JP2023141525A - Aluminum alloy material having anodized film and production method of the same - Google Patents
Aluminum alloy material having anodized film and production method of the same Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 40
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 72
- 238000011282 treatment Methods 0.000 claims abstract description 52
- 239000010407 anodic oxide Substances 0.000 claims description 11
- 238000007743 anodising Methods 0.000 claims description 11
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 36
- 230000007797 corrosion Effects 0.000 abstract description 36
- 230000002087 whitening effect Effects 0.000 abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 28
- 238000012360 testing method Methods 0.000 description 24
- 238000000034 method Methods 0.000 description 21
- 238000012545 processing Methods 0.000 description 19
- 229910052759 nickel Inorganic materials 0.000 description 14
- 239000000463 material Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- -1 amine compounds Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910000676 Si alloy Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910001680 bayerite Inorganic materials 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- WMWXXXSCZVGQAR-UHFFFAOYSA-N dialuminum;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3] WMWXXXSCZVGQAR-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical class [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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Abstract
Description
本発明は、陽極酸化皮膜を有するアルミニウム合金材及びその製造方法に関するものである。 The present invention relates to an aluminum alloy material having an anodic oxide film and a method for manufacturing the same.
アルミニウム合金は私達の身の回りで広く使われている。しかし、空気中においては緻密で安定的な自然酸化皮膜を形成しているものの、その膜厚は２ｎｍ程度と非常に薄く、使用環境によっては容易に腐食してしまう。そこで、耐食性を向上させるために人工的な酸化処理（陽極酸化処理）による酸化皮膜の形成が行われている。 Aluminum alloys are widely used around us. However, although a dense and stable natural oxide film is formed in the air, the film thickness is very thin, about 2 nm, and can easily corrode depending on the usage environment. Therefore, in order to improve corrosion resistance, an oxide film is formed by artificial oxidation treatment (anodic oxidation treatment).
陽極酸化処理後の材料表面の陽極酸化皮膜には、無数の細孔が形成される。この細孔は化学的に活性であり、酸素や他の化学物質と反応しやすい状態にあるため、封孔処理を施すことによってそれらの反応を防止する（耐食性を向上させる）のが一般的である。この封孔処理方法としては、沸騰水封孔、加圧水蒸気封孔、常温ニッケル封孔、高温ニッケル封孔等が知られている。 Countless pores are formed in the anodic oxide film on the surface of the material after the anodizing treatment. These pores are chemically active and easily react with oxygen and other chemicals, so it is common practice to prevent these reactions (improve corrosion resistance) by applying a sealing treatment. be. As this sealing treatment method, boiling water sealing, pressurized steam sealing, room temperature nickel sealing, high temperature nickel sealing, etc. are known.
アルミニウム合金を陽極酸化処理し、さらに封孔処理する表面処理方法において、耐食性を向上させるため、封孔処理の様々な見直しが行われている。 In a surface treatment method in which an aluminum alloy is anodized and further sealed, various improvements have been made to the sealing process in order to improve corrosion resistance.
特開昭５０－１１７６４８号公報（特許文献１）では、極性溶媒と金属フッ化物を含有させ耐食性を向上させる常温ニッケル封孔に関する発明が発表され、特開昭５６－０６２９９１号公報（特許文献２）では陽極酸化皮膜を形成させた後、第１封孔処理として金属塩、アンモニウム誘導体、アミン化合物、水酸化アルカリまたはホウ素化合物のように通常使用されている封孔剤の一種もしくはそれ以上を０．１ｇ／Ｌ～飽和濃度の範囲で含む５～８０℃の水溶液に浸漬し、次いで、第２封孔処理として６０～１００℃に加温した水中に浸漬し耐食性を向上させる２段封孔処理法を提供している。 JP-A-50-117648 (Patent Document 1) discloses an invention related to room-temperature nickel sealing that improves corrosion resistance by containing a polar solvent and metal fluoride, and JP-A-56-062991 (Patent Document 2) ), after forming an anodized film, one or more of the commonly used sealants such as metal salts, ammonium derivatives, amine compounds, alkali hydroxides, or boron compounds are added as the first sealing treatment. A two-stage sealing treatment that improves corrosion resistance by immersing in an aqueous solution at 5 to 80°C containing a concentration ranging from .1 g/L to saturation concentration, and then immersing in water heated to 60 to 100°C as a second sealing treatment. provides law.
