JP2569422B2 - Aluminum oxide laminated structure film and method for producing the same - Google Patents
Aluminum oxide laminated structure film and method for producing the sameInfo
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- JP2569422B2 JP2569422B2 JP5238947A JP23894793A JP2569422B2 JP 2569422 B2 JP2569422 B2 JP 2569422B2 JP 5238947 A JP5238947 A JP 5238947A JP 23894793 A JP23894793 A JP 23894793A JP 2569422 B2 JP2569422 B2 JP 2569422B2
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- aluminum
- aluminum oxide
- film
- electrolysis
- current density
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Description
【０００１】[0001]
【産業上の利用分野】この出願の発明は、アルミニウム
又はアルミニウム合金の陽極酸化処理技術に関するもの
であり、より具体的には、密着性とともに、耐食性、耐
摩耗性、電気絶縁性などの諸特性に優れた酸化アルミニ
ウムによる皮膜体とその製造方法に関するものである。BACKGROUND OF THE INVENTION of this application invention, aluminum
Or those related to the anodic oxidation treatment technique of the aluminum alloy
By weight, more specifically, adhesion between both corrosion, abrasion resistance, oxidation excellent in various properties such as electrical insulation properties Arumini
It relates coating material and manufacturing method thereof according um.
【０００２】[0002]
【従来の技術とその課題】アルミニウム又はアルミニウ
ム合金については、硫酸や蓚酸などの水溶液中で陽極酸
化処理すると、一般に、その表面に、多孔質層とバリア
ー層とからなる多孔質構造の酸化アルミニウム皮膜が生
成することが知られている。 For BACKGROUND OF and THE INVENTION aluminum or aluminum <br/> arm alloy, the anodic oxidation treatment in an aqueous solution of sulfuric acid or oxalic acid, typically, on the surface thereof, a porous consisting of a porous layer and a barrier layer It is known that an aluminum oxide film having a structure is formed.
【０００３】直流電解を常法により行うと、通常、セル
（孔壁部）が垂直に成長したシリンダー状の多孔質層が
得られ、一方、常法の正弦波交流により陽極酸化する
と、直流電解によるシリンダー状構造に比べてセルの歪
んだ構造が得られる。また、蓚酸皮膜については、常法
より実効電圧（以下、単に「電圧」と略す）を高める
と、多孔質層及びバリアー層からなる多孔質構造は基本
的に保持されるが、それらの層はともにスポンジ状とな
り、微細構造に乱れが生ずる。このように、多孔質層の
セルがスポンジ状となるのは、電解時に発生する水素ガ
スの影響ではないかと考えられている。[0003] performed by a conventional method DC electrolysis usually cell (hole wall portion) is obtained porous layer of shaped cylinder grown vertically, whereas, when anodized sinusoidal alternating conventional method, DC electrolysis strain <br/> I structure of the cell as compared to the cylindrical structure by the Ru obtained. As for the oxalic acid film , if the effective voltage (hereinafter simply abbreviated as “voltage”) is increased from the ordinary method, the porous structure composed of the porous layer and the barrier layer is basically
Although to be held, the layers are both a sponge, that may arise from the disturbance in the microstructure. Thus, the <br/> cells of the porous layer becomes spongy is considered that it is the effect of hydrogen gas generated during electrolysis.
【０００４】バリアー層は、直流電解皮膜では、一般
に、電圧に比例して厚くなり、緻密な層となる。しかし
ながら、交流電解では、蓚酸皮膜の場合、低電圧印加時
には直流電解皮膜と同様に電圧に比例して厚くなるもの
の、４０Ｖ前後からは直線関係からずれた低い値とな
る。このような現象に関して、皮膜の厚さ及び形態への
水素ガスの影響が示唆されてはいるが、それ以上の報告
はこれまでになされてはいない。特に、皮膜の微細構造
に関しては、前述したような、多孔質構造が保たれたま
ま、多孔質層のセルがスポンジ状化するという程度のこ
とが分かっているに過ぎない。高電流密度での交流電解
によりアルミニウム又はアルミニウム合金材を陽極酸化
し、その表面に酸化アルミニウム皮膜を生成させること
は従来では行われていない。これは、一つに、常法によ
る交流電解では、電圧を上げれば上げるほど、多孔質層
のセルとバリアー層の微細構造が乱れ、耐食性、耐摩耗
性等の諸特性が低下することによるものと推定される。 [0004] In a direct current electrolytic film, a barrier layer is generally used.
