200914627 九、發明說明 【發明所屬之技術領域】 本發明涉及鋁合金材料’特別是欲使用於形成製造， 如CVD系統、PVD系統、離子植入系統、濺射系統、乾 式鈾刻系統等的半導體和液晶裝置用之真空腔或設備的構 件和設於其真空腔內部的構件的陽極化鋁合金材料。 【先前技術】 反應氣體、蝕刻氣體、含有鹵素做爲清潔氣體的腐飩 性氣體被導入用於製造如CVD系統、PVD系統、離子植 入系統、濺射系統、乾式蝕刻系統等的半導體裝置和液晶 裝置的設備之真空腔內部。因此要求真空腔對於腐蝕性氣 體有耐腐蝕性（以下稱爲「耐氣體腐蝕性」）。因爲於真 空腔中總是生成鹵系電漿’所以也重視對於電漿的耐性（ 以下稱爲「耐電漿性」）（參照JP-A-2003-34894號與 2004-225113號）。近年來，因爲鋁和鋁合金材料輕量而 且熱傳導性優異，已採用鋁和鋁合金材料來形成真空腔的 構件。 然而，鋁和鋁合金不具有充分的耐氣體腐蝕性及耐電 漿性，因此紛紛提出有用於使這些特性提高的表面改質技 術。可是，對於這些特性來說仍不充分，因此期望進一步 提高這些特性。 使鋁和鋁合金材料的表面覆有高硬度的硬陽極氧化皮 膜有效提高耐電槳性。該硬陽極氧化皮膜對於電漿的高物 -4- 200914627 理能量帶來的構件磨耗具有耐性，因此能夠提 (參照 JP-A-2004-225113 號）。 雖然僅僅在鋁和鋁合金材料上覆以硬陽極 可使耐電漿性提高，但是硬陽極氧化皮膜容易 一旦裂紋貫通陽極氧化皮膜時，腐蝕性氣體便 通的裂紋（以下稱爲「貫通裂紋」）侵入陽極 到達陽極化鋁和鋁合金構件的鋁和鋁合金本體 銘和銘合金材料_。 因此，期望不僅要具有高硬度且也具有耐 紋性和耐氣體腐蝕性）的陽極氧化皮膜。 另外，從抑制半導體晶圓或液晶顯示器基 染的觀點出發，若減少鋁合金中的Fe含量， F e含量低的陽極氧化皮膜。但是，這樣的陽 較硬，所以耐裂紋性和耐久性較差。因此，此 不提高污染性下期望能提高耐久性（耐裂紋性 蝕性）。 【發明內容】 本發明鑒於前述問題而做，其目的在於， 有高硬度、耐久性和低污染性的陽極化鋁合金 本發明第一方面爲一種陽極化鋁合金材料 有Mg含量爲〇.1至2.0% (文中除非另有說 表示「質量％」）、Si含量爲0.1至2.0%、 0.1至2.0%與Fe、Cr和Cu的含量爲0.03% 高耐電漿性 氧化皮膜即 發生裂紋。 會通過該貫 氧化皮膜而 ，因而腐蝕 久性（耐裂 板被Fe污 則能夠形成 極氧化皮膜 領域中，在 和耐氣體腐 提供一種具 〇 ，係由一具 明，「％」 Μη含量爲 或以下，以 200914627 及含AI和不可避免的雜質做爲其他成份的錯合金所成 且覆有陽極氧化皮膜；其中該陽極氧化皮膜在其厚度方 上的不同部位之部分各具有不同硬度，且硬度最大的部 和硬度最小的部分的維氏硬度差値爲Hv 5或以上。 該陽極化鋁合金材料具有高硬度、耐久性和低污染 〇 本發明第一方面的陽極化鋁合金材料中，該陽極氧 皮膜之硬度最小部位的硬度爲Η ν 3 6 5或以上，據此導 耐電漿性提高。 形成陽極化鋁合金材料的鋁合金具有的Mg含量 0.1至2_0%、Si含量爲0.1至2.0% ' Μη含量爲0.1 2.0%與Fe、Cr和Cu的含量爲0.03%或以下，以及含 和不可避免的雜質做爲其他成份，該陽極化鋁合金材料 有陽極氧化皮膜，該陽極氧化皮膜在其厚度方向上的不 部位之部分各具有不同硬度，且硬度最大的部分和硬度 小的部分的維氏硬度差値爲Hv 5或以上。所以該陽極 銘合金材料具有高硬度、耐久性和低污染性。 【實施方式】 以較佳實施方式詳細地說明本發明。 形成陽極化鋁合金材料的鋁合金之構成 本發明的陽極化鋁合金材料係由一具有Mg含量 0·1至2.0%、Si含量爲0.1至2.0%、Μη含量爲0.1 向 分 性 化 致 爲 至 Α1 覆 同 最 化 爲 至 200914627 2.0%與Fe、Cr和Cu的含量爲0.03%或以下，以及含A1 和不可避免的雜質做爲其他成份的鋁合金所成，且覆有陽 極氧化皮膜。該陽極氧化皮膜在其厚度方向上的不同部位 之部分各具有不同硬度，且硬度最大的部分和硬度最小的 部分的維氏硬度差値爲Hv 5或以上。所以此陽極化鋁合 金材料具有高硬度、耐久性和低污染性。 以下’對於達到上述構成的理由進行詳述。 本發明的發明者們首先限制鋁合金中的Fe、Cr、Cu 的含量，使之不會污染半導體等的工件。限制Fe含量於 低水準使陽極氧化皮膜硬度提高，從而能夠確保耐電漿性 這一特性’另外硏究找出避免陽極氧化皮膜上形成的裂紋 生長進展到陽極化鋁合金材料本體。硏究結果發現，通過 控制陽極氧化皮膜的形成條件，使該陽極氧化皮膜在其厚 度方向上的不同部位之部分各具有不同硬度，且硬度最大 的部分和硬度最小的部分的維氏硬度差値爲Hv 5或以上 ’能夠避免使陽極氧化皮膜上形成的裂紋生長進展到陽極 化鋁合金材料本體。據此，氣體透過陽極氧化皮膜向鋁合 金材料的侵入也得到抑制，使整體耐久性得以確保。說到 原因’成爲這樣的結構而能夠解決上述課題的詳細機制尙 不明確。但是，認爲是引起裂紋生長的應力被陽極氧化皮 膜硬度小的部分吸收，結果是裂紋不會生長進展至陽極化 鋁合金材料的鋁合金本體。 以下詳述本發明。 200914627 鋁合金中的成分 雖然機制詳情不明，但是認爲存在於鋁合金中的Mg 、Si和Μη組合成Mg2Si化合物、與Al-Mn-Si化合物或 者Α1-Μη化合物，強化陽極氧化皮膜。200914627 IX. INSTRUCTIONS OF THE INVENTION [Technical Field] The present invention relates to an aluminum alloy material 'especially for use in forming a semiconductor such as a CVD system, a PVD system, an ion implantation system, a sputtering system, a dry uranium engraving system, and the like. And an anodized aluminum alloy material for a vacuum chamber or device for a liquid crystal device and a member provided inside the vacuum chamber. [Prior Art] A reactive gas, an etching gas, and a corrosive gas containing a halogen as a cleaning gas are introduced into a semiconductor device for manufacturing a CVD system, a PVD system, an ion implantation system, a sputtering system, a dry etching system, and the like. The inside of the vacuum chamber of the device of the liquid crystal device. Therefore, the vacuum chamber is required to have corrosion resistance to corrosive gases (hereinafter referred to as "gas corrosion resistance"). Since the halogen-based plasma is always formed in the true cavity, resistance to plasma is also emphasized (hereinafter referred to as "plasma resistance") (refer to JP-A-2003-34894 and 2004-225113). In recent years, aluminum and aluminum alloy materials have been used to form members of a vacuum chamber because aluminum and aluminum alloy materials are lightweight and excellent in thermal conductivity. However, aluminum and aluminum alloys do not have sufficient gas corrosion resistance and plasma resistance, and thus surface modification techniques for improving these characteristics have been proposed. However, these characteristics are still insufficient, and it is therefore desired to further improve these characteristics. The surface of the aluminum and aluminum alloy material is coated with a hard anodized film of high hardness to effectively improve the electric pad resistance. The hard anodized film is resistant to the wear of the member due to the high energy of the plasma -4-200914627, and therefore can be referred to (refer to JP-A-2004-225113). Although the hard anodic coating is applied to the aluminum and aluminum alloy materials only to improve the plasma resistance, the hard anodic oxide film is likely to infiltrate cracks (hereinafter referred to as "through cracks") when the crack penetrates the anodic oxide film. The anode reaches the anodized aluminum and aluminum alloy components of the aluminum and aluminum alloy body