201207132 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種铭合金表面防腐處理方法及其製品。 【先前技術】 [〇〇〇2] 鋁合金具有品質輕、散熱性能好等優點，在通訊、電子 、交通運輸、建桌及航太航空等領域應用廣泛。在空氣 中紹合金表面會形成氧化铭保護膜，於一般大氣環境下 ’紹合金表面的氧化紹膜能夠有效地對合金基體進行 保護，但在含有電解質的濕氣中，例如海洋表面大氣環 土兄，is合金表面容易出現點|虫”嚴重破環麵合金製品的 外觀，同時導致製品使用壽命縮短。 [_為了提高銘合金的_霧性能，通要對銘合金表面 進行表面成膜處理，常見的處理手段有陽極氧化處理、 烤漆等’然，該等工藝均存在較大的環境污染問題。而 真空鍍膜（PVD)技術雖係一種非常環保的鍍膜工藝，且可 鍍製的膜層種類豐富、耐磨性能優異，然，PVD工藝沉積 的薄膜往往係以柱狀晶形轉生長，敌膜層存在大量的晶 間間隙，導致溥膜緻饴性不夠而無法有效地防止鹽霧的 侵钱。 【發明内容】 [0004] 有鑒於此，有必要提供一種有效的鋁合金表面防腐處理 方法。 [0005] 另外，還有必要提供一種由上述方法製得的鋁合金製品 099126857 表單編號Α0101 第4頁/共13頁 0992047143-0 201207132 [0006] [0007] [0008] [0009] Ο [0010] c [0011] [0012] [0013] 一種鋁合金表面防腐處理方法，包括以下步驟： (1 )採用無水乙醇對鋁合金基材進行超聲波清洗； (2)以純鉻為靶材，以氬氣為工作氣體，氮氣和氧氣為 反應氣體，採用磁控濺射法在鋁合金基材表面濺鍍一鉻 氧氮化合物薄膜，所述氧氣流量為10〜150sccm，氮氣流 量為 1 0〜1 0Osccm。 一種經上述方法處理的銘合金製品，包括銘合金基材及 形成於鋁合金基材表面的一鉻氧氮化合物薄膜，該鉻氧 氮化合物薄膜中鉻原子個數百分比為46%〜70%，氧原子個 數百分比為20%〜5 0°/。，氮原子個數百分比為5%〜10%。 相較於習知技術，由上述鋁合金表面防腐處理方法所製 得的鋁合金製品由於其表面具有一鉻氧氮化合物薄膜， 該鉻氧氮化合物薄膜由比較細小的晶粒組成，晶間間隙 比較小，使得鉻氧氮化合物薄膜比較緻密，可有效防止 鹽霧侵蝕，故可有效提高鋁合金的抗腐蝕性能。 實施方式】 本發明鋁合金表面防腐處理方法主要包括如下步驟： (1 )採用無水乙醇對鋁合金基材進行超聲波清洗，以除 去試樣表面油污。 (2)以純鉻為靶材，以氬氣為工作氣體，氮氣和氧氣為 反應氣體，採用磁控濺射法在經清洗後的鋁合金基材表 面鍍製一鉻氧氮化合物（Cr-0-Ν)薄膜。濺射參數如下： 真空腔内真空度為5xl〇-3Pa〜9xlO-3Pa，腔體溫度為 100〜180°C，轉架轉速為0.5〜1轉/分鐘，氬氣流量為 099126857 表單編號A0101 第5頁/共13頁 0992047143-0 201207132 150〜300sccm (標準狀態毫升/分鐘），氧氣流量為 10〜150sccm，氮氣流量為10〜lOOsccm，鉻乾功率為 6〜12kw，偏壓為-100~-300V，佔空比為40%〜60%，濺射 0. 5~2小時。由此在鋁合金基材表面獲得厚度大約0. 4〜2 // m的所述鉻氧氮化合物薄膜。 [0014] 由上述鋁合金表面防腐處理方法所獲得的鋁合金製品， 包括銘合金基材及形成於銘合金基材表面的鉻氧氮化合 物薄膜，該鉻氧氮化合物薄膜中鉻原子個數百分比為 46%〜70%，氧原子個數百分比為20%〜50%，氮原子個數百 分比為5°/。~10%。該鉻氧氮化合物薄膜由直徑大約為 5~8nm的晶粒組成。 [0015] 下面藉由實施例來對本發明進行具體說明。 [0016] 實施例1 [0017] 採用無水乙醇對鋁合金試樣進行超聲波清洗大約30分鐘 。將清洗好的鋁合金試樣放入中頻磁控濺射鍍膜機的真 空腔中。本實施例所使用的中頻磁控濺射鍍膜機為深圳 南方創新真空技術有限公司生產，型號為SM-1100H。 [0018] 開啟真空泵對真空腔抽真空並設定真空度為8x10-3Pa， 開啟轉架並設定轉速為0. 5轉/分鐘，開啟真空腔烘烤並 設定腔内溫度為120°C。 [0019] 待真空腔的真空度抽至上述設定值後，通入工作氣體氬 氣及反應氣體氧氣和氮氣，氬氣流量為150sccm (標準狀 態毫升/分鐘），氧氣流量為40seem，氮氣流量為 30sccm ;開啟鉻靶並調節鉻靶功率為8kw，偏壓-200V， 099126857 表單編號A0101 第6頁/共13頁 0992047143-0 201207132 [0020] [0021] [0022] Ο [0023] [0024] [0025] 〇 099126857 佔空比為50%，濺射1小時，由此在鋁合金表面獲得一鉻 氧氮化合物薄膜。 實施例2 實施例2與實施例1類似，不同之處在於，本實施例的氧 氣流量為lOOsccm，氮氣流量為60sccm，其他條件均與 實施例1相同。按照實施例2也可以製得表面形成有一鉻 氧氮化合物薄膜的鋁合金製品。 由實施例1和實施例2製得的鋁合金製品的鉻氧氤化合物 薄膜形貌、結構比較類似，且具有類似的防腐性能。 對比例 採用與實施例1相同的中頻磁控濺射鍍膜機對鋁合金試樣 進行濺射，與實施例1不同之處在於反應氣體為氮氣，氮 氣流量為3 0〜10 0 sccm，其他條件與實施例1相同，在銘 合金試樣表面濺鍍一單組分氮化鉻（CrN)薄膜。 對實施例1鍍製的鉻氧氮化合物薄膜和對比例鍍製的氮化 鉻（CrN)薄膜分別用掃描電鏡觀察其表面形貌，所用掃描 電鏡儀為曰本精工生產的型號為JSM-6701F的場發射掃 描電鏡儀。圖1為對比例鍍製的氮化鉻（CrN)薄膜的掃描 電鏡圖，圖2及圖3為本發明實施例1鍍製的鉻氧氮化合物 薄膜的掃描電鏡圖。從圖1、圖2及圖3可以看出，單組分 氮化鉻（C r N )薄膜由比較粗大的柱狀晶構成，且表面存在 大量較大的晶間間隙，而鉻氧氮化合物薄膜由比較細小 的晶粒組成（參圖3)，晶粒平均直徑大約為5〜8nm，晶 間間隙比較小，使得鉻氧氮化合物薄膜比較緻密。 表單編號A0101 第7頁/共13頁 0992047143-0 201207132 [0026] 對由本發明的方法所製備的鍍覆有鉻氧氮化合物薄膜的 ί呂合金試樣和對比例所製得的鑛覆氮化鉻（C r N)薄膜的銘 合金試樣進行35°C中性鹽霧（NaCl濃度為5%)測試。結 果發現，表面鍍覆氮化鉻（CrN)薄膜的鋁合金試樣4小時 後就發生明顯腐蝕；而表面鍍覆鉻氧氮化合物薄膜的鋁 合金試樣於72小時後才出現腐蝕現象。 [0027] 可見，由本發明的鋁合金表面防腐處理方法所製得的鋁 合金製品由於其表面具有一鉻氧氮化合物薄膜，該鉻氧 氮化合物薄膜可有效防止鹽霧侵蝕，故可提高鋁合金的 抗腐钮性能。 【圖式簡單說明】 [0028] 圖1為一採用磁控濺鍍法製備的氮化鉻薄膜的放大5萬倍 的掃描電鏡圖。 [0029] 圖2為本發明一實施例製備的鉻氧氮化合物薄膜的放大5 萬倍的掃描電鏡圖。 [0030] 圖3為圖2所示的鉻氧氮化合物薄膜放大30萬倍的掃描電 鏡圖。 