Then, it becomes thicker in proportion to the voltage and becomes a dense layer. However
While, in the alternating current electrolysis in the case of oxalic acid coating, when a low voltage is applied
It made thicker in proportion to the voltage similar to the DC electrolytic coating to
Of I and low value deviating from the linear relationship from around 40V
You. In this phenomenon, although Ru Yes to influence of <br/> hydrogen gas to the thickness and form of the coating is suggested, further reports no yes been made heretofore. In particular, with regard to the microstructure of the coating, as described above, the porous structure coercive Taretama
Also , the degree to which the cells of the porous layer are sponge-like
I just know that. AC electrolysis at high current density
Anodic oxidation of aluminum or aluminum alloy material
To form an aluminum oxide film on the surface
Is not done conventionally. This is partly due to the
In AC electrolysis, the higher the voltage, the more porous layer
Cell and barrier layer microstructure is disturbed, corrosion resistance, abrasion resistance
It is presumed that various properties such as gender are reduced.
【０００５】この出願の発明は、以上の通りの事情に鑑
みてなされたものであり、高電流密度での交流電解を積
極的に応用し、陽極酸化により、密着性に優れ、しかも
耐食性、耐摩耗性、電気絶縁性などの諸特性にも優れた
酸化アルミニウム皮膜をアルミニウム又はアルミニウム
合金表面に生成させる技術を提供することを目的として
いる。[0005] The invention of this application is based on the above situation.
It has been done with AC electrolysis at high current density.
And actively applicable, by anodic oxidation, excellent adhesion, yet <br/> corrosion, abrasion resistance, excellent in various properties such as electrical insulation properties
Aluminum or aluminum oxide film
As an object to provide a technique for generating on the alloy surface
There Ru.
【０００６】[0006]
【課題を解決するための手段】この出願の発明の発明者
らは、特性に優れた機能性酸化皮膜の実現に向け、負成
分を含む波形の定電圧の印加により、可能な限り高電流
密度で均一皮膜を生成させる技術について鋭意研究した
結果、この出願の発明を完成した。Means for Solving the Problems The inventor of the invention of this application
Al is directed to realization of superior functionality oxide film on the characteristics, by applying a constant voltage of waveform including a negative component was studied intensively to have techniques Nitsu to produce a uniform coating at a high current density as possible <br / > a result, have completed the invention of this application.
【０００７】すなわち、この出願の請求項１に係る発明
は、無機酸、有機酸又は無機酸と有機酸の混酸溶液中で
アルミニウム又はアルミニウム合金材を陽極酸化処理す
るに当たって、電解開始直後の電流密度が０．５Ａ／ｃ
ｍ ２ 以上の高電流密度となるように、負成分を含む波形
の定電圧を、一段の電解として、表層多孔質層の直下に
複数の層が積層した積層構造が形成された層状の酸化ア
ルミニウム皮膜が、アルミニウム又はアルミニウム合金
材の表面上に生成するのに十分な時間印加することを特
徴とする酸化アルミニウム積層構造皮膜体の製造方法を
要旨とするものである。Namely, invention according to claim 1 of this application, an inorganic acid, an aluminum or aluminum alloy material in a mixed acid solution of an organic or inorganic acid and an organic acid against the anodic oxidation treatment, electrolytic immediately after the start of Current density 0.5A / c
As will be m 2 or more high current densities, waveforms including a negative component
A constant voltage, as the electrolyte of one stage, directly under the surface layer porous layer
A layered aluminum oxide film having a laminated structure in which a plurality of layers are laminated is formed of aluminum or aluminum alloy
Ru der those summarized as a manufacturing method of the aluminum oxide laminated structure film material and applying sufficient time to produce on the surface of the wood.