また、アルミニウム合金の陽極酸化皮膜に関する国内規格では、ＪＩＳ Ｈ８６０１－１９６８で封孔方法として水和封孔を規定し、ＪＩＳ Ｈ９５００－１９７１及びＪＩＳ Ｈ９５０１－１９７１で加圧水蒸気封孔または沸騰水封孔における処理条件を規定して、沸騰水封孔の場合には封孔助剤の添加を認めている。 Furthermore, in the domestic standards for anodic oxide coatings on aluminum alloys, JIS H8601-1968 specifies hydration sealing as a sealing method, and JIS H9500-1971 and JIS H9501-1971 specify hydration sealing as a sealing method. Processing conditions are specified, and in the case of boiling water sealing, the addition of sealing aids is permitted.
封孔処理とはベーマイト（Ｂｏｅｈｍｉｔｅ Ａｌ２Ｏ３・Ｈ２Ｏ）またはバイヤライト（Ｂａｙｅｒｉｔｅ Ａｌ２Ｏ３・３Ｈ２Ｏ）などのアルミニウム酸化物の水和物やニッケルの水酸化物を形成し、その体積膨張によって多孔質を封孔するもので、非特許文献１では加圧水蒸気封孔処理は沸騰水封孔処理の約１．５倍の耐食性を示すことを報告している。 Sealing treatment involves forming aluminum oxide hydrates and nickel hydroxides such as boehmite (Boehmite Al 2 O 3 .H 2 O) or Bayerite (Bayerite Al 2 O 3 .3H 2 O), The volumetric expansion seals porous materials, and Non-Patent Document 1 reports that pressurized steam sealing treatment exhibits about 1.5 times the corrosion resistance of boiling water sealing treatment.
発明者らが各種封孔法により封孔したアルミニウム合金のサンプルについて実施した簡易的な耐酸性試験、具体的にはサンプルを３５℃の１０規定塩酸に浸漬し、水素が発生するまでの時間を測定した耐酸性試験の結果を図１に示す。図１から明らかなように、現在単独の封孔方法としては加圧水蒸気封孔法が最も信頼性が高いが、それでも約５００分で水素が発生している。 A simple acid resistance test was carried out by the inventors on aluminum alloy samples sealed using various sealing methods. Specifically, the sample was immersed in 10 N hydrochloric acid at 35°C, and the time until hydrogen was generated was measured. The results of the measured acid resistance test are shown in FIG. As is clear from FIG. 1, the pressurized steam sealing method is currently the most reliable as a single sealing method, but hydrogen is still generated in about 500 minutes.
これは、非特許文献２で報告されているように、封孔で形成される水和物が陽極酸化処理によって形成される酸化物より酸溶液に溶解しやすく、最も封孔度の高い加圧水蒸気封孔処理を施したとしても、自動車等の外装部品の分野では耐食性が十分ではないことを示している。 As reported in Non-Patent Document 2, hydrates formed during pore sealing are more soluble in acid solutions than oxides formed during anodizing treatment, and pressurized steam This indicates that even if sealing treatment is performed, corrosion resistance is not sufficient in the field of exterior parts for automobiles and the like.
特許６６６７１９１号公報（特許文献３）では、第１封孔処理として低温のニッケル塩水溶液に浸漬する低温封孔処理を行い、次いで第２封孔処理として水蒸気による加圧水蒸気封孔処理を行い、さらに第３封孔処理としてゾル－ゲル法によるシリカ質皮膜を形成している。 In Japanese Patent No. 6,667,191 (Patent Document 3), a low-temperature sealing process of immersing in a low-temperature nickel salt aqueous solution is performed as a first sealing process, then a pressurized steam sealing process using water vapor is performed as a second sealing process, and then As the third sealing process, a siliceous film is formed by a sol-gel method.
