201226617 六、發明說明： 【發明所屬之技術領域】 [0001]本發明涉及一種殼體及其製造方法，特別涉及一種鋁或 紹合金的殼體及其製造方法。 【先前技術】 [〇〇〇2]鋁或鋁合金目前被廣泛應用於航空、航天、汽車及微電 子等工f領域。但is或⑪合金的標準電極電位很低耐 腐蚀差’暴露於自然:環境中會引起表面快速腐钱。 Ο 闺冑高㈣18合金防腐祕財法通f餘其表面形成保 濩性的塗層。傳統的陽極氧化、電沉積、化學轉化膜技 術及電鍍等鋁或鋁合金的表面處理方法存在生產工藝複 雜、效率低、環境污染嚴重等缺點。 [0004] 真空鍍膜（PVD)為一清潔的成膜技術。然而，由於鋁或 銘合金的標準電極電位很低，且PVD塗層本身不可避免的 會存在微小的孔隙，因此形成於銘與録令金表面的PVD塗 層容易發生電化學腐蝕，導致該pVI)塗層的防腐蝕性能降201226617 VI. Description of the Invention: [Technical Field] The present invention relates to a casing and a method of manufacturing the same, and more particularly to a casing of aluminum or a smelting alloy and a method of manufacturing the same. [Prior Art] [〇〇〇2] Aluminum or aluminum alloy is currently widely used in the fields of aviation, aerospace, automotive, and microelectronics. However, the standard electrode potential of is or 11 alloy is very low and the corrosion resistance is poor. Exposure to nature: the environment will cause rapid surface decay. Ο 闺胄 闺胄 (4) 18 alloy anti-corrosion secrets, the surface of the surface of the formation of a protective coating. Conventional anodizing, electrodeposition, chemical conversion film technology, and surface treatment methods for aluminum or aluminum alloys such as electroplating have disadvantages such as complicated production processes, low efficiency, and serious environmental pollution. [0004] Vacuum coating (PVD) is a clean film forming technique. However, since the standard electrode potential of aluminum or alloy is very low, and the PVD coating itself inevitably has tiny pores, the PVD coating formed on the surface of the gold and the gold is prone to electrochemical corrosion, resulting in the pVI. ) the corrosion resistance of the coating is reduced
D v 低’對銘或銘合金的防腐蝕能力的提高有限。 【發明内容】 [0005] 鑒於此’提供一種具有較好的耐腐蝕性的鋁或鋁合金的 殼體。 [0006]另外’還提供一種上述殼體的製造方法。 一種殼體，包括鋁或鋁合金基體，該殼體還包括依次形 成於該銘或鋁合金基體上的鋁膜和防腐蝕膜，該防腐蝕 膜為通過離子注入摻雜鑭（La)金屬離子的氧化鋁梯度膜 099146986 表單編號A0101 第3頁/共15頁 0992080759-0 201226617 ，所述氧化銘梯度膜中氧的原子百分含量由靠近銘或銘 合金基體至遠離鋁或鋁合金基體的方向呈梯度增加。 [0008] 一種殼體的製造方法，其包括如下步驟： [0009] 提供鋁或鋁合金基體； [0010] 於該鋁或鋁合金基體的表面磁控濺射鋁膜； [0011] 於鋁膜上磁控濺射氧化鋁梯度膜，該氧化鋁梯度膜中氧 的原子百分含量由靠近紹或铭合金基體至遠離紹或铭合 金基體的方向呈梯度增加； [0012] 於氧化鋁梯度膜注入鑭金屬離子，形成防腐蝕膜。 [0013] 本發明所述殼體的製造方法，在鋁或鋁合金基體上依次 形成的鋁膜和防腐蝕膜，該防腐蝕膜為通過離子注入摻 雜鑭（La)金屬離子的氧化鋁梯度膜該，鋁膜和防腐蝕膜 的複合膜層可顯著提高所述殼體的耐腐蝕性，且該殼體 的製造工藝簡單、幾乎無環境污染。 【實施方式】 [0014] 請參閱圖1，本發明一較佳實施例的殼體10包括鋁或鋁合 金基體11、依次形成於該鋁或鋁合金基體11表面的鋁膜 13、防腐蝕膜15，該防腐蝕膜15為通過離子注入摻雜鑭 (La)金屬離子的氧化鋁梯度膜。 [0015] 所述防腐蝕膜15的厚度為0.5〜2.0#m。所述防腐蝕膜15 通過磁控濺射鍍膜法形成。 [0016] 該殼體10還包括形成於該鋁或鋁合金基體11與防腐蝕膜 15之間的鋁膜13。所述鋁膜13的形成用以增強所述防腐 099146986 表單編號A0101 第4頁/共15頁 0992080759-0 201226617 蝕膜15與鋁或鋁合金基體11之間的結合力。所述鋁膜13 的厚度為1〇〇〜300nm。 剛所述殼體10的製造方法主要包括如下步驟： [0018]提供銘或銘合金基體n，該銘或紹合金基體11可以通過 沖壓成型得到，其具有待製得的殼體1G的結構。 []將所述Is或！g合金基體丨丨放人盛裝有乙醇或丙嗣溶液的 超♦波/月洗益中進行震動清洗，以除去銘或紹合金基體 丨 11表面的雜質和油污。清洗完畢後烘乾備用。 [2〇] m述處理後的銘或銘合金基體u的表面進行氮氣電 漿β洗’進一步去除鋁或鋁合金基體11表面的油污，以 改善銘或銘合金基體u表面與後續塗層的結合力。 [_提供一錢膜機100，鑛媒機剛包括-鍵膜室20，該鑛膜 至20内叹有轉架（未圖示），將銘或銘合金基體11固定 於轉架上’轉架帶動銘或銘合金基體11沿圓形執跡21運 订’且銘或18合金基體11在沿軌跡21運行時亦自轉。在 ’ 該鑛膜室20側壁上安裝二娜，該二乾材22關於轨跡 21的中心相對稱。在二把材22的兩端設有氣源通道^， 工作氣體通過該氣源通道24進人㈣室2G，轟擊把材U 的表面，以使把材22表面賤射出粒子。當铭或叙合金基 體11通過二$材22之間時，將鍍上二抑22表面賤射的 粒子’完成磁控濺射過程。 闺肖電漿清洗的具體操作及工藝參數可為：對該錢膜室2〇 進打抽真空處理至本底真空度為8 〇xl〇-3Pa，以 300〜500sCCm (標準狀態毫升/分鐘）的流量向鍍骐室 099146986 表單編號腦！ 第5 W 15頁 ' 0992080759-0 201226617 内通入純度為99. 999%的氬氣（工作氣體），於鋁或鋁合 金基體11上施加-300 — 800V的偏壓，在所述鍍膜室2〇中 形成高頻電壓’使所述氬氣產生氬氣電漿對鋁或鋁合金 基體11的表面進行物理轟擊，而達到對鋁或鋁合金基體 11表面清洗的目的。所述氬氣電漿清洗的時間為 3〜1Omin 〇 [0023] [0024] [0025] [0026] 採用磁控濺射的方式在鋁或鋁合金基體11表面依次形成 鋁膜13及防腐蝕膜15。形成該鋁膜13工藝參數為：在所 述電漿清洗完成後，通入高純氬氣（ 99. 999%) 100~300sccm，開啟鋁靶22，設置鋁把22功率為2~8kw ’調節鋁或鋁合金基體11的偏壓為-300 —500V，在鋁或 紹合金基體11表面沉積鋁膜13，沉積5~10分鐘。 制備防腐蝕膜1 5，該防腐蝕膜1 5為通過離子注入摻雜鑭 (La)金屬離子的氧化鋁梯度膜。 氧化鋁梯度膜的製備工藝：以氬氣為工作氣體，向所述 鑛膜至中通入初始流量為1 〇〜2〇scCm的反應氣體氧氣， 於紹或紹合金基體11上施加-1 50 — 500V的偏壓，在沉積 該氧化鋁梯度膜的過程中，每沉積1〇〜15min將氧氣的流 量增大10〜20sccm ’使0原子在防腐蝕膜15中的原子百分 含量由靠近鋁或鋁合金基體1丨至遠離鋁或鋁合金基體^ 的方向呈梯度增加。沉積時間為3〇〜9〇min。 所述氧化鋁梯度瞑在其形成過程中可形成A丨_〇相，增強 所述氡化鋁梯度暝的緻密性，以提高所述殼體1〇的耐腐 餘性。 099146986 I單編號A0101 第6頁/共15頁 0992080759-0 201226617 [0027] Ο [0028] Ο [0029] 所述氧化鋁梯度膜中Ο的原子百分含量由靠近鋁或紹合金 基體11至遠離鋁或鋁合金基體11的方向呈梯度增加可 降低防腐蝕膜15與鋁膜13之間晶格不匹配的程度，有利 於將濺射氧化鋁梯度膜的過程中產生的殘餘應力向鋁戈 鋁合金基體11方向傳遞；又因為在氧化鋁梯度膜和鋁或 鋁合金基體11之間沉積了塑性較好的鋁膜13，可改善氣 化鋁梯度膜與銘或銘合金基體11之間的介面錯配度当 氧化鋁梯度膜中的殘餘應力較大時，可以借助於該鋁膜 13以及鋁或鋁合金基體11的局部塑性變形實現殘餘應力 的釋放，從而減少氧化鋁梯度膜内的殘餘應力，使殼體 10不易發生應力腐蝕，以提高所述殼體1〇的耐腐蝕性。 所述應力腐蚀是指在殘餘或/和外加應力及腐姓介質的作 用下，引起的金屬失效現象。 完成氧化鋁梯度膜的沉積後，於該防氧化鋁梯度膜表面 注入鋼金屬離子。所述的注入鋼金屬離子的過程是：將 鍍覆有所述鋁膜13及氧化鋁梯度膜的鋁或鋁合金基體u 置於強流金屬離子.注入機（M.EVVA)(未圖示）中，該離子 注入機中採用鑭金屬靶材’該離子注入機首先將鑭金屬 進行電離’使其產生鑭金屬離子蒸氣，並經高壓電場加 速使該鑭金屬離子蒸氣形成具有幾萬甚至幾百萬電子伏 特能量的鑭金屬離子束，射入氧化鋁梯度膜的表面，與 氧化铭梯度膜表層中及其表面的原子或分子發生的物理 反應，使該氧化鋁梯度膜中注入有鑭金屬離子，形成所 述防腐蝕層15。 注入爛金屬離子的參數為：離子注入機的真空度為1χ1〇- 099146986 表單編號Α0101 第7頁/共15頁 0992080759-0 201226617 4Pa，離子源電壓為30〜100kV，離子束流強度為 0. 1〜5mA，控制鑭金屬離子注入劑量在lxl016ions/cm2 到 lxl018ions/cm2之間。 [0030] 所述鑭（La)金屬離子與所述氧化鋁梯度膜中的原子為 冶金結合，因此，該注入的鑭金屬離子不易脫落，且由 於是在高能離子注入的條件下形成，該鑭（La)金屬注 入氧化鋁梯度膜中後形成為非晶態層，由於非晶態結構 具有各向同性、表面無晶界、無位錯、偏析，均相體系 等特點，故，經離子注入鑭（La)金屬離子後的氧化鋁 梯度膜使殼體10在腐蝕性介質中不易形成腐蝕微電池， 發生電化學腐蝕的可能性小，大大提高了殼體10的耐蝕 性。 [0031] 以下結合具體實施例對殼體10的製備方法及殼體10進行 說明： [0032] 實施例1 [0033] 電聚清洗：氬氣流量為2 8 0、sccm，銘或銘合金基體11的 偏壓為-300V，電漿清洗的時間為9分鐘； [0034] 濺鍍鋁膜1 3 :以鋁乾22為乾材，通入氬氣1 OOsccm，開 啟鋁靶22，設置鋁靶22功率為2kw，設置鋁或鋁合金基體 11的偏壓為-500V，沉積5分鐘； [0035] 製備防腐蝕層15 :濺鍍氧化鋁梯度膜，以氬氣為工作氣 體，其流量為lOOsccra，以氧氣為反應氣體，設置氧氣的 初始流量分別為1 0 s c c m，在銘或IS合金基體11上施加-500V的偏屋；每沉積10min將氧氣的流量增大lOsccm， 099146986 表單編號A0101 第8頁/共15頁 0992080759-0 201226617 沉積時間控制為30min ; [0036] 於氡化鋁梯度膜注入鑭金屬離子：設置真空度為lx l〇-4Pa，離子源電壓為30kV ’離子束流強度為0. 1mA， 控制鑭金屬離子注入劑量為lxl〇16i〇ns/cm2。 [〇〇37] 實施例2 [〇〇38] 電漿清洗：氬氣流量為230sccm ’金屬銘或鋁合金基體 11的偏壓為-480V，電漿清洗的時間為7分鐘； [0039] 濺鍍鋁膜13 :以鋁靶22為靶材’通入氬氣20〇sccm，開 啟鋁靶22，設置鋁靶22功率為5kw，設置銘或鋁合金基體 11的偏壓為-400V，沉積7分鐘； [0040] 製備防腐蝕層15 :濺鍍氧化鋁梯度膜’以氬氣為工作氣 體，其流量為200sccm，以氧氣為反應氣體’設置氧氣的 初始流量分別為15sccm，在銘或銘合金基體11上施加_ 300V的偏壓；每沉積12min將氧氣的流量增大15sccm， 沉積時間控制為60min ; [0041] 於氧化鋁梯度膜注入鑭金屬離子：設置真空度為lx 10-4Pa，離子源電壓為60kV，離子束流強度為2mA，控 17 2 制鑭金屬離子注入劑量在lxl〇 ions/cm ° [0042] 實施例3 [0043] 電漿清洗：氬氣流量為160sccm，鋁或鋁合金基體11的 偏壓為-400V，電漿清洗的時間為6分鐘； 濺鍍鋁膜13 :以鋁靶22為靶材，通入氬氣3〇〇sccm，開 啟鋁靶22，設置鋁靶22功率為8kw ’設置銘或銘合金基體 099146986 表單編號A0101 第9頁/共15頁 0992 [0044] 201226617 11的偏壓為-30 0V，沉積10分鐘； [0045] 製備防腐蝕層15 :濺鍍氧化鋁梯度膜，以氬氣為工作氣 體，其流量為300sccm，以氧氣為反應氣體，設置氧氣的 初始流量分別為20 sccm，在銘或銘合金基體11上施加-150V的偏壓；每沉積15min將氧氣的流量增大20sccm， 沉積時間控制為90min ; [0046] 於氧化鋁梯度膜注入鑭金屬離子的工藝參數為：設置真 空度為lxlO_4Pa，離子源電壓為100kV，離子束流強度 為5mA，控制鑭金屬離子注入劑量lxl018ions/cm2。 [0047] 本發明較佳實施方式的殼體10的製造方法，在鋁或鋁合 金基體11上依次形成鋁膜13及防腐蝕膜15，該防腐蝕膜 15為氧化鋁梯度膜，其離子注入有鑭（La)金屬離子。該 鋁膜13、防腐触膜15組成的複合膜層顯著地提高了所述 殼體10的耐腐蝕性，且該製造工藝簡單、幾乎無環境污 染。 【圖式簡單說明】 [0048] 圖1係本發明較佳實施方式殼體的刳視示意圖。 [0049] 圖2係圖1殼體的製作過程中所用鍍膜機結構示意圖。 【主要元件符號說明】 [0050] 殼體：10 [0051] 鋁或鋁合金基體：11 [0052] 鋁膜：13 [0053] 防腐蝕膜：15 表單編號A0101 099146986 第10頁/共15頁 0992080759-0 201226617 [0054] 鍍膜機：100 [0055] 鍍膜室：20 [0056] 軌跡：21 [0057] 靶材：22 [0058] 氣源通道：24 ❹ 099146986 表單編號A0101 第11頁/共15頁 0992080759-0D v Low 'The improvement in corrosion resistance of Ming or Ming alloy is limited. SUMMARY OF THE INVENTION [0005] In view of this, a housing of aluminum or aluminum alloy having better corrosion resistance is provided. Further, a method of manufacturing the above casing is also provided. A casing comprising an aluminum or aluminum alloy substrate, the casing further comprising an aluminum film and an anti-corrosion film sequentially formed on the inscription or aluminum alloy substrate, the anti-corrosion film being doped with lanthanum (La) metal ions by ion implantation Alumina Gradient Membrane 099146986 Form No. A0101 Page 3 of 15 0992080759-0 201226617 The atomic percentage of oxygen in the oxidized gradient film is from the direction of the Ming or Ming alloy matrix to the direction away from the aluminum or aluminum alloy matrix. Increased in gradient. [0008] A method of manufacturing a casing, comprising the steps of: [0009] providing an aluminum or aluminum alloy substrate; [0010] magnetron sputtering an aluminum film on the surface of the aluminum or aluminum alloy substrate; [0011] An upper magnetron sputtered alumina gradient film in which the atomic percentage of oxygen increases in a gradient from the Schröming alloy substrate to the direction away from the Schumacher alloy matrix; [0012] in the alumina gradient film The ruthenium metal ions are implanted to form an anti-corrosion film. [0013] The method for manufacturing the casing of the present invention, an aluminum film and an anti-corrosion film sequentially formed on an aluminum or aluminum alloy substrate, the anti-corrosion film being an alumina gradient