Ming and Ming alloy materials _. Therefore, an anodic oxide film which not only has high hardness but also has striated property and gas corrosion resistance is desired. Further, from the viewpoint of suppressing the dyeing of the semiconductor wafer or the liquid crystal display, the anodic oxide film having a low Fe content and a low Fe content is reduced. However, such a yang is hard, so crack resistance and durability are inferior. Therefore, it is desirable to improve durability (crack resistance) without increasing the degree of contamination. SUMMARY OF THE INVENTION The present invention has been made in view of the foregoing problems, and an object thereof is to provide an anodized aluminum alloy having high hardness, durability, and low pollution. The first aspect of the present invention is an anodized aluminum alloy material having a Mg content of 〇.1. To 2.0% (unless otherwise stated "% by mass"), the Si content is 0.1 to 2.0%, 0.1 to 2.0%, and the content of Fe, Cr, and Cu is 0.03%. The high plasma-resistant oxide film is cracked. Will pass through the oxide film, and thus the corrosion resistance (the crack-resistant plate is contaminated by Fe, which can form a polar oxide film, and provides a kind of flaw in the gas corrosion resistance, which is determined by a certain, "%" Μη content or Hereinafter, it is made of 200914627 and a wrong alloy containing AI and unavoidable impurities as other components and coated with an anodized film; wherein the anodized film has different hardnesses in different portions of the thickness portion thereof, and hardness The maximum portion and the portion having the smallest hardness have a Vickers hardness difference H of Hv 5 or more. The anodized aluminum alloy material has high hardness, durability, and low pollution. In the anodized aluminum alloy material of the first aspect of the invention, The hardness of the anodic oxygen film at the minimum hardness is Η ν 3 6 5 or more, thereby improving the plasma resistance. The aluminum alloy forming the anodized aluminum alloy material has a Mg content of 0.1 to 2_0% and a Si content of 0.1 to 2.0. The % ' Μη content is 0.1 2.0% and the content of Fe, Cr and Cu is 0.03% or less, and the unavoidable impurities are used as other components. The anodized aluminum alloy material has an anode. The anodic oxide film has different hardnesses in portions of the anodic oxide film in the thickness direction thereof, and the Vickers hardness difference 値 of the portion having the highest hardness and the portion having a small hardness is Hv 5 or more. The present invention is described in detail with reference to preferred embodiments. The composition of the aluminum alloy forming the anodized aluminum alloy material is an anodized aluminum alloy material of the present invention having a Mg The content is from 0.1 to 2.0%, the Si content is from 0.1 to 2.0%, and the Μη content is from 0.1 to the Α1, and the maximum is to 200914627 2.0% and the content of Fe, Cr and Cu is 0.03% or less. And an aluminum alloy containing A1 and unavoidable impurities as other components, and covered with an anodized film. The portion of the anodic oxide film having different hardnesses at the different portions in the thickness direction thereof and having the highest hardness The difference in Vickers hardness of the portion having the smallest hardness is Hv 5 or more. Therefore, the anodized aluminum alloy material has high hardness, durability, and low pollution. The reason for the above-described configuration will be described in detail. The inventors of the present invention firstly limit the content of Fe, Cr, and Cu in an aluminum alloy so as not to contaminate a workpiece such as a semiconductor, and limit the Fe content to a low level to increase the hardness of the anodic oxide film. Therefore, it is possible to ensure the property of resisting plasma resistance. In addition, it is found that the growth of cracks formed on the anodized film is prevented from progressing to the body of the anodized aluminum alloy material. As a result, it was found that by controlling the formation conditions of the anodized film, The anodic oxide film has different hardnesses in portions of different portions in the thickness direction thereof, and the Vickers hardness difference 値Hv 5 or more in the portion having the largest hardness and the portion having the smallest hardness can avoid the crack formed on the anodic oxide film. The growth progresses to the anodized aluminum alloy body. As a result, the intrusion of the gas through the anodized film to the aluminum alloy material is also suppressed, and the overall durability is ensured. When it comes to the reason, the detailed mechanism that can solve the above problems is such a structure. However, it is considered that the stress causing the crack growth is absorbed by the portion where the hardness of the anodized film is small, and as a result, the crack does not grow and progresses to the aluminum alloy body of the anodized aluminum alloy material. The invention is described in detail below. 200914627 Composition in Aluminum Alloy Although the mechanism details are unknown, it is considered that Mg, Si and Μη present in the aluminum alloy are combined into a Mg2Si compound, an Al-Mn-Si compound or a Α1-Μη compound to strengthen the anodic oxide film.