【主要元件符號說明】 [0031] 無 099126857 表單編號A0101 第8頁/共13頁 0992047143-0201207132 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a surface alloy anti-corrosion treatment method and an article thereof. [Prior Art] [〇〇〇2] Aluminum alloy has the advantages of light weight, good heat dissipation performance, and is widely used in communications, electronics, transportation, construction, and aerospace. In the air, the surface of the alloy will form an oxidized protective film. Under normal atmospheric conditions, the oxide film on the surface of the alloy can effectively protect the alloy matrix, but in the moisture containing electrolyte, such as the ocean surface atmosphere Brother, the surface of the alloy is prone to occur. The appearance of the severely broken toroidal alloy product and the shortened service life of the product. [_ In order to improve the _ fog performance of the alloy, it is necessary to perform surface film formation on the surface of the alloy. Common treatment methods include anodizing, baking varnish, etc. These processes all have large environmental pollution problems, while vacuum coating (PVD) technology is a very environmentally friendly coating process, and the types of coatings that can be plated. Rich and wear-resistant performance is excellent. However, the film deposited by PVD process tends to grow in a columnar crystal shape. There are a large number of intergranular gaps in the enemy film layer, which leads to insufficient tantalum enthalpy and cannot effectively prevent salt fog from invading. SUMMARY OF THE INVENTION [0004] In view of the above, it is necessary to provide an effective aluminum alloy surface anti-corrosion treatment method. [0005] In addition, there must be An aluminum alloy article made by the above method is provided. 099126857 Form No. 1010101 Page 4 / Total 13 Page 0992047143-0 201207132 [0006] [0008] [0009] [0010] [0012] [0012] 0013] A method for preserving the surface of an aluminum alloy, comprising the following steps: (1) ultrasonic cleaning of the aluminum alloy substrate with anhydrous ethanol; (2) using pure chromium as a target, argon gas as working gas, nitrogen and oxygen as reaction The gas is sputtered on the surface of the aluminum alloy substrate by a magnetron sputtering method, and the oxygen flow rate is 10 to 150 sccm, and the nitrogen flow rate is 10 to 1 0 Osccm. The invention comprises an alloy substrate and a chromium oxynitride film formed on the surface of the aluminum alloy substrate, wherein the chromium oxide compound film has a percentage of chromium atoms of 46% to 70% and an oxygen atom percentage of 20%. 50 ° /., the number of nitrogen atoms is 5% ~ 10%. Compared with the prior art, the aluminum alloy product prepared by the above aluminum alloy surface anti-corrosion treatment method has a chromium oxynitride film on its surface. , the chromoxy nitrogen The film is composed of relatively fine crystal grains, and the intergranular gap is relatively small, so that the chromium oxynitride film is relatively dense and can effectively prevent salt spray erosion, so that the corrosion resistance of the aluminum alloy can be effectively improved. The alloy surface anti-corrosion treatment method mainly includes the following steps: (1) ultrasonic cleaning of the aluminum