doped with lanthanum (La) metal ions by ion implantation The film, the composite film layer of the aluminum film and the anti-corrosion film can significantly improve the corrosion resistance of the casing, and the manufacturing process of the casing is simple and almost free from environmental pollution. [0014] Referring to FIG. 1, a housing 10 according to a preferred embodiment of the present invention includes an aluminum or aluminum alloy substrate 11, an aluminum film 13 sequentially formed on the surface of the aluminum or aluminum alloy substrate 11, and an anti-corrosion film. 15. The anti-corrosion film 15 is an alumina gradient film doped with lanthanum (La) metal ions by ion implantation. [0015] The thickness of the anti-corrosion film 15 is 0.5 to 2.0 #m. The anticorrosive film 15 is formed by a magnetron sputtering coating method. [0016] The housing 10 further includes an aluminum film 13 formed between the aluminum or aluminum alloy substrate 11 and the anti-corrosion film 15. The aluminum film 13 is formed to enhance the corrosion resistance. 099146986 Form No. A0101 Page 4 of 15 0992080759-0 201226617 The bonding force between the etching film 15 and the aluminum or aluminum alloy substrate 11. The aluminum film 13 has a thickness of 1 Å to 300 nm. The manufacturing method of the housing 10 has mainly included the following steps: [0018] An inscription or alloy base body 11 is provided, which can be obtained by press forming having the structure of the casing 1G to be produced. [] will be the Is or! The g-alloy matrix is subjected to vibration cleaning in an ultra-short wave/month wash containing ethanol or a propionate solution to remove impurities and oil on the surface of the alloy substrate. After cleaning, dry and set aside. [2〇] m after the treatment of the surface of the Ming or Ming alloy matrix u is subjected to nitrogen plasma β washing to further remove the oil stain on the surface of the aluminum or aluminum alloy substrate 11 to improve the surface of the alloy or the subsequent coating of the Ming or Ming alloy matrix. Binding force. [_ Providing a money film machine 100, the mineral media machine just includes - the key film chamber 20, the mineral film to 20 inside sighs (not shown), the Ming or Ming alloy substrate 11 is fixed on the rotating frame The frame drives the Ming or Ming alloy substrate 11 to be transported along the circular track 21 and the Ming or 18 alloy substrate 11 also rotates as it travels along the track 21. On the side wall of the film chamber 20, two diapers 22 are mounted, and the two dry materials 22 are symmetrical with respect to the center of the trajectory 21. At both ends of the two materials 22, a gas source passage is provided, and the working gas enters the human (4) chamber 2G through the gas source passage 24 to bombard the surface of the material U so that the surface of the material 22 is ejected. When the inscription or alloy substrate 11 passes between the two materials 22, the particles of the surface of the film 22 are plated to complete the magnetron sputtering process. The specific operation and process parameters of the 电 电 plasma cleaning can be as follows: the vacuum membrane chamber is vacuumed to a background vacuum of 8 〇 xl 〇 -3 Pa, 300 to 500 sCCm (standard state ML / min) The flow rate to the rhodium chamber 099146986 form number brain! On the 5th W 15 page '0992080759-0 201226617, an argon gas (working gas) having a purity of 99.999% is applied, and a bias of -300 - 800 V is applied to the aluminum or aluminum alloy substrate 11 in the coating chamber 2 The formation of a high-frequency voltage in the crucible causes the argon gas to generate an argon plasma to physically bombard the surface of the aluminum or aluminum alloy substrate 11 to achieve the purpose of cleaning the surface of the aluminum or aluminum alloy substrate 11. The argon plasma cleaning time is 3 to 10 min. [0023] [0025] [0025] An aluminum film 13 and an anti-corrosion film are sequentially formed on the surface of the aluminum or aluminum alloy substrate 11 by magnetron sputtering. 15. The process parameters for forming the aluminum film 13 are as follows: after the plasma cleaning is completed, high purity argon gas (99.999%) is passed through 100~300 sccm, the aluminum target 22 is turned on, and the aluminum power is set to 2~8 kw. The aluminum or aluminum alloy substrate 11 has a bias voltage of -300 to 500 V, and an aluminum film 13 is deposited on the surface of the aluminum or alloy substrate 11 for 5 to 10 minutes. An anti-corrosion film 15 is prepared, which is an alumina gradient film doped with ytterbium (La) metal ions by ion implantation. The preparation process of the alumina gradient film: using argon gas as the working gas, introducing a reaction gas oxygen having an initial flow rate of 1 〇 2 〇 scCm to the mineral film to the medium, and applying -1 50 to the alloy substrate 11 of the Shao or Shao alloy. — 500V bias voltage, during the deposition of the alumina gradient film, the flow rate of oxygen is increased by 10~20sccm for every deposition of 1~15min'. The atomic percentage of 0 atom in the anti-corrosion film 15 is close to aluminum. Or the aluminum alloy substrate 1 丨 is increased in gradient from the direction of the aluminum or aluminum alloy substrate ^. The deposition time is 3 〇 to 9 〇 min. The alumina gradient crucible can form an A丨_〇 phase during its formation, enhancing the compactness of the aluminum telluride gradient crucible to improve the corrosion resistance of the shell. 