Mg 含量：0.1 〜2.0% 鎂（Mg)是形成Mg2Si化合物所需要的元素。當Mg 含量低於〇 1 %時，幾乎不會形成M g2 S i化合物，因此得 不到陽極氧化皮膜期望的耐久性提高效果。當Mg含量超 過2.0%時’ MgiSi化合物形成粗粒，反而阻礙正常的陽 極氧化皮膜的形成。因此’適宜的Mg含量爲0.1%至2.0 %，較佳爲〇 · 8 %。Mg content: 0.1 to 2.0% Magnesium (Mg) is an element required for forming a Mg2Si compound. When the Mg content is less than 〇 1%, the Mg 2 S i compound is hardly formed, so that the desired durability improvement effect of the anodized film is not obtained. When the Mg content exceeds 2.0%, the 'MgiSi compound forms coarse particles, which in turn hinders the formation of a normal anode oxide film. Therefore, a suitable Mg content is from 0.1% to 2.0%, preferably 〇·8%.
Si 含量：0.1 〜2.0% 矽（Si)與Mg都是形成MgzSi化合物所需要的元素 。當Si含量低於0.1%時，幾乎不會形成Mg2Si化合物， 因此得不到陽極氧化皮膜期望的耐久性提高效果。當W 含量超過2.0%時，Mg2 Si化合物形成粗粒，反而阻礙正 常的陽極氧化皮膜的形成。因此，適宜的Si含量爲〇 至2.0%，較佳爲1.2%。 Μη 含量：〇· 1 〜2.0% 錳（Μη)是形成Al-Mn-Si化合物或者Al_Mn化合物 所w要的兀素。g Mn曰重:低於o.i%時，幾乎不會形成 200914627Si content: 0.1 to 2.0% Both bismuth (Si) and Mg are elements required for forming a MgzSi compound. When the Si content is less than 0.1%, the Mg2Si compound is hardly formed, and thus the desired durability improvement effect of the anodized film is not obtained. When the W content exceeds 2.0%, the Mg2Si compound forms coarse particles, which in turn hinders the formation of a normal anodized film. Therefore, a suitable Si content is 〇 to 2.0%, preferably 1.2%. Μη Content: 〇·1 to 2.0% Manganese (Μη) is a halogen which is formed by forming an Al-Mn-Si compound or an Al_Mn compound. g Mn 曰 weight: when it is lower than o.i%, it will hardly form 200914627
Al-Mn-Si化合物或Al-Mn化合物，因此得不到陽極氧化 皮膜期望的耐久性提高效果。當Μη含量超過2.0%時， 上述化合物形成粗粒，反而阻礙正常的陽極氧化皮膜的形 成。因此，適宜的Μη含量爲0.1%至2_〇%，較佳爲1.6 % 。Since the Al-Mn-Si compound or the Al-Mn compound does not have the desired durability improvement effect of the anodized film. When the Μη content exceeds 2.0%, the above compound forms coarse particles, which in turn hinders the formation of a normal anodic oxide film. Therefore, a suitable content of Μη is from 0.1% to 2%, preferably 1.6%.
Fe、Cr和Cu含量：分別在〇.〇3 %或以下 陽極化中所使用的電力係用於鋁的離子化和經由水電 解的氧發生。因此，若用於氧發生的電量的比例變大，則 用於鋁離子化的電量的比例變小，使氧化鋁無法有效製造 而減緩成膜速率。若Fe、Cr、Cu存在於銘合金中，則這 些元素成爲氧發生的起點，導致用於氧發生的電量比例變 大，成膜速率變慢。若Fe、Cr、Cu的含量分別超過0.03 % ’則Fe、Cr、Cu從鋁合金本體和陽極氧化皮膜排出進 入氣體，從而污染半導體等工件。因此，Fe、Cr和Cu的 各含量分別在0.03%或以下，較佳分別在0.01%或以下 做爲其他成份之A1和不可避免的雜質 實質上，A1爲僅有的其他成份。但是，鋁合金除了 含Fe、Cr、Cu以外，也含不可避免地少量之Ni、Zn、B 、Ca、Na、K不可避免雜質元素。較佳，Fe、Cr、Cu以 外的不可避免的雜質含量的總和在〇· 1 %或以下。 在陽極氧化皮膜中形成結晶狀圖案，若錯合金的晶粒 -9- 200914627 粗則陽極氧化皮膜具有不均一的色調。因此爲了防止鋁合 金的粗晶粒生長’也可以將鈦（Ti)加入鋁合金中。若Ti 的含量過少’則得不到晶粒的控制效果，若含量過多，則 反而造成污染。當鋁合金中加有Ti時，Ti含量下限爲 0.01% ’較佳爲0.015% ’ Ti含量上限爲0.03%，較佳爲 0.02 5 %。 鋁合金材料的製造方法 接下來’說明鋁合金材料的製造方法。 首先，適宜選擇例如連續鑄造法、半連續鑄造法（ DC鑄造法）等一般鑄造法，製造具有上述組成的鋁合金 鑄錠。其次’對該鋁合金鑄錠實施均質化熱處理（即，「 均熱法」（soaking process ))。耐久性優異的陽極氧化 皮膜係如下形成：以均熱法處理該鋁合金鑄錠，溫度（即 ’ 「均質化溫度」或「均熱溫度」）爲50(TC或以上。耐 I 久性更優異的陽極氧化皮膜可由550°C以上的均質化溫度 以均質化處理加工該鋁合金鑄錠而形成。若均質化溫度超 過60(TC，則燒損（burning)發生而破壞鋁合金鑄錠的表 面性狀。因此，均質化溫度推薦爲5 00。(：（較佳不低於 55〇°C )至6 00 °C的範圍。關於均質化溫度對陽極氧化皮 膜形成的效應雖然尙未判明，但如上述，認爲是均質化溫 度與Al-Mn-Si化合物或者Al-Mn化合物的形成有關。 然後’將實施了均質化處理的鋁合金鑄錠進行如軋製 、鍛造、擠出等適宜的塑性加工，得到鋁合金材料。然後 -10- 200914627 ，對該鋁合金材料進行固溶處理、淬火處理、人工時效處 理（以下僅稱爲「時效處理」）。然後，該鋁合金材料以 機械加工成適宜的形狀。由鋁合金鑄錠加工得到的鋁合金 扁胚也可以接受固溶處理、淬火處理、人工時效處理製作 成銘合金材料。固溶處理、淬火處理與時效處理可以作爲 通常的T6處理’例如於515〜550°c的固溶處理、水淬火 處理與1 7 0 °C X 8小時或1 5 5〜1 6 5它X丨8小時的時效處理。 陽極氧化皮膜 其次’說明錦合金材料的陽極氧化皮膜。作爲陽極氧 化皮膜形成方法’其進行只要適宜選擇進行電解的條件， 即包括電解質的組成與濃度、電壓、電流密度、電流-電 壓波形、與電解的溫度即可。陽極電解需要用到含有C、 s、N、P、B之中至少一種元素的陽極化溶液。例如’使 用含有草酸、甲酸、胺基磺酸、磷酸、亞磷酸、硼酸、硝 酸或其複合物、酞酸或其複合物中至少之一的水溶液是有 效的。陽極氧化皮膜的厚度沒有特別限制。陽極氧化皮膜 的厚度爲約0.1至約200/zm，較佳爲0.5至7〇Am ’更佳 爲約1至約5 0 // m。 如前述，因爲陽極氧化皮膜在其厚度方向上具有硬度 不同的部分，該硬度最大的部分和硬度最小的部分 維氏硬度計爲Hv 5或以上。所以該陽極氧化皮膜具有高 硬度，可抑制裂紋的生長，故耐裂紋性優異。如此’因爲 該陽極氧化皮膜的耐裂紋性優異’所以氣體經由該陽極氧 -11 - 200914627 化皮膜向鋁合金本體的侵入也被抑制’確保了整體耐久性 。若硬度最大的部分和硬度最小的部分的差以維氏硬度計 低於Hv 5時，此陽極氧化皮膜的行爲等同於在厚度方向 上硬度實質上均一的陽極氧化皮膜’所以難以抑制裂紋的 生長。結果，該陽極氧化皮膜的耐裂紋性低，且耐氣體腐 鈾性也差。 本發明中，在陽極氧化皮膜的厚度方向上硬度不同的 部分應至少有2個。該部分的數量沒有特別限定，但數量 是2個或以上。陽極氧化皮膜的硬度可以斷續地變化，或 者也可以連續地（傾斜地）變化。 另外，從抑制陽極氧化皮膜產生的裂紋之生長這一觀 點出發，考慮硬度最小的部分的維氏硬度以盡可能小的方 面爲宜。但是，若把對於電漿的物理能量造成的磨耗的耐 性也考慮在內，則較佳以維氏硬度計爲Η ν 3 6 5或以上。 