alloy substrate by using anhydrous ethanol to remove oil stain on the surface of the sample. (2) using pure chromium as a target material, argon gas as working gas, nitrogen gas and Oxygen is a reactive gas, and a chromium oxynitride (Cr-0-Ν) film is plated on the surface of the cleaned aluminum alloy substrate by magnetron sputtering. The sputtering parameters are as follows: The vacuum degree in the vacuum chamber is 5xl〇-3Pa~9xlO-3Pa, the cavity temperature is 100~180°C, the rotating speed is 0.5~1 rev/min, and the argon flow rate is 099126857. Form No. A0101 5 pages/total 13 pages 0992047143-0 201207132 150~300sccm (standard state cc/min), oxygen flow rate is 10~150sccm, nitrogen flow rate is 10~lOOsccm, chromium dry power is 6~12kw, bias voltage is -100~- 5〜2小时。 With a duty of 40% ~ 60%, sputtering 0. 5~2 hours. The chromium oxynitride film having a thickness of about 0.4 to 2 // m is obtained on the surface of the aluminum alloy substrate. [0014] The aluminum alloy article obtained by the above-mentioned aluminum alloy surface anti-corrosion treatment method comprises an alloy substrate and a chromium oxynitride film formed on the surface of the alloy substrate, and the percentage of chromium atoms in the chromium oxide compound film It is 46% to 70%, the percentage of oxygen atoms is 20% to 50%, and the percentage of nitrogen atoms is 5°/. ~10%. The chromium oxynitride film is composed of crystal grains having a diameter of about 5 to 8 nm. [0015] The present invention will be specifically described below by way of examples. [0016] Example 1 [0017] An aluminum alloy sample was ultrasonically cleaned using absolute ethanol for about 30 minutes. The cleaned aluminum alloy sample was placed in the true cavity of an intermediate frequency magnetron sputtering coater. The intermediate frequency magnetron sputtering coating machine used in this embodiment is produced by Shenzhen Southern Innovation Vacuum Technology Co., Ltd., model SM-1100H. [0018] The vacuum pump is turned on to vacuum the vacuum chamber and the vacuum is set to 8x10-3Pa, the turntable is turned on and the rotation speed is set to 0.5 rpm, the vacuum chamber is opened and the temperature in the chamber is set to 120 °C. [0019] After the vacuum of the vacuum chamber is drawn to the above set value, the working gas argon gas and the reaction gas oxygen and nitrogen are introduced, the flow rate of the argon gas is 150 sccm (standard state ML/min), the oxygen flow rate is 40 seem, and the nitrogen flow rate is 30sccm; turn on the chrome target and adjust the chrome target power to 8kw, bias -200V, 099126857 Form No. A0101 Page 6 / Total 13 Page 0992047143-0 201207132 [0020] [0022] [0022] [0023] [0024] 0025] 〇099126857 A duty ratio of 50%, sputtering for 1 hour, thereby obtaining a chromium oxynitride film on the surface of the aluminum alloy. Example 2 Example 2 was similar to Example 1, except that the oxygen gas flow rate of this example was 100 sccm, and the nitrogen gas flow rate was 60 sccm, and other conditions were the same as in Example 1. An aluminum alloy article having a chromium oxynitride film formed on the surface thereof was also