しかしながら、従来技術で製造されるアルミニウム合金製品においては、屋外で使用した場合、例えば１年程度の短期間で図２に示すような白い斑点（白化）が発生することが問題となっており、その解決には至っていない。 However, when aluminum alloy products manufactured using conventional technology are used outdoors, white spots (whitening) as shown in Figure 2 occur after a short period of about one year, for example, which has become a problem. The solution has not yet been reached.
一方、発明者らは、電界放出型走査電子顕微鏡（ＦＥ－ＳＥＭ）を用いて白化箇所付近を詳細に観察し、白化が材料のごく表面、すなわち陽極酸化皮膜の細孔上部に形成されている薄い封孔層付近が侵食されたことにより荒れ、光が乱反射することによって起こっていることを把握した（図３）。 On the other hand, the inventors used a field emission scanning electron microscope (FE-SEM) to closely observe the area around the whitening site, and found that the whitening was formed on the very surface of the material, that is, above the pores of the anodic oxide film. We found that this was caused by the erosion of the thin sealing layer, which caused the roughness and diffused reflection of light (Figure 3).
また、発明者らは、陽極酸化皮膜を有する従来のアルミニウム合金製品の表面には幅５ｎｍ以上の微小クラックが多数存在していることをＦＥ－ＳＥＭ観察により把握しており、これら微小クラックを低減させることが材料表面の耐食性の向上（白化の抑制）につながる点も明らかにした。 In addition, the inventors have found through FE-SEM observation that there are many microcracks with a width of 5 nm or more on the surface of conventional aluminum alloy products with anodized coatings, and these microcracks can be reduced. It has also been clarified that this leads to improved corrosion resistance (suppression of whitening) on the material surface.
本発明は、上記従来の課題に鑑みてなされたものであり、加圧水蒸気封孔処理条件を見直すことにより陽極酸化皮膜の耐食性を向上させたアルミニウム合金材及びその製造方法を提供することを目的とする。 The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to provide an aluminum alloy material with improved corrosion resistance of an anodized film by reviewing the pressurized steam sealing treatment conditions, and a method for manufacturing the same. do.
発明者らは、従来のような耐食性試験のみからではなく、陽極酸化皮膜の表面形態と耐食性試験の両方から白化対策（耐食性の向上）の検討を重ねた結果、最適な封孔処理条件を見出し、本発明の完成に至った。 The inventors have repeatedly investigated countermeasures against whitening (improving corrosion resistance) not only from conventional corrosion resistance tests, but also from both the surface morphology of the anodic oxide film and corrosion resistance tests, and have found the optimal sealing treatment conditions. This led to the completion of the present invention.
すなわち、本発明のアルミニウム合金材のうち、第１の形態は、封孔処理が行われた陽極酸化皮膜を有するアルミニウム合金材であって、
前記陽極酸化皮膜の表面に観察される幅５ｎｍ以上の微小クラックの合計長さが、合金材表面の単位面積１平方マイクロメートル当たり０．６マイクロメートル以上３．３マイクロメートル以下である。
That is, the first form of the aluminum alloy material of the present invention is an aluminum alloy material having an anodized film subjected to a sealing treatment,
The total length of microcracks with a width of 5 nm or more observed on the surface of the anodic oxide film is 0.6 micrometer or more and 3.3 micrometer or less per unit area of the alloy material surface of 1 square micrometer.
他の形態のアルミニウム合金材は、前記形態の発明において、前記アルミニウム合金材にＪＩＳで定めるＡ５０００番台またはＡ６０００番台の合金を用いるものである。 Another form of aluminum alloy material is one in which, in the invention of the above form, an alloy of A5000 series or A6000 series defined by JIS is used for the aluminum alloy material.
本発明のアルミニウム合金材の製造方法は、陽極酸化処理を行ったアルミニウム合金に、封孔処理法として少なくとも加圧水蒸気封孔処理法を適用し、加圧水蒸気封孔処理の温度を１０５～１２５℃とした。 The method for producing an aluminum alloy material of the present invention includes applying at least a pressurized steam sealing method as a sealing treatment to an aluminum alloy that has been subjected to an anodizing treatment, and setting the temperature of the pressurized steam sealing treatment to 105 to 125°C. did.
