201226583 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 鋁合金的殼體及其製造方法。 【先前技術】 [0002] 鋁或鋁合金目前被廣泛應用於航空、航天、汽車及微電 子等工業領域。但鋁或鋁合金的標準電極電位很低，耐 腐蝕差，暴露於自然環境中會引起表面快速腐蝕。 ❸ ❹ [0003] 提高鋁或鋁合金防腐蚀性的方法通常係在其表面形成保 — 護性的塗層。傳統的陽極氧化、電沉積、化學轉化膜技 術及電鍍等鋁或銘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] 真空鑛膜（PVD)為一清潔的成膜技術。然而’由於銘或 鋁合金的標準電極電位报低，且PVD塗層本身不可避免的 會存在微小的孔隙’因此形成於銘或銘合金表面的PVD塗 層容易發生電化學腐姓，導致該PVD塗層的防腐蝕性能降 低，對鋁或鋁合金的括腐敍能力的提高有限。 【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。 [0007] —種殼體，包括鋁或鋁合金基體，該殼體還包括形成於 該鋁或鋁合金基體上的Al-Cu膜，所述A1_Cu膜注入有錳 金屬離子。 099146985 表單編號A0101 第3頁/共12頁 0992080758-0 201226583 [0008] [0009] [0010] [0011] [0012] [0013] [0014] [0015] [0016] [0017] [0018] 099146985 一種殼體的製造方法，其包括如下步驟： 提供鋁或鋁合金基體； 於該鋁或鋁合金基體的表面磁控濺射形成A卜Cu膜； 於該A卜CU膜上注入錳金屬離子。 本發明所述殼體的製造方法，在鋁或鋁合金基體上形成 A卜Cu膜，對該Al-Cu膜注入錳離子，該注入有锰金屬離 子的A卜Cu膜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】 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、及形成於該鋁或鋁合金基體11表面的鋁銅（201226583 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 aluminum alloy and a method of manufacturing the same. [Prior Art] [0002] Aluminum or aluminum alloys are currently widely used in aerospace, aerospace, automotive, and microelectronics industries. However, the standard electrode potential of aluminum or aluminum alloy is very low, and the corrosion resistance is poor, and exposure to the natural environment causes rapid surface corrosion. ❸ ❹ [0003] The method of improving the corrosion resistance of aluminum or aluminum alloys is usually to form a protective coating on the surface. Conventional anodizing, electrodeposition, chemical conversion film technology, and surface treatment methods of aluminum or alloys such as electroplating have disadvantages such as complicated production processes, low efficiency, and serious environmental pollution. [0004] Vacuum mineral film (PVD) is a clean film forming technique. However, because the standard electrode potential of Ming or aluminum alloy is low, and the PVD coating itself inevitably has tiny pores, the PVD coating formed on the surface of Ming or Ming alloy is prone to electrochemical corrosion, resulting in the PVD. The corrosion resistance of the coating is reduced, and the improvement of the ability of the aluminum or aluminum alloy is limited. SUMMARY OF THE INVENTION [0005] In view of the above, 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 Al-Cu film formed on the aluminum or aluminum alloy substrate, the A1_Cu film being implanted with manganese metal ions. Form number A0101 Page 3/12 page 0992080758-0 201226583 [0008] [0009] [0011] [0012] [0014] [0018] [0018] [0018] [9918] A method of manufacturing a casing, comprising the steps of: providing an aluminum or aluminum alloy substrate; magnetron sputtering on the surface of the aluminum or aluminum alloy substrate to form an A-Cu film; and implanting manganese metal ions on the A-CU film. In the method for manufacturing the casing of the present invention, an A-Cu film is formed on the aluminum or