覆有這種陽極氧化皮膜的鋁合金材料（以下稱爲「陽 極化鋁合金」）適合形成在高溫的腐鈾氣氛下使用的構件 。此陽極化鋁合金特別適合形成半導體裝置製造設備等之 中電漿處理設備用的真空腔和設於真空腔內部的構件（例 如’電極）’該真空腔和內部的構件曝露於高溫環境下之 腐餓氣體中’且必須具有不污染工件的低污染性。 爲了在陽極氧化皮膜的厚度方向上使陽極氧化皮膜的 硬度變化’可採用在陽極化的途中斷續或連續地使陽極化 溶液的溫度變化的方法’或是中斷使用陽極化溶液之陽極 化而從陽極化溶液中取出鋁合金材料，然後在不同組成和 -12- 200914627 /或不同溫度的陽極化溶液中恢復陽極化的方法 些方法，能夠使陽極氧化皮膜的厚度方向的硬度 外，溫度低的陽極化溶液有效抑制陽極化時與形 氧化皮膜時之陽極氧化皮膜的化學溶解。 如前述，考慮到對工件，例如’半導體晶圓 ，當鋁合金中的Fe的含量降低至0.03%或以下 氧化皮膜中的Fe的含量可降低至500ppm或以 鋁合金中的Fe的含量降低至0.01%或以下，則 氧化皮膜中的Fe的含量降低至150ppm或以下。 如以上說明，上述陽極化鋁合金材料具有高 能夠滿足耐久性（耐裂紋性和耐氣體腐蝕性）和 實施例 以下，闡述本發明實施例。但是，下述實施 制本發明，在不背離前述與後述宗旨的改變均包 明的技術範圍內。 首先，鑄造具有下述表1所示成分組成（本 之試料編號1、2、4、5，比較例之試料編號3、 經冷卻（冷卻速度：1 0〜1 5 t /秒）形成的鋁合 尺寸：寬220mmx長250mmx厚100mm)。切割 銘並硏磨得銘合金扁胚（尺寸：寬220mmx長1 6 0 m m )。銘合金扁胚於5 4 0 °C均熱4小時處理 且厚60mm的鋁合金扁胚通過熱軋製成6mm厚 。根據這 變化。另 成硬陽極 ，的污染 ，則陽極 下。若將 能將陽極 硬度，也 低污染性 例並不限 含在本發 案實施例 6 〜1 4 ) 金鑄錠（ 錫合金鑄 5 Ommx厚 。均熱後 的鋁合金 -13- 200914627 板。此 鐘）後 8小時 3 5mm 而具有 鋁合金板進行固溶處理（溫度510°C〜520 °C X30分 進行水淬火，然後時效處理（溫度1 6 (TC〜1 8 0°C X )，得到合金板試樣。從該合金板上切割25mmx (軋製方向）厚x3 mm的試料片，對其表面進行硏磨 Ra 1 .6的表面糙度。 -14- 200914627 靶9 哿E g c〇 g (Ο g CO m CO ΙΟ fe g CO § c〇 § CO g CO § CO ο σ> ΓΟ ο CO g CO g CO A3 厚度 (pm) ΙΟ tf) to in ΙΟ VO lO IT) in in ΙΛ ΙΟ in l〇 電壓 (V) § s s § s g g s S § § s § § i溫度 ：(°〇 ιη m lO ΙΟ lO 1Λ to in 40 ΙΟ in to l〇 Ί 陽極化溶液 ^ οι 效Κ ^ 〇) 姨K 效K 炒K 炒氏 ^ i 轶氏 起CT 效氏 ^ B) 钱S t身 g AM ^ s 糾 g * 1 z ^ ^ g s « ώ *| sf ^ ^ 1 ««< · · -s η § 硬度 1 _ ο οο C0 S CO s to m 男 s CO g CO g c〇 § CO o oo to S c〇 g CO O 男 s CO § CO 厚度 ! (pm) ιη lO lO lO tf> ΙΟ m m in ΙΟ »〇 ΙΟ ΙΛ ΙΟ 電壓 (V) ί 埤 1 城 S § § S s s S § s § s § S g 溫度 (°〇 ο CO 卜 o o o o o o ο o o o ο 陽極化溶液 ^ ΐ ^ i 效K 炒s « i 效K ^ t 姨s 疼CT 效闵 ^ t 效K ιΐ 疼§> 妫s 趣ra ^ I ξ ^ g ««< . · g ^ Aj # 1 ««< · · $ ^ I 补g 2够 料g «»< ;昼 «tl Ϊ爸 ξ ^ g 判定 ◎ ◎ ◎ 〇 〇 ◎ ◎ ◎ ◎ ◎ ◎ X X X 污染性 Cu好 (叩m) ? g s s 490 i 〇 § 1 § ο i g ο 〇含量 (PPm) g g g § o m o s s 另 S s O o CO m s Fe含量 (ppm) g s i § o § g o i S g 另 m o o 判定 ◎ 〇 X 0 〇 X X X X X X ◎ ◎ ◎ k 窄a η ο CM o c〇 CO 二 CO 〇} ο σ> o o o 制地1 ο lf> o o o o o ο ο ο o o o δ 0.007 0.007 0.007 0.027 0.028 0.009 0.008 0.008 0.009 oooa 0.007 0.008 0.009 1_ 0.03, Ο σ> ο 0.009 g 0.028 CD S g φ g m CM CO g ®W ο d o' d o d ο Ο ο o d o Φ g ο » o g q a> CM o c\i o g q δ q o o CO ο φ ο σ> ο s φ o r- o ο ο d d o <Γ〇 C CO CO (O d 00 o 卜 o GO Ο ο.〇9 O) d σ> o Oi o £Λ Oi OJ CS| τ- Ο o csi CO d CO o 0.08 csi τ— Ο) ο 〇 q O) 6 σι CO d GO o oo d d σ» 0.09 csi q ο σ> ο 二 OJ d q q 苳 苳 馨 V aJ -Ο jj jj 紱t漣餒 - CNi CO ΙΟ (O 卜 CO σ> ο 二 CM CO 寸 -15- 200914627 將上述各試料片浸於60。(：的10% NaOH水溶液中2 分鐘後，以水潤洗，再浸於20°C的20% HN〇3水溶液中 2分鐘’然後以水潤洗而淨化其表面。之後利用陽極化於 試料片表面形成第一陽極氧化皮膜，於該第一陽極氧化皮 膜上形成第二陽極氧化皮膜。陽極化的條件如表1所述。 第一與第二陽極氧化皮膜均是以草酸濃度爲25g/L (在此 ‘‘ L ’’是升的意思）的處理溶液形成厚度爲丨5 # m。將浴 液電壓固定爲60V。形成第一與第二陽極氧化皮膜的陽極 化條件差異僅在於處理液的溫度。形成第一陽極氧化皮膜 的處理液溫度比形成第二陽極氧化皮膜的處理液溫度爲高 〇 測定陽極化鋁合金試料片（以下簡稱爲試料片）中的 F e、C r、C u含量與陽極氧化皮膜的硬度，以及測試陽極 氧化皮膜的耐久性。 陽極氧化皮膜中的F e、C r、C u含量的測定 評估試料片的污染性。在不露出鋁合金本體的程度下 使試料片浸於lOOmL 7%鹽酸中而溶解陽極氧化皮膜。根 據溶解前後的鹽酸溶液的重量變化計算陽極氧化皮膜的溶 解量W ( g )。其次’對該鹽酸溶液進行I c P分析，求得 鹽酸溶液中的Fe、Cr、Cu含量，計算含於i〇〇mL鹽酸中 的Fe、Cr、Cu的各重量WFe、WCr、WCu(g)。計算得 陽極氧化皮膜中的Fe、Cr、Cu各含量，即，WFe/W、 Wcr/W、WCu/W。以陽極氧化皮膜中的Fe、Cr、Cu含量 -16 - 200914627 ，根據下述基準評估試料片污染性。評估結果示於表丨中 〇 污染性評估基準 ◎ Fe、Cr、Cu含量全部都在300ppm或以下 〇：Fe、Cr、Cu含量至少一者超過3 00ppm且在 5〇〇Ppm或以下，其他元素爲3〇〇ppm或以下 X · Fe、Cr、Cu含量至少一者超過500ppm 污染性評估結果 如表1所示，比較例試料編號1 2〜1 4的陽極氧化皮 膜中有些Fe、Cr、Cu含量超過5 00ppm。實施例試料編號 1、2、4、5和比較例試料編號3、6〜丨1的所有Fe、Cr ' Cu含量都在令人滿意的低至5〇〇ppm或以下。如表1所示 ’實施例試料編號1、2和比較例試料編號3、6〜1 1的所 有Fe、Cr、Cu含量都在低至300ppm或以下，這些實施 例與比較例令人非常滿意。 陽極氧化皮膜的硬度測定 將各試料片沿截面方向（使陽極氧化皮膜截面和鋁合 金本體截面成爲硏磨面）埋入樹脂’進行硏磨。依 JIS Z2244 ( 1998)的方法測定陽極氧化皮膜截面的硬度 -17- 200914627 測定結果 貫施例試料編號1、2、4、5和比較例試料編號3、6 〜14各試料片均是第二陽極氧化皮膜的硬度比第一陽極 氧化皮膜的硬度高。此第一與第二陽極氧化皮膜的硬度差 異是由於形成第二陽極氧化皮膜的陽極化溶液溫度比形成 第一陽極氧化皮膜的陽極化溶液溫度低。實施例試料編號 2的第一與第二陽極氧化皮膜的硬度差爲Hv 5。此硬度差 是由於形成第二陽極氧化皮膜的陽極化溶液溫度爲5 r而 形成第一陽極氧化皮膜的陽極化溶液溫度爲8°c所造成。 另外，實施例試料編號3的第一與第二陽極氧化皮膜的硬 度差爲Hv 4。此硬度差是由於形成第二陽極氧化皮膜的 陽極化溶液溫度爲5 °C而形成第一陽極氧化皮膜的陽極化 溶液溫度爲7°C所造成。實施例試料編號1、4、5和其他 比較例試料編號6〜1 4的第一與第二陽極氧化皮膜的硬度 差爲Hv 10。此硬度差是由於形成第二陽極氧化皮膜的陽 極化溶液溫度爲5 °C而形成第一陽極氧化皮膜的陽極化溶 液溫度爲1 〇 °C所造成。如此，通過控制陽極化溶液的溫 度，可以任意設定陽極氧化皮膜的硬度。如表1所示，各 陽極氧化皮膜的硬度，除了比較例試料編號1 2，均爲Hv 3 65或以上。因此除了比較例試料編號1 2以外，所有陽 極氧化皮膜的耐電漿性均令人滿意。 陽極氧化皮膜的耐久性試驗 耐久性的試驗由第一階段的耐裂紋性試驗和第二階段 -18- 200914627 的耐氣體腐蝕性試驗構成。在耐裂紋性試驗中，將試料片 置於試驗容器內（氣氛爲大氣），於45 01加熱1小時， 其後從試驗容器中取出試料片，浸入2 7 t：的水中急冷。 將經歷過耐裂紋性試驗的試料片接受兩次耐氣體腐蝕性試 驗循環。每次的耐氣體腐蝕性試驗循環係將試料片靜置在 5% cl2_Ar氣體氣氛下（40(TC ) 4小時。然後，利用算 式：（腐餘面積率）={(腐触部分的面積）/ (試料片的 面積）xlOO}’ gf昇g式料片表面的腐餓面積率。根據下述 的基準進行試料片評估。評估結果示於表1中。 耐久性評估基準 ◎:腐蝕面積率0% 〇：腐蝕面積率爲0%至3% X·腐餓面積率超過3% 耐久性評估結果 如表1所示，比較例試料編號3、6〜1 1不合格。實 施例試料編號1、2、4、5和比較例試料編號〗2〜1 4的耐 久性令人滿意。如表1所示，實施例試料編號1和比較例 試料編號1 2〜1 4的耐久性令人非常滿意。 綜合判斷陽極氧化皮膜中的Fe、Cr、Cu含量的測定 結果、陽極氧化皮膜的硬度測定結果和陽極氧化皮膜的耐 久性試驗結果，得知只有實施例試料編號1、2、4、5能 夠滿足全部基準。滿足全部基準的實施例試料編號1、2 -19- 200914627 、4、5具有高硬度，並在耐久性和低污染性上均令人滿 音。 -20-Fe, Cr, and Cu contents: The electric power used in anodization of 〇.〇3 % or less, respectively, is used for ionization of aluminum and generation of oxygen via water electrolysis. Therefore, if the proportion of the amount of electricity used for oxygen generation becomes large, the proportion of the amount of electricity used for aluminum ionization becomes small, and alumina cannot be efficiently produced to slow down the film formation rate. If Fe, Cr, and Cu are present in the alloy, these elements become the starting point of oxygen generation, resulting in an increase in the proportion of electricity used for oxygen generation and a slower rate of film formation. When the contents of Fe, Cr, and Cu exceed 0.03 %, respectively, Fe, Cr, and Cu are discharged from the aluminum alloy body and the anodized film to contaminate the workpiece such as a semiconductor. Therefore, the respective contents of Fe, Cr and Cu are respectively 0.03% or less, preferably 0.01% or less, respectively, as the other components of A1 and unavoidable impurities. Essentially, A1 is the only other component. However, in addition to Fe, Cr, and Cu, the aluminum alloy also contains a small amount of inevitable impurity elements of Ni, Zn, B, Ca, Na, and K. Preferably, the sum of the unavoidable impurity contents other than Fe, Cr, and Cu is 〇·1% or less. A crystalline pattern is formed in the anodized film, and if the grain of the wrong alloy is thick, the anodic oxide film has a non-uniform color tone. Therefore, titanium (Ti) can also be added to the aluminum alloy in order to prevent coarse grain growth of the aluminum alloy. If the content of Ti is too small, the effect of controlling the crystal grains cannot be obtained, and if the content is too large, contamination is caused instead. When Ti is added to the aluminum alloy, the lower limit of the Ti content is 0.01%', preferably 0.015%, and the upper limit of the Ti content is 0.03%, preferably 0.025%. Method for Producing Aluminum Alloy Material Next, a method of manufacturing an aluminum alloy material will be described. First, an aluminum alloy ingot having the above composition is produced by selecting a general casting method such as a continuous casting method or a semi-continuous casting method (DC casting method). Next, the aluminum alloy ingot is subjected to a homogenization heat treatment (i.e., "soaking process"). An anodized film excellent in durability is formed by treating the aluminum alloy ingot by a soaking method, and the temperature (i.e., 'homogenization temperature' or 'soaking temperature') is 50 (TC or more. The excellent anodized film can be formed by homogenizing the aluminum alloy ingot by a homogenization temperature of 550 ° C or higher. If the homogenization temperature exceeds 60 (TC), burning occurs to destroy the aluminum alloy ingot. Surface properties. Therefore, the homogenization temperature is recommended to be 500. (: (preferably not lower than 55 ° ° C) to 600 ° C. The effect of homogenization temperature on the formation of anodized film is not known, However, as described above, it is considered that the homogenization temperature is related to the formation of the Al-Mn-Si compound or the Al-Mn compound. Then, the aluminum alloy ingot subjected to the homogenization treatment is suitably subjected to rolling, forging, extrusion, and the like. Plastic processing to obtain an aluminum alloy material. Then, -10-200914627, the aluminum alloy material is subjected to solution treatment, quenching treatment, and artificial aging treatment (hereinafter simply referred to as "aging treatment"). Then, the aluminum alloy material is The machine is processed into a suitable shape. The aluminum alloy flat embryo processed by the aluminum alloy ingot can also be prepared by solid solution treatment, quenching treatment and artificial aging treatment. The solution treatment, quenching treatment and aging treatment can be used as usual. The T6 treatment 'for example, solution treatment at 515 to 550 ° C, water quenching treatment with 1 70 ° C X 8 hours or 155 5 1 6 5 丨 8 hours aging treatment. Anodized film second 'description An anodic oxide film of a ruthenium alloy material. As a method of forming an anodic oxide film, it is preferable to select a condition for electrolysis, that is, a composition, a concentration, a voltage, a current density, a current-voltage waveform, and a temperature of electrolysis. Anodizing requires the use of an anodizing solution containing at least one of C, s, N, P, B. For example, 'Use oxalic acid, formic acid, aminosulfonic acid, phosphoric acid, phosphorous acid, boric acid, nitric acid or a composite thereof An aqueous solution