obtained in accordance with Example 2. The chromia oxyhalide compound films of the aluminum alloy articles obtained in Example 1 and Example 2 were similar in morphology and structure, and had similar corrosion resistance. Comparative Example The aluminum alloy sample was sputtered by the same intermediate frequency magnetron sputtering coater as in Example 1. The difference from Example 1 was that the reaction gas was nitrogen, and the flow rate of nitrogen was 30 to 10 0 sccm. The conditions were the same as in Example 1, and a single-component chromium nitride (CrN) film was sputtered on the surface of the alloy sample. The surface morphology of the chromium oxynitride film and the chromium nitride (CrN) film plated in the first example were observed by scanning electron microscopy. The scanning electron microscope used in this model was model JSM-6701F produced by Sakamoto Seiko. Field emission scanning electron microscope. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a scanning electron micrograph of a comparatively plated chromium nitride (CrN) film, and Figs. 2 and 3 are scanning electron micrographs of a chromium oxynitride film deposited in Example 1 of the present invention. It can be seen from Fig. 1, Fig. 2 and Fig. 3 that the one-component chromium nitride (CrN) film is composed of relatively coarse columnar crystals, and a large amount of intergranular gap exists on the surface, and the chromium oxide compound The film is composed of relatively fine crystal grains (refer to FIG. 3), and the average crystal grain diameter is about 5 to 8 nm, and the intergranular gap is relatively small, so that the chromium oxynitride film is relatively dense. Form No. A0101 Page 7 of 13 0992047143-0 201207132 [0026] The nitriding alloy prepared by the method of the present invention and coated with a chromia oxynitride film and a comparative example A sample of the alloy of chromium (C r N) film was tested at 35 ° C neutral salt spray (5% NaCl concentration). As a result, it was found that the aluminum alloy sample coated with the chromium nitride (CrN) film on the surface showed significant corrosion after 4 hours; and the aluminum alloy sample coated with the chromium oxide compound film on the surface did not corrode after 72 hours. [0027] It can be seen that the aluminum alloy product prepared by the aluminum alloy surface anti-corrosion treatment method of the present invention has a chromium oxynitride film on the surface thereof, and the chromium oxynitride film can effectively prevent salt spray erosion, thereby improving the aluminum alloy. Anti-corrosion button performance. BRIEF DESCRIPTION OF THE DRAWINGS [0028] FIG. 1 is a scanning electron micrograph of a 50,000-fold magnification of a chromium nitride film prepared by magnetron sputtering. 2 is a scanning electron micrograph of a 50,000-fold magnification of a chromium oxynitride film prepared according to an embodiment of the present invention. 3 is a scanning electron micrograph of the chromium oxynitride film shown in FIG. 2 magnified 300,000 times. [Main component symbol description] [0031] None 099126857 Form No. A0101 Page 8 of 13 0992047143-0