aluminum alloy substrate, and the Al-Cu film is implanted with manganese ions, and the A-Cu film implanted with the manganese metal ions can significantly increase the shell The corrosion resistance of the body, and the manufacturing process of the casing is simple and almost no environmental pollution. [Embodiment] Referring to Figure 1, a housing 10 according to a preferred embodiment of the present invention includes an aluminum or aluminum alloy base 11 and aluminum copper formed on the surface of the aluminum or aluminum alloy base 11 (
Al-Cu)膜13，該Al-Cu膜13注入有錳金屬離子。 所述Al-Cu膜13的厚度為0. 5〜6. 0#πι。所述Al-Cu膜13 通過磁控濺射鍍膜法形成。所述錳離子金屬通過離子注 入的方法注入Al-Cu膜13中。 其中，所述AhCu膜中注入錳離子的質量百分含量為 1%-30〇/〇。 所述殼體10的製造方法主要包括如下步驟： 提供鋁或鋁合金基體11，該鋁或鋁合金基體11可以通過 沖壓成型得到，其具有待製得的殼體10的結構。 將所述鋁或鋁合金基體11放入盛裝有乙醇或丙酮溶液的 超聲波清洗器中進行清洗，以除去鋁或鋁合金基體11表 面的雜質和油污。清洗完畢後烘乾備用。 表單編號A0101 第4頁/共12頁 0992080758-0 201226583 [0019] [0020] ❹ 再對銘或鋁合金基體11的表面進行氬氣電漿清洗，進— 步去除紹或鋁合金基體11表面的油污’以改善鋁或鋁合 金基體11表面與後續塗層的結合力。 提供一鍍膜機100，鍍膜機100包括一鍍膜室20及用以對 所述錄膜室20抽真空的一真空泵30，該鍍膜室20内設有 轉架（未圖示），將鋁或鋁合金基體11固定於轉架上， 轉架帶動鋁或鋁合金基體Η沿圓形軌跡21運行，且鋁或 銘合金基體11在沿軌跡21運行時亦自轉。在該鍍獏室2〇 側壁上安裝二靶材22，該二靶材22為二Al-Cu合金靶， 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24，工作氣體通過該氣源通道24進入鑛 膜室20，轟擊二靶材22的表面’以使二靶材22表面濺射 出粒子。當鋁或鋁合金基體U通過二靶材22之間時，將 鍍上二靶材22表面濺射的粒子，完成磁控濺射過程。 [0021]Ο 電漿清洗的具體操作及工藝參數可為：對該鍍膜室2〇進 行抽真空處理至真窣度為8. Oxio —3pa，以3〇〇~500sccm (標準狀態毫升/分鐘)的流量向鍍膜室2〇内通入純度為 99.999%的氬氣（工作氣體），於鋁或鋁合金基體丨^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n的表 面進行物理轟擊，而達到對鋁或鋁合金基體丨丨表面清洗 的目的。所述氬氣電漿清洗的時間為31〇min ^ [0022] 在對鋁或鋁合金基體11進行電漿清洗後，於該鋁或鋁合 金基體11上形成Al-Cu膜13。形成該Ai-cu膜13的具體 操作及工藝參數如下：以氬氣為工作氣體，調節氬氣流 099146985 表單編號A0101 第5頁/共12頁 0992080758-0 201226583 量為50〜300sccm，設置占空比為30%〜80%，於在呂或I呂人 金基體11上施加- 50~-200V的偏壓，並加熱鑛膜室至 100〜150°C (即濺射溫度為100〜150°C);開啟乾材22 電源，該乾材2 2為銘銅合金乾材，所述紹銅合金乾中銅 的質量百分含量為0. 5%〜25%，設置靶材22的功率為 2〜8kw ’沉積A卜Cu膜13。沉積該A卜Cu膜13的時間為 45〜120miη。 [0023] 形成所述Al-Cu膜13後，於該Α卜Cu膜13表面注入猛金屬 離子。 [0024] 所述的離子注入過程係：採用一離子注入機（圖未示） ’將形成有Al-Cu膜13的銘或銘合金基體11置於該離子 注入機的真空室中’該離子注入機將錳金屬進行電離， 使其產生猛金屬離子蒸氣，並經高壓電場加速使該猛金 屬離子蒸氣形成具有幾萬甚至幾百萬電子伏特能量的錳 離子束，射入A卜Cu膜13,表@，最終於窣Al-Cu膜13的 表面注入錳金屬離子。 [0〇25]根據本實施例A卜Cu膜1 3的特性並使最終形成的a卜Cu膜 此顯著提高殼體的耐腐蚀性，Al-Cu膜13進行所述猛離子 注入時的參數設定為：真空度為1χ1〇-4Pa，離子源電壓 為30〜l〇〇kV，離子束流強度為〇.卜5mA，所述Al-Cu膜 中注入猛離子的質量百分含量為1%-30%。 [0026] 以下結合具體實施例對殼體10的製備方法及殼體1〇進行 進一步說明： [0027] 實施例1 098146985 表單編號A0101 第6頁/共12頁 0992080758-0 201226583 [0028] 電漿清洗：氬氣流量為280sccm，設置鋁或鋁合金基體 11的偏壓為-300V，電漿清洗的時間為9分鐘； [0029] 濺鍵銅鋁膜13 :通入氬氣lOOsccm，開啟鋁銅合金靶， 設置A卜Cu合金靶功率為2kw，設置鋁或鋁合金基體11的 偏壓為-50V，沉積100分鐘； [0030] 銅鋁膜13注入錳金屬離子：設置真空度為lxlO_4Pa，離 子源電壓為30kV，離子束流強度為0. 1mA。 [0031] 實施例2 〇 [0032] 電漿清洗：氬氣流量為230sccm，鋁或鋁合金基體11的 偏壓為-480V，電漿清洗的時間為7分鐘； [0033] 濺鑛銘銅層13 :通入氬氣200sccm，開啟銘銅合金乾22 ，設置Al-Cu合金靶的功率為5kw，設置基體的偏壓為-100V，沉積60分鐘； [0034] 銅鋁膜13注入錳金屬離子：設置真空度為lxlO_4Pa，離 子源電壓為60kV，離子束流強度為2mA。 ❹ [0035] 實施例3 [0036] 電聚清洗：氬氣流量為1 60sccm，銘或紹合金基體11的 偏壓為-400V，電漿清洗的時間為6分鐘； [0037] 濺鍍鋁銅層13 :通入氬氣300sccm，開啟鋁銅合金靶22 ，設置Al-Cu合金靶功率為8kw，設置鋁或鋁合金基體11 的偏壓為-200V，沉積45分鐘； [0038] 銅鋁膜13注入錳金屬離子：設置真空度為lxlO_4Pa，離 099146985 表單編號A0101 第7頁/共12頁 0992080758-0 201226583 子源電壓為100kV，離子束流強度為5mA。 [0039] 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A卜Cu膜13。並對A卜Cu膜13注入 錳金屬離子，該錳金屬注入A卜Cu膜13中後形成一種非晶 態，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，經離子注入錳金屬離 子後的AhCu膜13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極小，大大提高了殼 體10的耐蝕性，且該製造工藝簡單、幾乎無環境污染。 【圖式簡單說明】 [0040] 圖1為本發明較佳實施方式殼體的剖視示意圖。 [0041] 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】 [0042] 殼體：10 [0043] 鋁或鋁合金基體：11 [0044] A 卜Cu膜：13 [0045] 鍍膜機：100 [0046] 鍍膜室：20 [0047] 真空泵：3 0 [0048] 軌跡：21 [0049] 靶材：22 [0050] 氣源通道：24 099146985 表單編號A0101 第8頁/共12頁 0992080758-0The Al-Cu film 13 is implanted with manganese metal ions. The thickness of the Al-Cu film is 0. 5~6. 0#πι. The Al-Cu film 13 is formed by a magnetron sputtering coating method. The manganese ion metal is injected into the Al-Cu film 13 by ion implantation. Wherein, the mass percentage of manganese ions implanted into the AhCu film is 1%-30〇/〇. The manufacturing method of the casing 10 mainly comprises the steps of: providing an aluminum or aluminum alloy base 11 which can be obtained by press forming having the structure of the casing 10 to be produced. The aluminum or aluminum alloy substrate 11 is placed in an ultrasonic cleaner containing an ethanol or acetone solution for cleaning to remove impurities and oil on the surface of the aluminum or aluminum alloy substrate 11. After cleaning, dry and set aside. Form No. A0101 Page 4 / Total 12 Page 0992080758-0 201226583 [0020] [0020] 氩 Argon plasma cleaning of the surface of the aluminum alloy substrate 11 or the surface of the aluminum alloy substrate 11 is further removed. Oil stains 'to improve the adhesion of the surface of the aluminum or aluminum alloy substrate 11 to the subsequent coating. A coating machine 100 is provided. The coating machine 100 includes a coating chamber 20 and a vacuum pump 30 for evacuating the recording chamber 20. The coating chamber 20 is provided with a rotating frame (not shown) for aluminum or aluminum. The alloy base 11 is fixed to the turret, and the turret drives the aluminum or aluminum alloy base Η to run along the circular trajectory 21, and the aluminum or alloy base 11 also rotates while running along the trajectory 21. Two targets 22 are mounted on the sidewalls of the crucible chamber 2, and the two targets 22 are two Al-Cu alloy targets, and the two dry materials 22 are symmetrical with respect to the center of the track 21. At both ends of the two members 22, a gas source passage 24 is provided through which the working gas enters the ore chamber 20 to bombard the surface of the two targets 22 so that the surfaces of the two targets 22 are sputtered out. When the aluminum or aluminum alloy substrate U passes between the two targets 22, the particles sputtered on the surface of the two targets 22 are plated to complete the magnetron sputtering process. [0021] 具体 the specific operation and process parameters of the plasma cleaning may be: vacuuming the coating chamber 2〇 to a true degree of 8. Oxio — 3pa, to 3 〇〇 ~ 500sccm (standard state ML / min) The flow rate is argon gas (working gas) having a purity of 99.999% into the coating chamber 2, and a bias of -300 - 800 V is applied to the aluminum or aluminum alloy substrate to form a high in the coating chamber 2 The frequency voltage causes the argon gas to generate an argon plasma to physically bombard the surface of the aluminum or aluminum alloy substrate n to achieve the purpose of cleaning the surface of the aluminum or aluminum alloy substrate. The argon plasma cleaning time is 31 〇 min ^ [0022] After the aluminum or aluminum alloy substrate 11 is plasma-cleaned, an Al-Cu film 13 is formed on the aluminum or aluminum alloy substrate 11. The specific operation and process parameters for forming the Ai-cu film 13 are as follows: argon gas is used as the working gas, and the argon gas flow is adjusted. 099146985 Form No. A0101 Page 5 / Total 12 Page 0992080758-0 201226583 The quantity is 50~300sccm, and the duty ratio is set. 30%~80%, applying a bias of -50~-200V on the Lu or Ilu people gold substrate 11, and heating the film chamber to 100~150 ° C (ie, the sputtering temperature is 100~150 ° C); The power of the target material 22 is 2~8kw, the power of the target 22 is set to be 0. 5%~25%, and the power of the target 22 is 2~8kw. 'Deposit A A Cu film 13. The time for depositing the A-Cu film 13 is 45 to 120 μη. After the Al-Cu film 13 is formed, a violent metal ion is implanted into the surface of the ruthenium Cu film 13. [0024] The ion implantation process is performed by using an ion implanter (not shown) to place an inscription or alloy substrate 11 formed with an Al-Cu film 13 in a vacuum chamber of the ion implanter. The implanter ionizes the manganese metal to produce a violent metal ion vapor, and accelerates it by a high voltage electric field to form a manganese ion beam having tens of thousands or even millions of electron volts of energy, which is injected into the A-Cu film 13 , Table @, finally implants manganese metal ions on the surface of the yttrium Al-Cu film 13. [0〇25] According to the present embodiment A, the characteristics of the Cu film 13 and the finally formed a-Cu film significantly improve the corrosion resistance of the case, and the parameters of the Al-Cu film 13 when the violent ion implantation is performed It is set as follows: the degree of vacuum is 1χ1〇-4Pa, the ion source voltage is 30~l〇〇kV, the ion beam current intensity is 〇. 5mA, and the mass percentage of the implanted ionic ions in the Al-Cu film is 1%. -30%. The preparation method of the casing 10 and the casing 1〇 are further described below in conjunction with specific embodiments: [0027] Embodiment 1 098146985 Form No. A0101 Page 6 / Total 12 Page 0992080758-0 201226583 [0028] Plasma Cleaning: argon gas flow rate is 280sccm, aluminum or aluminum alloy substrate 11 is set to -300V, plasma cleaning time is 9 minutes; [0029] splashing copper and aluminum film 13: argon gas 100sccm, open aluminum copper The alloy target, the A-Cu alloy target power is set to 2kw, the aluminum or aluminum alloy substrate 11 is set to a bias voltage of -50V, and deposited for 100 minutes; [0030] The copper-aluminum film 13 is implanted with manganese metal ions: the vacuum is set to lxlO_4Pa, the ion 1 欧姆。 