of at least one of citric acid or a composite thereof is effective. The thickness of the anodized film is not particularly limited. The thickness of the anodized film is about 0. From 1 to about 200/zm, preferably from 0.5 to 7 〇 Am ' more preferably from about 1 to about 50 // m. As described above, since the anodized film has a portion having a different hardness in the thickness direction thereof, the hardness The largest part and the smallest part of the Vickers hardness tester are Hv 5 or more. Therefore, the anodic oxide film has high hardness and can suppress the growth of cracks, so that the crack resistance is excellent. Thus 'because of the crack resistance of the anodic oxide film Excellent 'so gas intrusion into the aluminum alloy body through the anode oxygen-11 - 200914627 is also suppressed' to ensure the overall durability. If the difference between the hardest part and the hardest part is less than Hv in Vickers hardness At 5 o'clock, the behavior of the anodized film is equivalent to that of the anodized film having a substantially uniform hardness in the thickness direction, so that it is difficult to suppress the growth of cracks. As a result, the anodized film has low crack resistance and is inferior in gas rust resistance. In the present invention, at least two portions having different hardnesses in the thickness direction of the anodized film should be used. The number of the parts is not particularly limited, but the number is two or more. The hardness of the anodized film may be intermittently changed, or may be continuously (inclined). Further, from the viewpoint of suppressing the growth of cracks generated in the anodized film, it is preferable to consider the Vickers hardness of the portion having the smallest hardness as small as possible. However, if the resistance to abrasion due to the physical energy of the plasma is taken into consideration, it is preferably Η ν 3 6 5 or more in terms of Vickers hardness. An aluminum alloy material (hereinafter referred to as "positively polarized aluminum alloy") coated with such an anodized film is suitable for forming a member used in a high-temperature uranium atmosphere. The anodized aluminum alloy is particularly suitable for forming a vacuum chamber for a plasma processing apparatus among semiconductor device manufacturing apparatuses and the like and a member (such as an 'electrode) provided inside the vacuum chamber. The vacuum chamber and internal components are exposed to a high temperature environment. In hunger gas, it must have low pollution that does not contaminate the workpiece. In order to change the hardness of the anodized film in the thickness direction of the anodized film, 'the method of interrupting or continuously changing the temperature of the anodizing solution during the anodization may be employed' or the anodizing of the anodizing solution may be interrupted. The method of recovering the aluminum alloy material from the anodizing solution and then recovering the anodizing in different compositions and anodizing solutions of different temperatures from -12 to 2009 14627 / or different temperatures can make the thickness of the anodized film in the thickness direction and the temperature is low. The anodizing solution effectively suppresses chemical dissolution of the anodized film at the time of anodization and the formation of an oxide film. As described above, considering that for a workpiece such as a 'semiconductor wafer, when the content of Fe in the aluminum alloy is reduced to 0.03% or less, the content of Fe in the oxide film may be lowered to 500 ppm or the content of Fe in the aluminum alloy may be lowered to When 0.01% or less, the content of Fe in the oxide film is lowered to 150 ppm or less. As described above, the anodized aluminum alloy material described above has high durability (crack resistance and gas corrosion resistance) and examples. Hereinafter, the embodiments of the present invention will be described. However, the present invention is not limited to the technical scope of the invention described above and the modifications described below. First, aluminum having the composition shown in Table 1 below (sample Nos. 1, 2, 4, and 5, sample No. 3 of the comparative example, and cooling (cooling rate: 10 to 15 t / sec)) were cast. Combined size: width 220mmx length 250mmx thickness 100mm). Cutting Ming and honing the Ming alloy flat embryo (size: width 220mmx length 1600 m). The alloy flat embryo was heat treated at 540 °C for 4 hours and the aluminum alloy flat embryo with a thickness of 60 mm was hot rolled to a thickness of 6 mm. According to this change. Another hard anode, the