【０００８】この請求項１に係る発明は、上記方法によ
り得られた酸化アルミニウム積層構造皮膜体を熱水又は
加圧水蒸気で水和処理することを好ましい態様の一つと
している（請求項２）。The invention according to claim 1 is based on the above method .
Ri resulting aluminum oxide layered structure film body are <br/> with one preferred embodiment to hydration treatment with hot water or steam under pressure (claim 2).
【０００９】この出願の請求項３に係る発明は、電解開
始直後の電流密度が０．５Ａ／ｃｍ ２ 以上の高電流密度
となる負成分を含む波形の定電圧が印加されることによ
り、表層多孔質層の直下に複数の層が積層された積層構
造を有する層状の酸化アルミニウム皮膜が、アルミニウ
ム又はアルミニウム合金材の表面上に配設一体化されて
いることを特徴とする酸化アルミニウム積層構造皮膜体
をその要旨としている。[0009] The invention according to claim 3 of the present application is an electrolysis opening device.
High current density of 0.5 A / cm 2 or more immediately after starting
When a constant voltage with a waveform containing a negative component
Wherein a layered aluminum oxide film having a laminated structure in which a plurality of layers are laminated immediately below a surface porous layer is disposed and integrated on the surface of an aluminum or aluminum alloy material. The gist of the invention is a laminated structure film.
【００１０】以下、この出願の発明についてさらに詳し
く説明する。[0010] Hereinafter, more to further the invention of this application
I will explain.
【００１１】この出願の発明においては、電解開始直後
の電流密度が０．５／ｃｍ ２ 以上の高電流密度となるよ
うに、交流や、ＤＣ−ＰＲのような矩形波又はパルスな
どの負成分を含む波形を有する定電圧を印加し、一段の
電解により、アルミニウム又 はアルミニウム合金材を陽
極酸化処理し、表層多孔質層の直下に複数の層が積層し
た特異的な積層構造が形成された層状の酸化アルミニウ
ム皮膜をアルミニウム又はアルミニウム合金材の表面上
に生成させる。陽極酸化処理に際し、定電圧の印加時
間、すなわち電解時間は、アルミニウム又はアルミニウ
ム合金材の表面上に、上記した特異的な積層構造を有す
る酸化アルミニウム皮膜が形成されるのに十分な時間と
する。 In the invention of this application, immediately after the start of electrolysis,
As current density is 0.5 / cm 2 or more high current density, exchange and, square wave or pulse, such as DC-PR
A constant voltage having a waveform including a throat of the negative component is applied, a one-stage
By electrolysis, the aluminum or the aluminum alloy material positive
Extreme oxidation treatment, multiple layers are laminated immediately below the surface porous layer
A layered aluminum oxide film with a unique laminated structure on the surface of aluminum or aluminum alloy material
Ru is generated. When applying a constant voltage during anodizing
During the electrolysis time, aluminum or aluminum
Has the above-mentioned specific laminated structure on the surface of the alloy
Enough time for the aluminum oxide film to form
I do.
【００１２】例えば、硫酸水溶液中の交流電解では、電
解時間が１０分の時、電圧が２０Ｖ程度までで透明で黄
色を呈するシリンダー状の多孔質層が生成する。２５Ｖ
付近からは、皮膜は白味を帯び、徐々に不透明化する。
この現象から、皮膜の微細構造に変化が生じたことが理
解される。電圧が２５Ｖ以上になると、皮膜中に、複数
の層が積層した特異的な積層構造が出現する。そして、
４０Ｖ以上では、皮膜は、完全に不透明白色となる。こ
のような皮膜の色相及び透明性についての変化は、形成
された皮膜中の積層構造に起因する光の散乱効果による
ものと推定される。皮膜中に一旦積層構造が生成する
と、その後には、多孔質層は成長せず、積層構造のみが
成長し、皮膜はその厚さを増して行く。[0012] For example, in the alternating current electrolysis of aqueous sulfuric acid solution, when the electrolysis time is 10 minutes, cylindrical porous layer in which the voltage coloration transparent yellow <br/> color at up to about 20V is that generates. 25V
From the vicinity , the film becomes whitish and gradually becomes opaque.
