative Example 2, microcracks generated in a small amount tend to concentrate on the thin film thickness portion, so that the corrosion current cannot be dispersed, and the microfilm is originally formed on the thin film thickness portion having low corrosion resistance. It was shown that the corrosion resistance is further reduced by the formation of cracks. From these facts, it was shown that the present invention is a method that can be performed only by a sealing treatment using a sealing treatment liquid containing lithium ions.
（実施例３）
アルミニウム合金ダイカスト材ＡＤＣ１２を試験片として用いた。２００ｇ／Ｌの硫酸浴に試験片を陽極として浸漬し、電流密度１．５Ａ／ｄｍ２で直流を１０分間通電することにより、膜厚が３μｍの陽極酸化皮膜を作製した。陽極酸化処理後の試験片を、０．８ｇ／Ｌのリチウムイオンを含み、ｐＨを１２、温度を４０℃とした封孔処理液に1分間浸漬して封孔処理を行い、その後オーブンで１２０℃、３０ｍｉｎの乾燥を行った。乾燥後の試験片を、再びオーブンで４００℃、３０ｍｉｎの加熱処理を行った。
(Example 3)
Aluminum alloy die-cast material ADC12 was used as a test piece. The test piece was immersed as an anode in a 200 g / L sulfuric acid bath, and a direct current was applied for 10 minutes at a current density of 1.5 A / dm 2 to produce an anodized film having a thickness of 3 μm. The test piece after the anodization treatment was immersed in a sealing treatment solution containing 0.8 g / L lithium ion, pH 12 and temperature 40 ° C. for 1 minute, and then sealed in an oven. Drying was performed at ° C for 30 minutes. The test piece after drying was again subjected to heat treatment in an oven at 400 ° C. for 30 minutes.
得られた試験片について、加熱処理前後における試験片のＦＥ−ＳＥＭによる断面写真を撮影した。
一般に、アルミダイカスト材等のシリコンを多く含むアルミニウム合金部材に陽極酸化皮膜を作製した場合、シリコン量が少なくアルミニウム量が多い部分には厚い皮膜が生成し、シリコン量が多くアルミニウム量が少ない部分には薄い皮膜が生成するため、厚膜部と薄膜部が交互に存在し、全体的に不均一な膜厚の皮膜が得られる。そこで、加熱処理後の試験片については、厚膜部（膜厚約１０μｍ）と薄膜部（膜厚約２μｍ）の断面写真を撮影した。
加熱処理前における試験片の断面写真を図７（ａ）に、加熱処理後における厚膜部の断面写真を図８に、加熱処理後における薄膜部の断面写真を図９に、それぞれ示す。なお、図７（ｂ）中の矢印Ａは、写真の撮影方向を示している。
About the obtained test piece, the cross-sectional photograph by the FE-SEM of the test piece before and behind heat processing was image | photographed.
In general, when an anodized film is formed on an aluminum alloy member containing a large amount of silicon such as an aluminum die-cast material, a thick film is formed in a portion where the amount of silicon is small and the amount of aluminum is large, and a portion where the amount of silicon is large and the amount of aluminum is small. Since a thin film is formed, thick film portions and thin film portions exist alternately, and a film having a non-uniform film thickness can be obtained as a whole. Then, about the test piece after heat processing, the cross-sectional photograph of the thick film part (film thickness of about 10 micrometers) and the thin film part (film thickness of about 2 micrometers) was image | photographed.
FIG. 7A shows a cross-sectional photograph of the test piece before the heat treatment, FIG. 8 shows a cross-sectional photograph of the thick film portion after the heat treatment, and FIG. 9 shows a cross-sectional photograph of the thin film portion after the heat treatment. In addition, the arrow A in FIG.7 (b) has shown the photography direction of the photograph.
図７（ａ）より、アルミニウム合金ダイカスト材２１の表面に作製された陽極酸化皮膜２２の表面２２ｓには、表面から１μｍ程度の深さのマイクロクラック２３が生成していることが確認された。図８及び図９より、皮膜３２の厚膜部と薄膜部の両方において、マイクロクラック３３がアルミニウム合金ダイカスト材３１にまで達していることが確認された。このことから、陽極酸化皮膜の表面には、全体的に均一にマイクロクラックが生成していることが示された。 From FIG. 7A, it was confirmed that microcracks 23 having a depth of about 1 μm from the surface were generated on the surface 22 s of the anodized film 22 produced on the surface of the aluminum alloy die-cast material 21. 8 and 9, it was confirmed that the microcracks 33 reached the aluminum alloy die-cast material 31 in both the thick film portion and the thin film portion of the film 32. From this, it was shown that microcracks were generated uniformly on the entire surface of the anodized film.
１１ アルミニウム合金部材
１２ 陽極酸化皮膜
１３ 孔
１４ リチウム化合物
１５ ジアスポア
１６ シリコン
１７、１８ マイクロクラック
２１ アルミニウム合金部材
２２ 陽極酸化皮膜
２２ｓ 表面
２３ マイクロクラック
３１ アルミニウム合金部材
３２ 陽極酸化皮膜
３３ マイクロクラック
Ａ 写真の撮影方向
Ｐ 圧力
11 Aluminum alloy member 12 Anodized film 13 Hole 14 Lithium compound 15 Diaspore 16 Silicon 17, 18 Microcrack 21 Aluminum alloy member 22 Anodized film 22s Surface 23 Microcrack 31 Aluminum alloy member 32 Anodized film 33 Microcrack A Direction P Pressure
Claims (7)
前記陽極酸化皮膜の表面を、リチウムイオンを含む封孔処理液を用いて処理する工程と、
前記封孔処理された陽極酸化皮膜を加熱する工程と
を含む陽極酸化皮膜の製造方法。 Producing an anodized film on the surface of the aluminum or aluminum alloy member;
Treating the surface of the anodized film with a sealing treatment liquid containing lithium ions;
Heating the sealed anodic oxide film, and a method for producing the anodic oxide film.
前記陽極酸化皮膜の表面に細孔を備えており、前記細孔内に少なくともリチウム金属又はリチウムを主成分とする合金もしくは化合物を備えており、
前記陽極酸化皮膜の表面にマイクロクラックをさらに備える、陽極酸化皮膜。 An anodized film formed on the surface of an aluminum or aluminum alloy member,
The surface of the anodized film is provided with pores, and the pores are provided with at least lithium metal or an alloy or compound containing lithium as a main component,
An anodized film further comprising microcracks on the surface of the anodized film.
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| CN103938250A (en) | 2014-07-23 |
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