pollution, then the anode. If the anode hardness and low pollution are to be included, it is not limited to the examples in this case. Examples 6 to 14) Gold ingots (tin alloy cast 5 Ommx thick. Soaked aluminum alloy-13-200914627 boards). This clock) 8 hours after 3 5mm and with aluminum alloy plate for solution treatment (temperature 510 ° C ~ 520 ° C X30 minutes for water quenching, and then aging treatment (temperature 16 (TC ~ 1 80 ° CX), get Alloy plate sample. A 25 mmx (rolling direction) sample piece having a thickness of x3 mm was cut from the alloy plate, and the surface roughness of the surface of Ra 1.6 was honed. -14- 200914627 Target 9 哿E gc〇g (Ο g CO m CO ΙΟ fe g CO § c〇§ CO g CO § CO ο σ> ΓΟ ο CO g CO g CO A3 Thickness (pm) ΙΟ tf) to in VO VO lO IT) in in ΙΛ ΙΟ in l 〇Voltage (V) § ss § sggs S § § s § § i Temperature: (°〇ιη m lO ΙΟ lO 1Λ to in 40 ΙΟ in to l〇Ί Anodized solution ^ οι Κ ^ 〇) 姨K 效 K Fried K stir fry ^ i 轶 from CT 效^ B) Money S t body g AM ^ s correct g * 1 z ^ ^ gs « ώ *| sf ^ ^ 1 ««< · · -s η § Hardness 1 _ ο οο C0 S CO s to m Male s CO g CO gc〇§ CO o oo to S c〇g CO O Male s CO § CO Thickness! (pm) ιη lO lO lO tf> ΙΟ mm in ΙΟ »〇ΙΟ ΙΛ ΙΟ Voltage ( V) 埤 埤1 City S § § S ss S § s § s § S g Temperature (°〇ο CO oooooo ο ooo ο Anodized solution ^ ΐ ^ i 效 K 炒 s « i 效 K ^ t 姨s pain CT 闵^ t 效 K ιΐ 痛§> 妫s fun ra ^ I ξ ^ g ««< . · g ^ Aj # 1 ««< · · $ ^ I make g 2 enough g «»< ;昼«tl Ϊ ξ ξ ^ g judgment ◎ ◎ ◎ 〇〇 ◎ ◎ ◎ ◎ ◎ ◎ XXX Contaminant Cu good (叩m) ? gss 490 i 〇§ 1 § ο ig ο 〇 content (PPm) ggg § omoss Another S s O o CO ms Fe content (ppm) gsi § o § goi S g another moo judgment ◎ 〇X 0 〇XXXXXX ◎ ◎ ◎ k narrow a η ο CM oc〇CO two CO 〇} ο σ> ooo 1 ο lf> ooooo ο ο ο ooo δ 0.007 0.007 0.007 0.027 0.028 0.009 0.008 0.008 oooa 0.007 0.008 0.009 1_ 0.03, σ σ> ο 0.009 g 0.028 CD S g φ gm CM CO g ® W ο do' dod ο Ο ο odo Φ g ο » ogq a> CM oc\iogq δ qoo CO ο φ ο σ > ο s φ o r- o ο ο ddo <Γ〇C CO CO (O d 00 o 卜o GO Ο ο.〇9 O) d σ> o Oi o £Λ Oi OJ CS| τ- Ο o csi CO d CO o 0.08 csi τ — Ο) ο 〇q O) 6 σι CO d GO o oo dd σ» 0.09 csi q ο σ> ο 二OJ dqq 苳苳馨 V aJ -Ο jj jj 绂t涟馁- CNi CO ΙΟ (O 卜 CO σ> ; ο 2CM CO inch -15- 200914627 Immerse each of the above samples in 60. (: After 2 minutes in 10% NaOH aqueous solution, rinse with water, then immerse in 20% HN〇3 aqueous solution at 20 °C for 2 minutes' and then purify the surface with water. Then use anodization on the sample. A first anodized film is formed on the surface of the sheet, and a second anodized film is formed on the first anodized film. The conditions of the anodization are as described in Table 1. The first and second anodized films are each having an oxalic acid concentration of 25 g/ L (where ''L'' is liter) means that the treatment solution is formed to a thickness of 丨5 #m. The bath voltage is fixed to 60 V. The difference in the anodization conditions for forming the first and second anodized films is only in the treatment. The temperature of the liquid, the temperature of the treatment liquid forming the first anodized film is higher than the temperature of the treatment liquid forming the second anodized film, and the F e and C r in the anodized aluminum alloy sample piece (hereinafter referred to as a sample piece) are measured. The C u content and the hardness of the anodic oxide film, and the durability of the tested anodic oxide film. The determination of the content of F e, C r and C u in the anodized film evaluates the contamination of the sample piece. Under The sample piece was immersed in 100 mL of 7% hydrochloric acid to dissolve the anodic oxide film. The dissolved amount W ( g ) of the anodic oxide film was calculated according to the weight change of the hydrochloric acid solution before and after the dissolution. Secondly, the I c P analysis of the hydrochloric acid solution was performed. The Fe, Cr, and Cu contents in the hydrochloric acid solution were calculated for each of the weights of Fe, Cr, and Cu contained in i〇〇mL hydrochloric acid, WFe, WCr, and WCu (g). The Fe, Cr, and Cu in the anodized film were calculated. Each content, that is, WFe/W, Wcr/W, WCu/W. The Fe, Cr, and Cu contents in the anodized film were -16 - 200914627, and the contamination of the test piece was evaluated according to the following criteria. The evaluation results are shown in the table. China's pollution assessment criteria ◎ Fe, Cr, Cu content are all 300ppm or less 〇: Fe, Cr, Cu content of at least one of more than 300 ppm and 5 〇〇 Ppm or less, other elements of 3 〇〇 ppm or The following X, Fe, Cr, and Cu contents are at least one of more than 500 ppm. The results of the pollution evaluation are shown in Table 1. In the anodic oxide film of Comparative