The source voltage is 30kV, the ion beam current intensity is 0. 1mA. Example 2 〇[0032] Plasma cleaning: argon gas flow rate is 230 sccm, aluminum or aluminum alloy substrate 11 has a bias voltage of -480 V, and plasma cleaning time is 7 minutes; [0033] Splashing copper layer 13: argon gas 200sccm is introduced, the copper alloy dry 22 is opened, the power of the Al-Cu alloy target is set to 5kw, the bias voltage of the substrate is set to -100V, and deposition is performed for 60 minutes; [0034] the copper-aluminum film 13 is implanted with manganese metal ions. : Set the vacuum to lxlO_4Pa, the ion source voltage to 60kV, and the ion beam current to 2mA. 3 [0036] Embodiment 3 [0036] Electropolymer cleaning: argon gas flow rate is 1 60sccm, Ming or Shao alloy substrate 11 bias is -400V, plasma cleaning time is 6 minutes; [0037] sputtering aluminum copper Layer 13: argon gas is introduced into 300 sccm, the aluminum-copper alloy target 22 is turned on, the Al-Cu alloy target power is set to 8 kW, the bias voltage of the aluminum or aluminum alloy substrate 11 is set to -200 V, and deposition is performed for 45 minutes; [0038] copper-aluminum film 13 injection of manganese metal ions: set the vacuum degree to lxlO_4Pa, from 099146985 Form No. A0101 Page 7 / Total 12 pages 0992080758-0 201226583 The sub-source voltage is 100kV, and the ion beam current intensity is 5mA. In the method of manufacturing the casing 10 of the preferred embodiment of the present invention, the A-Cu film 13 is sequentially formed on the aluminum or aluminum alloy substrate 11. And implanting manganese metal ions into the A-Cu film 13, which is implanted into the A-Cu film 13 to form an amorphous state, since the amorphous structure is isotropic, the surface has no grain boundaries, no dislocations, segregation, The characteristics of the homogeneous system, etc., Therefore, the AhCu film 13 after ion implantation of the manganese metal ions makes the shell 10 less likely to form a corrosive microbattery in the corrosive medium, and the possibility of electrochemical corrosion is extremely small, and the corrosion resistance of the shell 10 is greatly improved. Sex, and the manufacturing process is simple and almost free of environmental pollution. BRIEF DESCRIPTION OF THE DRAWINGS [0040] FIG. 1 is a cross-sectional view of a housing in accordance with 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] [0042] Housing: 10 [0043] Aluminum or aluminum alloy substrate: 11 [0044] A Bu Cu film: 13 [0045] Coating machine: 100 [0046] Coating chamber: 20 [0047] Vacuum pump :3 0 [0048] Track: 21 [0049] Target: 22 [0050] Air source channel: 24 099146985 Form number A0101 Page 8 / Total 12 pages 0992080758-0