This phenomenon, management can change the microstructure of the coating has occurred
Ru is the solution. A voltage of more than 25V, in the coating, more
A specific laminated structure in which the layers are laminated appears. And
In above 40V, the coating becomes completely opaque white. Changes in the hue and transparency of such coatings are
According to the light scattering effect due to the stackup structures in the film
It is presumed that. <br/> and that generates Once stacked structure in the coating, after which the porous layer is not grown, only the laminated structure is grown, the coating going to increase its thickness.
【００１３】図１は、アルミニウム材を硫酸水溶液中
で、電解開始直後の電流密度を１．３Ａ／ｃｍ２ として
３０Ｖの交流定電圧を１０分間印加し、電解により陽極
酸化した時に得られた酸化アルミニウム皮膜の破断面Ｓ
ＥＭ像を示している。この図１から、アルミニウム材表
面には、表層多孔質層の直下に酸化アルミニウムによる
複数の層が積層した積層構造を有する層状皮膜が形成さ
れていることが確認される。このような積層化の原因
は、今のところ明確には解明されてはいないが、おそら
く、電流密度の増加に伴って、水素ガスが激しく発生す
ることが関与しているものと推察される。[0013] Figure 1, an aluminum material in an aqueous sulfuric acid solution, the current density immediately after the initiation of the electrolysis as 1.3A / cm 2
An AC constant voltage of 30 V is applied for 10 minutes , and the fracture surface S of the aluminum oxide film obtained when anodizing by electrolysis is performed.
That shows the EM image. From FIG. 1, the aluminum material table
The surface is made of aluminum oxide just below the surface porous layer.
A layered film having a laminated structure in which multiple layers are laminated is formed.
It Ru confirmed to. Cause of such laminated include, but are not yes been clarified clear at the moment, defer
Ku, with increasing current density, to vigorously generate hydrogen gas
It is assumed that Rukoto are involved.
【００１４】生成した皮膜は、このままの状態では、密
着強度が直流皮膜に比べ劣ってはいるが、その反面、耐
食性、耐摩耗性、断熱性などの諸特性には優れている。
とりわけ、多孔質層のみの皮膜に比べ、皮膜の比表面積
が増大するため、触媒皮膜をはじめとして、染料、無機
粉体、さらには金属吸着、電析等用の機能性膜への利用
が有望視される。[0014] The resulting coating, in this state, although adhesion strength Ru Yes I inferior compared to the DC film, on the other hand, corrosion resistance, wear resistance, are excellent in various properties such as thermal insulation.
Especially, compared with the film of the porous layer only, the specific surface area of the coating is increased, including the catalyst coating, promising dyes, inorganic powder, and further metal adsorption, the use of the functional film for electrodeposition such Is seen .
【００１５】このような積層構造を有する層状皮膜をア
ルミニウム又はアルミニウム合金材の表面上に生成させ
るためには、陽極酸化処理に当たって、負成分を含み、
電解開始直後の電流密度が０．５Ａ／ｃｍ ２ 以上の高電
流密度となるような定電圧を、表層多孔質層の直下に複
数の層が積層した積層構造が形成された層状の酸化アル
ミニウム皮膜が、アルミニウム又はアルミニウム合金材
の表面上に生成するのに十分な、例えば１０分程度の時
間印加することが欠かせない。特に、電解開始直後の電
流密度が０．５Ａ／ｃｍ２ 未満の場合には、均一な層状
皮膜が得られない。 A layered film having such a laminated structure is
For Ru <br/> is generated on the surface of the aluminum or aluminum alloy material, against the anodization, it sees contains a negative component,
High current density of 0.5 A / cm 2 or more immediately after the start of electrolysis
A constant voltage that gives the current density is applied immediately below the surface porous layer.
Layered Al Oxide with a laminated structure consisting of several layers
Minium film is made of aluminum or aluminum alloy
When it is enough to form on the surface of, for example, about 10 minutes
It is indispensable to apply the voltage for a while . In particular, when the current density immediately after the start of electrolysis is less than 0.5 A / cm 2 ,
No film is obtained.