099146986 I, single number A0101, page 6 of 15 0992080759-0 201226617 [0027] 原子 [0029] The atomic percentage of germanium in the alumina gradient film is close to the aluminum or the alloy substrate 11 A gradient increase in the direction of the aluminum or aluminum alloy substrate 11 can reduce the degree of lattice mismatch between the anti-corrosion film 15 and the aluminum film 13, and is advantageous for the residual stress generated during the process of sputtering the aluminum oxide gradient film to the aluminum aluminum The alloy substrate 11 is transferred in the direction; and because the plastic film 13 is deposited between the alumina gradient film and the aluminum or aluminum alloy substrate 11, the interface between the vaporized aluminum gradient film and the Ming or Ming alloy substrate 11 can be improved. Mismatch degree When the residual stress in the alumina gradient film is large, the residual stress can be released by means of the local plastic deformation of the aluminum film 13 and the aluminum or aluminum alloy substrate 11, thereby reducing the residual stress in the alumina gradient film. Therefore, the casing 10 is less likely to undergo stress corrosion to improve the corrosion resistance of the casing 1 . The stress corrosion refers to a metal failure phenomenon caused by residual or/and external stress and a humic medium. After the deposition of the alumina gradient film is completed, the steel metal ions are implanted into the surface of the alumina-resistant gradient film. The process of injecting the steel metal ions is: placing the aluminum or aluminum alloy matrix u plated with the aluminum film 13 and the aluminum oxide gradient film in a strong current metal ion implanter (M.EVVA) (not shown) In the ion implanter, a bismuth metal target is used. The ion implanter first ionizes the ruthenium metal to generate a ruthenium metal ion vapor, and accelerates the high pressure electric field to form the ruthenium metal ion vapor with tens of thousands or even several a ruthenium metal ion beam of one million electron volts, which is incident on the surface of the alumina gradient film, and physically reacts with atoms or molecules in the surface of the oxidized gradient film to inject the ruthenium metal into the gradient film. The ions form the anti-corrosion layer 15. The parameters for injecting rotten metal ions are: the vacuum degree of the ion implanter is 1χ1〇- 099146986 Form No. Α0101 Page 7/15 pages 0992080759-0 201226617 4Pa, the ion source voltage is 30~100kV, and the ion beam intensity is 0. 