また、前記陽極酸化処理の条件は、電流密度０．８～１．５Ａ／ｄｍ２とした。 Further, the conditions for the anodic oxidation treatment were a current density of 0.8 to 1.5 A/dm 2 .
本発明によれば、アルミニウム合金の陽極酸化皮膜を有するアルミニウム合金材において、微小クラックの長さを小さくすることで、アルミニウム合金材の白化現象を抑えることができる。 According to the present invention, the whitening phenomenon of the aluminum alloy material can be suppressed by reducing the length of microcracks in the aluminum alloy material having the anodized film of the aluminum alloy.
以下に、本発明の一実施形態による陽極酸化皮膜を有するアルミニウム合金材について、詳細に説明する。 Below, an aluminum alloy material having an anodic oxide film according to an embodiment of the present invention will be described in detail.
本実施形態のアルミニウム合金材は、封孔処理が行われた陽極酸化皮膜を有するアルミニウム合金材であって、前記陽極酸化皮膜の表面に観察される幅５ｎｍ以上の微小クラックの合計長さが、合金材表面の単位面積１平方マイクロメートル当たり０．６マイクロメートル以上３．３マイクロメートル以下であることを特徴とする。
幅が５ｎｍ未満の微小クラックは、白化が生じる要因とはなりにくいため除外している。
幅が５ｎｍ以上のクラックでは、単位面積１平方マイクロメートル当たりの長さが３．３マイクロメートル以下であれば白化を抑制することができるため、３．３マイクロメートルを上限とする。また、単位面積１平方マイクロメートル当たりの長さが０．６マイクロメートル未満のものは製造が困難であるため、０．６マイクロメートルを下限とする。
The aluminum alloy material of this embodiment is an aluminum alloy material having an anodic oxide film that has been subjected to a sealing treatment, and the total length of microcracks with a width of 5 nm or more observed on the surface of the anodic oxide film is It is characterized in that the surface area of the alloy material is 0.6 micrometers or more and 3.3 micrometers or less per unit area of 1 square micrometer on the surface of the alloy material.
Microcracks with a width of less than 5 nm are excluded because they are unlikely to cause whitening.
For cracks with a width of 5 nm or more, whitening can be suppressed if the length per unit area of 1 square micrometer is 3.3 micrometers or less, so 3.3 micrometers is set as the upper limit. Further, since it is difficult to manufacture a material having a length per unit area of 1 square micrometer of less than 0.6 micrometer, the lower limit is set to 0.6 micrometer.
本実施形態のアルミニウム合金材に用いられる合金種別は、特定のものに限定されないが、例えば、ＪＩＳで定めるＡ５０００番台やＡ６０００番台の合金を好適に用いることができ、用途などにしたがって材料の選択を行うことができる。
なお、ＪＩＳで定めるＡ５０００番台はＡ５０５２、Ａ５０５６、Ａ５０８３等のＭｇを含有する材料、ＪＩＳで定めるＡ６０００番台はＡ６０６１、Ａ６０６３等のＭｇとＳｉを含有する材料であり、ともに耐食性と強度に優れた材料として知られている。
The type of alloy used for the aluminum alloy material of this embodiment is not limited to a specific one, but for example, alloys in the A5000 series and A6000 series defined by JIS can be suitably used, and the material can be selected according to the application. It can be carried out.
The A5000 series specified by JIS refers to materials containing Mg such as A5052, A5056, and A5083, and the A6000 series specified by JIS refers to materials containing Mg and Si such as A6061 and A6063, both of which are materials with excellent corrosion resistance and strength. known as.
本実施形態のアルミニウム合金材では、陽極酸化処理が施されたものが使用される。
陽極酸化処理は常法により行うことができ、本実施形態としては特にその条件が限定されるものではない。陽極酸化処理としては、例えば、硫酸浴（硫酸水溶液）や電解硫酸浴（電解硫酸水溶液）を使用することができ、電流密度も特に限定されないが、０．８～１．５Ａ／ｄｍ２であることが好ましい。
陽極酸化では、Ａｌの溶解速度と酸化速度がバランスするように行う。このような観点で電流密度の好ましい範囲を上記に規定している。
The aluminum alloy material of this embodiment is anodized.