【００１６】その他の電解条件については特別な制限は
ない。例えば、陽極酸化処理溶液には、硫酸、リン酸、
クロム酸等の無機酸又はこれらの混酸を使用することが
できる。或いは、蓚酸、酒石酸、スルホフタル酸等の有
機酸を単独で、また、上記無機酸との混酸として使用す
ることも可能である。[0016] There is no special restriction on the other electrolysis conditions. For example, the anodization solution, sulfuric acid, phosphoric acid,
It is possible to use inorganic acids such as chromic acid or their mixed acids
it can. Alternatively,蓚 acid, alone tartaric acid, organic acids such as sulphophthalic acid, also Ru also der be used as mixed acid of the inorganic acids.
【００１７】得られた酸化アルミニウム積層構造皮膜体
は、次いで、熱水又は水蒸気処理などの水和処理を行う
と、皮膜の剥離（密着性）が改善され、耐食性、耐摩耗
性、電気絶縁性等の諸特性が向上する。これは、皮膜の
各層の表面が水和化し、層間がより強固に接合されるこ
とがその一因と考えられる。このように、水和処理した
酸化アルミニウム積層構造皮膜体は諸特性に優れるた
め、従来からの用途に限られず、新たな用途への展開が
期待される。The obtained aluminum oxide laminated structure film
It is then carried out hydration treatment such as hot water or steam treatment
In addition , the peeling (adhesion) of the film is improved, and various properties such as corrosion resistance, abrasion resistance, and electrical insulation are improved. This is this the surface of <br/> each layer of the film was Mizuwaka, between layers are firmly bonded
Is considered to be one of the causes . Thus, the hydration treatment
Aluminum oxide laminated structure film material is excellent in various properties
Because, without being limited to the application of conventional and development into new applications
Ru is expected.
【００１８】次に、この出願の実施例を示す。Next , examples of this application will be described.
【００１９】[0019]
【実施例】実施例１ 高純度（９９．９９％以上）のアルミニウム材につい
て、濃度１００ｍｌ／ｌ、液温１５℃の硫酸水溶液中で
対極にカーボンを使用し、交流２５Ｖの定電圧を印加
し、電解開始直後の電流密度を０．８Ａ／ｃｍ２ として
電解により陽極酸化処理を行った。その結果、黄色味を
帯びた不透明の酸化アルミニウムの積層構造皮膜がアル
ミニウム材の表面上に生成した。The aluminum material of EXAMPLE 1 High purity (99.99%), concentration 100 ml / l, using carbon as a counter electrode in sulfuric acid aqueous solution of a liquid temperature of 15 ° C., a constant voltage of AC 25V applied
And, a current density immediately after the initiation of the electrolysis as 0.8 A / cm 2
Anodizing treatment was performed by electrolysis . As a result, the laminated structure film of aluminum oxide opaque tinged yellow taste Al
Formed on the surface of the minium material .
【００２０】実施例２ 高純度（９９．９９％以上）のアルミニウム材につい
て、濃度５０ｍｌ／ｌ、液温２０℃の硫酸水溶液中で対
極にカーボンを使用し、交流３０Ｖの定電圧を印加し、
電解開始直後の電流密度を１．３Ａ／ｃｍ２ として電解
により陽極酸化処理を行った。その結果、乳白色の酸化
アルミニウム積層構造皮膜がアルミニウム材の表面上に
生成した。[0020] The aluminum material of Example 2 High purity (99.99%), using carbon as a counter electrode at a concentration of 50 ml / l, solution temperature 20 ° C. in aqueous sulfuric acid solution, and a constant voltage of AC 30V ,
The current density immediately after the start of electrolysis is 1.3 A / cm 2 and electrolysis is performed.
For anodic oxidation. As a result, milky white oxidation
Aluminum laminated structure coating on the surface of aluminum material
Generated .