1~5mA, control the amount of bismuth metal ion implantation between lxl016ions/cm2 and lxl018ions/cm2. [0030] the lanthanum (La) metal ion is metallurgically bonded to the atom in the alumina gradient film, and therefore, the implanted ruthenium metal ion is not easily detached, and since it is formed under high energy ion implantation conditions, the ruthenium (La) metal is implanted into the alumina gradient film to form an amorphous layer. Since the amorphous structure has isotropy, no surface boundary, no dislocation, segregation, homogeneous system, etc., it is ion implanted. The alumina gradient film after the lanthanum (La) metal ion makes the casing 10 less likely to form a corrosive microbattery in a corrosive medium, and the possibility of electrochemical corrosion is small, and the corrosion resistance of the casing 10 is greatly improved. [0031] The method for preparing the casing 10 and the casing 10 will be described below in conjunction with specific embodiments: [0032] Electropolymer cleaning: argon flow rate is 280, sccm, Ming or Ming alloy matrix The bias voltage of 11 is -300V, and the plasma cleaning time is 9 minutes; [0034] Sputtering aluminum film 13: using aluminum dry 22 as a dry material, introducing argon gas to 100 sec, opening aluminum target 22, setting aluminum target 22 power is 2kw, the aluminum or aluminum alloy substrate 11 is set to a bias voltage of -500V, deposited for 5 minutes; [0035] Preparation of anti-corrosion layer 15: sputtered alumina gradient film, argon gas as working gas, the flow rate is lOOsccra With oxygen as the reaction gas, the initial flow rate of oxygen is set to 10 sccm, and the partial housing of -500V is applied to the Ming or IS alloy substrate 11; the flow rate of oxygen is increased by 10sc per deposition for 10 minutes, 099146986 Form No. A0101 No. 8 Page / Total 15 pages 0992080759-0 201226617 The deposition time is controlled to 30 min; [0036] Injecting ruthenium metal ions into the bismuth telluride gradient film: setting the vacuum degree to lx l〇-4Pa, the ion source voltage is 30kV 'the ion beam intensity is 0. 1 mA, the control bismuth metal ion implantation dose is lxl 〇 16 i 〇 ns / cm 2 . [〇〇37] Example 2 [〇〇38] Plasma cleaning: argon gas flow rate is 230 sccm 'Metal or aluminum alloy substrate 11 has a bias voltage of -480 V, and plasma cleaning time is 7 minutes; [0039] Aluminized film 13: The aluminum target 22 is used as a target material to pass argon gas 20 〇 sccm, open the aluminum target 22, set the power of the aluminum target 22 to 5 kW, and set the bias voltage of the aluminum alloy substrate 11 to -400 V, and deposit 7 [0040] Preparation of anti-corrosion layer 15: Sputtered alumina gradient film 'with argon gas as working gas, its flow rate is 200sccm, with oxygen as the reaction gas 'the initial flow rate of oxygen is 15sccm, respectively, in Ming or Ming alloy A bias voltage of _300 V was applied to the substrate 11; the flow rate of oxygen