The anodic oxidation treatment can be performed by a conventional method, and the conditions are not particularly limited in this embodiment. For the anodizing treatment, for example, a sulfuric acid bath (sulfuric acid aqueous solution) or an electrolytic sulfuric acid bath (electrolyzed sulfuric acid aqueous solution) can be used, and the current density is also not particularly limited, but is 0.8 to 1.5 A/dm 2 . It is preferable.
Anodic oxidation is performed so that the rate of dissolution of Al and the rate of oxidation are balanced. From this point of view, the preferred range of current density is defined above.
アルミニウム合金材には、陽極酸化処理後に封孔処理が施される。封孔処理としては、少なくとも加圧水蒸気封孔処理法を行う。本発明者らは前記した微小クラックは、封孔の際に加圧水蒸気封孔処理の温度を低くすることにより、クラックの長さが短くなることを見出している。
加圧水蒸気封孔処理の条件は特に限定されないが、処理温度１０５～１２５℃、処理時間６０～１２０分であることが好ましく、特に処理温度１１５℃、処理時間７５分であることがより好ましい。装置内部の圧力は飽和水蒸気圧で決まるため、処理温度によりその圧力は異なる。
The aluminum alloy material is subjected to a sealing treatment after the anodizing treatment. As the sealing treatment, at least a pressurized steam sealing treatment method is performed. The present inventors have discovered that the length of the above-mentioned microcracks can be shortened by lowering the temperature of the pressurized steam sealing treatment during sealing.
The conditions for the pressurized steam sealing treatment are not particularly limited, but preferably the treatment temperature is 105 to 125°C and the treatment time is 60 to 120 minutes, and particularly preferably the treatment temperature is 115°C and the treatment time is 75 minutes. Since the pressure inside the device is determined by the saturated water vapor pressure, the pressure varies depending on the processing temperature.
また、封孔処理は多段階で行うことができ、前記加圧水蒸気封孔処理の前処理として、常温ニッケル封孔処理、高温ニッケル封孔処理等を適宜選択できる。
加圧水蒸気封孔処理以外に、他の封孔処理を行う場合は、既知の方法により行うことができる。封孔処理では、形成されるクラックは、概ね幅２０ｎｍ以下となる。したがって、クラックの分布観察では、幅が２０ｎｍ以下の微小クラックを対象にして行うものとしても問題はない。
Further, the sealing treatment can be performed in multiple stages, and as a pretreatment for the pressurized steam sealing treatment, room temperature nickel sealing treatment, high temperature nickel sealing treatment, etc. can be appropriately selected.
When performing other sealing treatments in addition to the pressurized steam sealing treatment, known methods can be used. In the sealing process, the cracks formed have a width of approximately 20 nm or less. Therefore, when observing the distribution of cracks, there is no problem even if the observation is performed targeting microcracks with a width of 20 nm or less.
本発明のアルミニウム合金材では、合金表面における幅が５ｎｍ以上の微小クラックの合計長さが、単位面積１平方マイクロメートル当たり０．６マイクロメートル以上３．３マイクロメ－トル以下に抑制されており、良好な耐食性を示す。 In the aluminum alloy material of the present invention, the total length of microcracks with a width of 5 nm or more on the alloy surface is suppressed to 0.6 micrometers or more and 3.3 micrometers or less per unit area of 1 square micrometer, Shows good corrosion resistance.
また、本発明のアルミニウム合金材は、耐食性試験で白化までの回数が１７０回以上を有しており、良好な耐食性を有しているといえる。その一方で、従来のアルミニウム合金製品は、耐食性試験で白化までの回数が７５回以下であり、耐食性が十分とはいえない。 In addition, the aluminum alloy material of the present invention can be said to have good corrosion resistance, as the number of times it turned white in the corrosion resistance test was 170 times or more. On the other hand, conventional aluminum alloy products can be tested for corrosion resistance only 75 times or less before turning white, and therefore cannot be said to have sufficient corrosion resistance.