【００２１】実施例３ 純度９９．０％以上の工業用純アルミニウム材につい
て、濃度５０ｍｌ／ｌ、液温２０℃の硫酸水溶液中で対
極にカーボンを使用し、交流５０Ｖの定電圧を印加し、
電解開始直後の電流密度を４Ａ／ｃｍ２ として電解によ
り陽極酸化処理を行った。その結果、白色の酸化アルミ
ニウム積層構造皮膜がアルミニウム材の表面上に生成し
た。[0021] For Example 3 99.0% or more of the industrial pure aluminum material, using carbon as a counter electrode at a concentration of 50 ml / l, solution temperature 20 ° C. in aqueous sulfuric acid solution, and a constant voltage of AC 50V ,
Immediately after the start of electrolysis, the current density was set to 4 A / cm 2 ,
Anodizing treatment was performed. As a result, white aluminum oxide
A layered structure film of aluminum was formed on the surface of the aluminum material .
【００２２】実施例４ Ａ５０５２アルミニウム合金材について、濃度１００ｍ
ｌ／ｌ、液温２０℃の硫酸水溶液中で対極にアルミニウ
ムを使用し、交流４０Ｖの定電圧を印加し、電解開始直
後の電流密度を０．８Ａ／ｃｍ２ として電解により陽極
酸化処理を行った。その結果、乳白色の酸化アルミニウ
ムの積層構造皮膜がアルミニウム材の表面 上に生成し
た。[0022]Example 4 A5052 aluminum alloy material, concentration 100m
l / l, sulfuric acid with a liquid temperature of 20 ° CwaterAluminum in counter electrode in solution
Use a 40V ACofConstant voltageAnd applyImmediately after the start of electrolysis
Later current densityTo0.8A / cm2 As by electrolysisanode
An oxidation treatment was performed. The result is a milky whiteAluminum oxide
OfThe laminated structure filmAluminum material surface Generate on
Was.
【００２３】実施例５ 純度９９．９９％以上の純アルミニウム材について、濃
度３％、液温２０℃の蓚酸水溶液中で対極にカーボンを
使用し、交流１００Ｖの定電圧を印加し、電解開始直後
の電流密度を０．５Ａ／ｃｍ２ として電解により陽極酸
化処理を行った。その結果、白色の酸化アルミニウム積
層構造皮膜がアルミニウム材の表面上に生成した。[0023] For Example 5 99.99% purity or more pure aluminum material, 3% concentration, using carbon as a counter electrode with oxalic acid aqueous solution at a liquid temperature 20 ° C., applying a constant voltage of AC 100 V, starting electrolytic Immediately after the current density was set to 0.5 A / cm 2 , anodizing treatment was performed by electrolysis . As a result, a white aluminum oxide laminated film was formed on the surface of the aluminum material .
【００２４】[0024]
【発明の効果】以上詳しく説明した通り、この出願の発
明によって、アルミニウム又はアルミニウム合金材の表
面上に特異的な積層構造を有する酸化アルミニウム積層
構造皮膜を簡便かつ容易に生成させることができる。し
かもこの皮膜は、密着性に優れるとともに、耐食性、耐
摩耗性、電気絶縁性、断熱性等の諸特性が改善されてお
り、新たな機能性膜として、その利用が大いに期待され
る。 As described [Effect Invention above in detail, I by the originating <br/> light of this application, simple and easy to aluminum oxide layered structure film having a specific multilayer structure on the surface of the aluminum or aluminum alloy material Ru can be generated. I
Or Again coating, Rutotomoni excellent adhesion, corrosion resistance, wear resistance, electrical insulating properties, it is improved characteristics of heat insulation, etc.
Ri, as a new functional film, use of that is Ru is greatly expected <br/>.
【図１】陽極酸化皮膜（薄膜）の破断面のＳＥＭ像を示
した図面代用の写真である。FIG. 1 shows an SEM image of a fractured surface of an anodized film (thin film).
It is a photograph as a substitute for a drawing .