Example No. 1 2 to 14 4, some Fe, Cr, and Cu contents exceeded 500 ppm. Example sample numbers 1, 2, 4, 5 and comparative sample number 3, 6 ~ 丨 1 All Fe, Cr' Cu contents were satisfactorily as low as 5 〇〇 ppm or less. As shown in Table 1, 'Example Sample No. 1, 2 and Comparative Sample No. 3, 6 to 1 1 all Fe, The Cr and Cu contents were all as low as 300 ppm or less, and these examples and the comparative examples were very satisfactory. The hardness of the anodized film was measured in the cross-sectional direction of the sample sheets (the anodized film section and the aluminum alloy body section were honed). Face) embedded in resin' for honing. The hardness of the cross section of the anodic oxide film was measured according to the method of JIS Z2244 (1998). -17- 200914627 Measurement results The sample numbers 1, 2, 4, and 5 of the sample and the sample numbers 3, 6 to 14 of the comparative sample were the second. The hardness of the anodized film is higher than that of the first anodized film. The difference in hardness between the first and second anodized films is because the temperature of the anodizing solution forming the second anodized film is lower than the temperature of the anodizing solution forming the first anodized film. The difference in hardness between the first and second anodized films of Example No. 2 was Hv 5 . This difference in hardness is caused by the temperature of the anodizing solution forming the second anodized film being 5 r and the temperature of the anodizing solution forming the first anodized film being 8 °c. Further, the difference in hardness between the first and second anodic oxide films of Example No. 3 was Hv 4 . This difference in hardness was caused by the temperature of the anodizing solution forming the second anodized film being 5 ° C and the temperature of the anodizing solution forming the first anodized film being 7 °C. EXAMPLES Sample Nos. 1, 4, and 5 and Comparative Examples Sample Nos. 6 to 14 have a hardness difference of Hv 10 between the first and second anodized films. This difference in hardness is caused by the temperature of the anode solution forming the second anodic oxide film being 5 ° C and the temperature of the anodizing solution forming the first anodic oxide film being 1 〇 ° C. Thus, by controlling the temperature of the anodizing solution, the hardness of the anodized film can be arbitrarily set. As shown in Table 1, the hardness of each of the anodized films was Hv 3 65 or more in addition to the sample No. 1 of Comparative Example. Therefore, all of the anode oxide films were satisfactory in plasma resistance except for the comparative sample No. 1 2 . Durability test of anodized film The durability test consisted of the first stage crack resistance test and the gas corrosion resistance test of the second stage -18-200914627. In the crack resistance test, the test piece was placed in a test container (atmosphere was atmospheric), and heated at 45 01 for 1 hour, after which the sample piece was taken out from the test container and immersed in 2 7 t: of water to be quenched. The test piece subjected to the crack resistance test was subjected to two gas corrosion resistance test cycles. Each time the gas corrosion resistance test cycle was carried out, the test piece was allowed to stand under a 5% cl 2_Ar gas atmosphere (40 (TC) for 4 hours. Then, using the formula: (corrosion area ratio) = { (area of the corrosion contact portion) / (area of the test piece) xlOO}' gf liters of the area of the rotted area on the surface of the granule. The evaluation of the test piece was carried out according to the following criteria. The evaluation results are shown in Table 1. Durability evaluation standard ◎: Corrosion area ratio 0% 〇: Corrosion area ratio is 0% to 3% X· Hurt area ratio exceeds 3% The durability evaluation results are shown in Table 1, and the comparative sample No. 3, 6 to 1 1 is unacceptable. Example sample No. 1 The durability of the sample Nos. 2, 4, and 5 and the comparative sample Nos. 2 to 1 4 was satisfactory. As shown in Table 1, the durability of the sample No. 1 of the example and the sample No. 1 2 to 1 of the comparative example was very Satisfactory. The results of measurement of Fe, Cr, and Cu contents in the anodized film, the hardness measurement results of the anodized film, and the durability test results of the anodized film were comprehensively judged, and only the sample numbers 1, 2, 4, and 5 were found. Can satisfy all benchmarks. Example sample number 1 that satisfies all benchmarks 2-19-200914627, 4, 5 have a high hardness and satisfactory tone both in durability and low fouling properties. -20-