以下に実施例及び比較例を示し、本発明をより具体的に説明する。ただし、本発明はこれらの記載により何ら限定されるものではない。 EXAMPLES The present invention will be explained in more detail by showing Examples and Comparative Examples below. However, the present invention is not limited in any way by these descriptions.
なお、各実施例及び比較例で得られたアルミニウム合金材表面の微小クラック長さの計測及び耐食性試験は、以下の方法により実施した。 Note that the measurement of the length of microcracks on the surface of the aluminum alloy material obtained in each Example and Comparative Example and the corrosion resistance test were carried out by the following method.
［表面の微小クラック長さの計測］
電界放出形走査電子顕微鏡（日立ハイテクノロジーズ(株)製、Ｓ－４８００）を用いて材料表面の１００，０００倍の画像を取得した後、当該視野内において観察される幅５ｎｍ以上の各微小クラックの長さを２点間距離計測により求め、さらにそれらを合計した『単位面積当たりの微小クラックの合計長さ』を微小クラック長さとした（図４）。
[Measurement of surface microcrack length]
After acquiring a 100,000x image of the material surface using a field emission scanning electron microscope (manufactured by Hitachi High-Technologies, Ltd., S-4800), each microcracks with a width of 5 nm or more observed within the field of view. The length was determined by measuring the distance between two points, and the total length of the microcracks per unit area was determined as the microcrack length (Figure 4).
［耐食性試験］
屋外を想定した耐食性試験として、図１で示した簡易的な耐酸性試験を参考に鋭意検討を重ね、独自の試験方法を開発した。具体的にはサンプル表面を６５℃に温め、その表面にスポイト（径２ｍｍ）で１０規定塩酸１滴を滴下し、自然乾燥（例えば５分～１０分）と、乾燥後直ちに滴下を行うことを繰り返し、目視で表面が白化するまでの滴下回数から耐食性を評価した。
この耐食性試験で実際に自動車に搭載されている製品を評価したところ、４０回で表面が白くなった。次に、本発明のサンプルを複数評価したところ、いずれも１７０回以上であった。従来品の４倍以上「白化していない（耐食性あり）」として評価できる。
[Corrosion resistance test]
As a corrosion resistance test assuming outdoor use, we have developed a unique test method based on extensive research using the simple acid resistance test shown in Figure 1 as a reference. Specifically, warm the sample surface to 65°C, drop one drop of 10 N hydrochloric acid onto the surface with a dropper (diameter 2 mm), let it air dry (for example, 5 to 10 minutes), and then immediately add the drop after drying. Corrosion resistance was evaluated repeatedly based on the number of drops until the surface became white by visual observation.
When a product actually installed in a car was evaluated using this corrosion resistance test, the surface became white after 40 tests. Next, when multiple samples of the present invention were evaluated, all of them were evaluated 170 times or more. It can be evaluated as "no whitening (corrosion resistance)" more than four times that of conventional products.
[実施例１]
アルミニウム－マグネシウム－シリコン系合金のＪＩＳ Ａ６０６３板について、以下の条件で硫酸浴（硫酸水溶液）を用いて陽極酸化処理を行った後、常温ニッケル封孔処理を経て加圧水蒸気封孔を行い、表面の微小クラック長さの計測及び耐食性試験を実施した。
＜硫酸浴での陽極酸化処理＞
・処理槽の容積：３，３００Ｌ
・ＪＩＳ Ａ６０６３板の寸法：２，０００ｍｍ×５０ｍｍ×厚さ２０ｍｍ
・陰極の材質：ＪＩＳ Ａ１０５０（工業用純アルミニウム）
・ＪＩＳ Ａ６０６３板と陰極との距離：２０ｍｍ
・電流密度：１．５Ａ／ｄｍ２
・硫酸濃度：１８質量％
・浴温度：２０℃
・処理時間：２５分
＜常温ニッケル封孔条件＞
・封孔液中ニッケル濃度：５ｇ／L
・処理温度：２０℃
・処理時間：２０分
・ｐＨ：５．７
＜加圧水蒸気封孔条件＞
・圧力：０．１８ＭＰａ
・処理温度：１１５℃
・処理時間：７５分
＜評価試験結果＞
微小クラックの合計長さ及び耐食性試験結果を表１に示す。
[Example 1]
A JIS A6063 plate made of aluminum-magnesium-silicon alloy was anodized using a sulfuric acid bath (sulfuric acid aqueous solution) under the following conditions, followed by room temperature nickel sealing and pressurized steam sealing. Micro crack length measurements and corrosion resistance tests were conducted.