Claims (3)
酸溶液中でアルミニウム又はアルミニウム合金材を陽極
酸化処理するに当たって、電解開始直後の電流密度が
０．５Ａ／ｃｍ ２ 以上の高電流密度となるように、負成
分を含む波形の定電圧を、一段の電解として、表層多孔
質層の直下に複数の層が積層した積層構造が形成された
層状の酸化アルミニウム皮膜が、アルミニウム又はアル
ミニウム合金材の表面上に生成するのに十分な時間印加
することを特徴とする酸化アルミニウム積層構造皮膜体
の製造方法。1. A mineral acid, an aluminum or aluminum alloy material in a mixed acid solution of an organic or inorganic acid and an organic acid against the anodic oxidation treatment, current density immediately after the start of electrolysis is
In order to obtain a high current density of 0.5 A / cm 2 or more, a constant voltage having a waveform containing a negative component is applied as a single-stage electrolysis to the surface layer.
Layered structure formed by stacking multiple layers immediately below the porous layer
If the layered aluminum oxide film is aluminum or aluminum
Applied enough time to form on the surface of minium alloy material
A method for producing an aluminum oxide laminated structure film, characterized in that:
体を、熱水又は加圧水蒸気で水和処理する請求項１記載
の酸化アルミニウム積層構造皮膜体の製造方法。2. The resulting aluminum oxide layered structure film body according to claim 1 wherein the hydration treatment with hot water or steam under pressure
A method for producing a laminated body of aluminum oxide according to the above.
ｍ ２ 以上の高電流密度となる負成分を含む波形の定電圧
が印加されることにより、表層多孔質層の直下に複数の
層が積層された積層構造を有する層状の酸化アルミニウ
ム皮膜が、アルミニウム又はアルミニウム合金材の表面
上に配設一体化されていることを特徴とする酸化アルミ
ニウム積層構造皮膜体。3. The current density immediately after the start of electrolysis is 0.5 A / c.
Constant voltage with a waveform containing a negative component that has a high current density of m 2 or more
Is applied , a layered aluminum oxide film having a laminated structure in which a plurality of layers are laminated immediately below the surface porous layer is disposed and integrated on the surface of the aluminum or aluminum alloy material. Characteristic aluminum oxide laminated structure film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5238947A JP2569422B2 (en) | 1993-08-30 | 1993-08-30 | Aluminum oxide laminated structure film and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5238947A JP2569422B2 (en) | 1993-08-30 | 1993-08-30 | Aluminum oxide laminated structure film and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0762595A JPH0762595A (en) | 1995-03-07 |
| JP2569422B2 true JP2569422B2 (en) | 1997-01-08 |
Family
ID=17037656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5238947A Expired - Lifetime JP2569422B2 (en) | 1993-08-30 | 1993-08-30 | Aluminum oxide laminated structure film and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2569422B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3803353B2 (en) * | 2003-06-17 | 2006-08-02 | 中国電化工業株式会社 | Surface-treated aluminum material and manufacturing method thereof |
| KR100929934B1 (en) * | 2009-05-19 | 2009-12-04 | 통일방폭전기 주식회사 | Method for manufacturing sealing fitting used in flameproof electric wire piping |
| KR100929929B1 (en) * | 2009-05-19 | 2009-12-04 | 통일방폭전기 주식회사 | Method for manufacturing union coupling used in flameproof electric wire piping |
| KR100929935B1 (en) * | 2009-05-19 | 2009-12-04 | 통일방폭전기 주식회사 | Method for manufacturing junction box used in flameproof electric wire piping |
| KR100935638B1 (en) * | 2009-05-19 | 2010-01-07 | 통일방폭전기 주식회사 | Method for manufacturing elbow used in flameproof electric wire piping |
| JP5642640B2 (en) | 2011-09-12 | 2014-12-17 | トヨタ自動車株式会社 | Internal combustion engine and manufacturing method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5950196A (en) * | 1982-09-17 | 1984-03-23 | Nippon Light Metal Co Ltd | Multilayered alumite and its manufacture |
| JPS6029493A (en) * | 1983-07-20 | 1985-02-14 | Pentel Kk | Manufacture of aluminum or aluminum alloy substrate having oxide film |
| JPH0375638A (en) * | 1989-08-16 | 1991-03-29 | Konica Corp | Cartridge of roll film for photography |
-
1993
- 1993-08-30 JP JP5238947A patent/JP2569422B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0762595A (en) | 1995-03-07 |
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