was increased by 15 sccm every 12 min of deposition, and the deposition time was controlled to 60 min; [0041] Injecting ruthenium metal ions into the gradient film of alumina: setting the degree of vacuum to be lx 10-4 Pa, ion The source voltage is 60 kV, the ion beam current intensity is 2 mA, and the control ion 17 ion metal ion implantation dose is lxl〇ions/cm ° [0042] Example 3 [0043] Plasma cleaning: argon gas flow rate is 160 sccm, aluminum or aluminum The alloy substrate 11 has a bias voltage of -400 V and a plasma cleaning time of 6 minutes; 13: With the aluminum target 22 as the target, argon gas 3 〇〇 sccm, open the aluminum target 22, set the aluminum target 22 power to 8kw 'Set Ming or Ming alloy matrix 099146986 Form No. A0101 Page 9 / Total 15 Page 0992 [0044] 201226617 11 bias voltage is -30 0V, deposition 10 minutes; [0045] Preparation of anti-corrosion layer 15: sputtering alumina gradient film, argon gas as a working gas, the flow rate is 300sccm, with oxygen as the reaction gas The initial flow rate of oxygen is set to 20 sccm, and a bias voltage of -150 V is applied to the Ming or Ming alloy substrate 11; the flow rate of oxygen is increased by 20 sccm every 15 min, and the deposition time is controlled to be 90 min; [0046] The process parameters of the membrane for injecting bismuth metal ions are: setting the vacuum degree to lxlO_4Pa, the ion source voltage to 100kV, the ion beam current intensity to 5 mA, and controlling the bismuth metal ion implantation dose lxl018ions/cm2. In the manufacturing method of the casing 10 according to the preferred embodiment of the present invention, an aluminum film 13 and an anti-corrosion film 15 are sequentially formed on the aluminum or aluminum alloy substrate 11, and the anti-corrosion film 15 is an alumina gradient film, and the ion implantation is performed. There are lanthanum (La) metal ions. The composite film layer composed of the aluminum film 13 and the anti-corrosion touch film 15 remarkably improves the corrosion resistance of the casing 10, and the manufacturing process is simple and almost free of environmental pollution. BRIEF DESCRIPTION OF THE DRAWINGS [0048] FIG. 1 is a schematic view of a housing of a preferred embodiment of the present invention. 2 is a schematic structural view of a coating machine used in the manufacturing process of the housing of FIG. 1. [Main Component Symbol Description] [0050] Housing: 10 [0051] Aluminum or Aluminum Alloy Substrate: 11 [0052] Aluminum Film: 13 [0053] Corrosion Resistant Film: 15 Form No. A0101 099146986 Page 10 of 15 0992080759 -0 201226617 [0054] Coating machine: 100 [0055] Coating chamber: 20 [0056] Track: 21 [0057] Target: 22 [0058] Air source channel: 24 ❹ 099146986 Form number A0101 Page 11 of 15 0992080759-0