<Anodizing treatment in sulfuric acid bath>
・Capacity of treatment tank: 3,300L
・JIS A6063 board dimensions: 2,000mm x 50mm x thickness 20mm
・Cathode material: JIS A1050 (industrial pure aluminum)
・Distance between JIS A6063 plate and cathode: 20mm
・Current density: 1.5A/dm 2
・Sulfuric acid concentration: 18% by mass
・Bath temperature: 20℃
・Processing time: 25 minutes <room temperature nickel sealing conditions>
・Nickel concentration in sealing liquid: 5g/L
・Processing temperature: 20℃
・Processing time: 20 minutes ・pH: 5.7
<Pressure steam sealing conditions>
・Pressure: 0.18MPa
・Processing temperature: 115℃
・Processing time: 75 minutes <Evaluation test results>
Table 1 shows the total length of microcracks and the corrosion resistance test results.
[実施例２]
アルミニウム－マグネシウム－シリコン系合金のＪＩＳ Ａ６０６３板について、以下の条件で硫酸浴（硫酸水溶液）を用いて陽極酸化処理を行った後、常温ニッケル封孔処理を経て加圧水蒸気封孔を行い、表面の微小クラック長さの計測及び耐食性試験を実施した。
＜硫酸浴での陽極酸化処理＞
処理条件は以下の通りである。
・処理槽の容積：２５Ｌ
・ＪＩＳ Ａ６０６３板の寸法：１５０ｍｍ×５０ｍｍ×厚さ２０ｍｍ
・陰極の材質：ＪＩＳ Ａ１０５０（工業用純アルミニウム）
・ＪＩＳ Ａ６０６３板と陰極との距離：２０ｍｍ
・電流密度：０．８Ａ／ｄｍ２
・硫酸濃度：１８質量％
・浴温度：２０℃
・処理時間：３０分
＜常温ニッケル封孔条件＞
・封孔液中ニッケル濃度：５ｇ／L
・処理温度：２０℃
・処理時間：２０分
・ｐＨ：５．７
＜加圧水蒸気封孔条件＞
・圧力：０．１８ＭＰａ
・処理温度：１１５℃
・処理時間：７５分
＜評価試験結果＞
微小クラックの合計長さ及び耐食性試験結果を表１に示す。
[Example 2]
A JIS A6063 plate made of aluminum-magnesium-silicon alloy was anodized using a sulfuric acid bath (sulfuric acid aqueous solution) under the following conditions, followed by room temperature nickel sealing and pressurized steam sealing. Micro crack length measurements and corrosion resistance tests were conducted.
<Anodizing treatment in sulfuric acid bath>
The processing conditions are as follows.
・Capacity of processing tank: 25L
・JIS A6063 board dimensions: 150mm x 50mm x thickness 20mm
・Cathode material: JIS A1050 (industrial pure aluminum)
・Distance between JIS A6063 plate and cathode: 20mm
・Current density: 0.8A/ dm2
・Sulfuric acid concentration: 18% by mass
・Bath temperature: 20℃
・Processing time: 30 minutes <room temperature nickel sealing conditions>
・Nickel concentration in sealing liquid: 5g/L
・Processing temperature: 20℃
・Processing time: 20 minutes ・pH: 5.7
<Pressure steam sealing conditions>
・Pressure: 0.18MPa
・Processing temperature: 115℃
・Processing time: 75 minutes <Evaluation test results>
Table 1 shows the total length of microcracks and the corrosion resistance test results.
[実施例３]から[実施例７]については、[実施例２]と同じ処理槽等を用いて、表１に示すように、合金の種類、陽極酸化処理の電流密度、加圧水蒸気封孔条件を変更したサンプルを作製し、表面の微小クラック長さの計測及び耐食性試験を実施した。 For [Example 3] to [Example 7], the same treatment tank as [Example 2] was used, and as shown in Table 1, the type of alloy, the current density of anodizing treatment, the pressurized steam sealing, etc. Samples were prepared under different conditions, and the length of microcracks on the surface was measured and a corrosion resistance test was conducted.
[比較例１]
比較のために、アルミニウム－マグネシウム－シリコン系合金のＪＩＳ Ａ６０６３板について、以下の条件で硫酸浴（硫酸水溶液）を用いて陽極酸化処理を行った後、常温ニッケル封孔処理を経て加圧水蒸気封孔を行い、表面の微小クラック長さの計測及び耐食性試験を実施した。
＜硫酸浴での陽極酸化処理＞
・処理槽の容積：３，３００Ｌ
・ＪＩＳ Ａ６０６３板の寸法：２，０００ｍｍ×５０ｍｍ×厚さ２０ｍｍ
・陰極の材質：ＪＩＳ Ａ１０５０（工業用純アルミニウム）
・ＪＩＳ Ａ６０６３板と陰極との距離：２０ｍｍ
・電流密度：１．５Ａ／ｄｍ２
・硫酸濃度：１８質量％
・浴温度：２０℃
・処理時間：２５分
＜常温ニッケル封孔条件＞
・封孔液中ニッケル濃度：５ｇ／L
・処理温度：２０℃
・処理時間：２０分
・ｐＨ：５．７
＜加圧水蒸気封孔条件＞
・圧力：０．４５ＭＰａ
・処理温度：１４５℃
・処理時間：２０分
＜評価試験結果＞
微小クラックの合計長さ及び耐食性試験結果を表１に示す。
[Comparative example 1]
For comparison, a JIS A6063 plate made of aluminum-magnesium-silicon alloy was anodized using a sulfuric acid bath (aqueous sulfuric acid solution) under the following conditions, followed by room-temperature nickel sealing and pressurized steam sealing. The length of micro cracks on the surface was measured and a corrosion resistance test was carried out.
<Anodizing treatment in sulfuric acid bath>
・Capacity of treatment tank: 3,300L
・JIS A6063 board dimensions: 2,000mm x 50mm x thickness 20mm
・Cathode material: JIS A1050 (industrial pure aluminum)
・Distance between JIS A6063 plate and cathode: 20mm
・Current density: 1.5A/dm 2
・Sulfuric acid concentration: 18% by mass
・Bath temperature: 20℃
・Processing time: 25 minutes <room temperature nickel sealing conditions>
・Nickel concentration in sealing liquid: 5g/L
・Processing temperature: 20℃
・Processing time: 20 minutes ・pH: 5.7
<Pressure steam sealing conditions>
・Pressure: 0.45MPa
・Processing temperature: 145℃
・Processing time: 20 minutes <Evaluation test results>
Table 1 shows the total length of microcracks and the corrosion resistance test results.
[比較例２]については、[比較例１]と同じ処理槽等を用いて、加圧水蒸気封孔条件を変更したサンプルを作製し、表面の微小クラック長さの計測及び耐食性試験を実施した。 For [Comparative Example 2], a sample was prepared using the same treatment tank as in [Comparative Example 1] with different pressurized steam sealing conditions, and the length of micro cracks on the surface was measured and a corrosion resistance test was conducted.
表１から明らかな通り、実施例１～７で作製した陽極酸化皮膜を有するアルミニウム合金材は、従来製品である比較例１よりもクラックが抑制され、高い耐食性を有することがわかった。 As is clear from Table 1, the aluminum alloy materials having anodized films produced in Examples 1 to 7 had more suppressed cracking than Comparative Example 1, which is a conventional product, and had high corrosion resistance.
本発明のアルミニウム合金材は、屋外の露天状態においても良好な耐食性を発揮するため、種々の用途に利用できる。例えば、自動車用のキャリーレールやモールの材料として好適に利用することができる。 The aluminum alloy material of the present invention exhibits good corrosion resistance even in outdoor outdoor conditions, so it can be used for various purposes. For example, it can be suitably used as a material for carrying rails and moldings for automobiles.
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