201229285 六、發明說明： 【發明所屬之技術領域】 [麵]本發明涉及一種鎂合金表面防腐處理方法及其鎂製品。 [先前技術3 [0002]鎂合金具有品質輕、散熱性能好等優點，在通訊、電子 、交通運輸、建築及航太航空等領域應用廣泛。然，由 於鎂合金的化學活性較高’在空氣中很容易氧化，生成 疏鬆、保護能力差的氧化膜，導致鎂合金在潮濕的大氣 、土壤*海水巾發生嚴$腐採肖鎮合金製 作的產品的使用壽命縮短’阻礙了鎂合金的廣泛應用。 闺為了提祕合金的_純能，通t需要對鎮合金表面 崎表面成膜處理，常見的處理手段有陽極氧化處理、 烤漆等，然料工藝都存在較大㈣境污染問題。 ⑽膜（PVD)技術雖係-種非常環保的鍍膜卫蓺，且可 製的膜層種類豐富、耐磨性能優異，然，當承妓又 面具有微觀凹陷或空隙時，PVD工藝沉積的膜層^ 〇 基體表面的仿形結構，且沉積於該等凹陷或空隙内、 層往往其他區域的要薄，故在使用過程中，二述凹1膜 空隙區域往往更容易發生雜，使縣無=陷或 鎂合金基體被防腐。 防止 【發明内容】201229285 VI. Description of the invention: [Technical field to which the invention pertains] [Face] The present invention relates to a method for preserving a surface of a magnesium alloy and a magnesium product thereof. [Prior Art 3 [0002] Magnesium alloys have advantages such as light weight and good heat dissipation performance, and are widely used in fields such as communication, electronics, transportation, construction, and aerospace. However, due to the high chemical activity of magnesium alloys, it is easily oxidized in the air to form an oxide film with poor porosity and poor protection ability, resulting in the production of magnesium alloy in a humid atmosphere, soil * sea water towel. The shortened service life of the product has hindered the widespread use of magnesium alloys. In order to improve the _ pure energy of the alloy, it is necessary to form a film on the surface of the alloy surface. The common treatment methods are anodizing treatment, baking varnish, etc., and there are large (four) environmental pollution problems. (10) Although the film (PVD) technology is a very environmentally-friendly coating, it has a wide variety of film layers and excellent wear resistance. However, when the bearing has microscopic depressions or voids, the film deposited by PVD process The contour of the surface of the substrate is deposited in the depressions or voids, and the layers are often thinner in other regions. Therefore, in the process of use, the void regions of the two concave membranes are more likely to be miscellaneous, so that the county has no = trap or magnesium alloy substrate is preserved. Prevention [invention content]
剛㈣於此，有必要提供—種可效提高鎂合金 A 防腐處理方法。 性能的 剛科，還有必要提供―㈣上述枝製得的錢製。 100100106 表單編號A0101 第3頁/共13頁 1〇〇2〇〇〇1 201229285 [0006] 一種鎂合金表面防腐處理方法，包括以下步驟： [0007] 提供鎂合金基體； [0008] 對鎂合金基體進行化學除油； [0009] 用植物油酸為成膜劑的溶液對鎂合金基體進行化學轉化 處理，以於鎂合金基體上形成一層植物油酸轉化膜； [0010] 藉由真空鍍膜方法在該植物油酸轉化膜上形成由難熔化 合物組成的陶曼塗層。 [0011] 由上述鎂合金表面防腐處理方法所獲得的鎂製品，包括 鎂合金基體、形成於鎂合金基體表面的植物油酸轉化膜 及形成於該植物油酸轉化膜上的由難熔化合物組成的陶 瓷塗層。 [0012] 其中，該植物油酸轉化膜經用植物油酸為成膜劑的溶液 對鎂合金基體進行化學轉化處理而形成。 [0013] 本發明的鎂合金表面防腐處理方法先藉由化學轉化處理 於鎂合金基體上製備一層植物油酸轉化膜，然後於該植 物油酸轉化膜上鍍覆耐磨陶瓷塗層。其中該植物油酸轉 化膜一方面將鎂合金基體表面平整化，另一方面植物油 酸轉化膜自身結構緻密，阻擋性好，化學穩定性高，與 鎂合金基體結合力強，具有良好的防腐功能。而外層耐 磨的陶瓷塗層，可保護植物油酸轉化膜不易受到機械損 傷。故，經該方法處理的鎂製品具有良好的抗腐蝕性能 〇 【實施方式】 100100106 表單編號A0101 第4頁/共13頁 1002000188-0 201229285 [〇_本發日顿佳實施纏合金表面_處理方法包括如 驟： _請參閲圖卜提供鎮合金基體2〇。 [_純學除油。化學除純祕合金基 ^於6G_8GC的除油溶液中3G-6Gs。所用除油溶 為 325 30g/L碳酸鈉（Na^oy、2〇_25g/L磷酸三 (a3p〇4’12H2〇)及卜3g/L乳化劑的水溶液，其中所 、〈乳化4丨可用⑽心乳化劑，其主要組分為烧基紛與環氡 〇 乙烷的縮合物。 [ 丨鎮α至基體20進行驗餘處理。該驗钱處理步驟係將鎂 合金基體20浸潰於40_5(rc的驗性蚀刻液中3七。所用 驗性蝕刻液為含40-70g/L氫氧化鈉 (NaOH) ' 1〇 2〇g/LNa3P04'12H2〇 ' 25-30g/LNa2€〇3^ 40 5〇g/L氟化鈉（NaF)的水溶液。該鹼蝕處理—方面 用於消低鎂合金基體2〇上突出的部位，使鎂合金基體2〇 表面趨於平整’另一亨面可進一步去除鎂合金基體20表 面的油污》 [0018] 接著可對鎂合金基體20進行活化處理。該活化處理步驟 係將鎮合金基體20浸潰於含品質百分比濃度為1%-3%HF 的水溶液中3-5s，以去除鎂合金基體20因暴露於空氣中 的時間過長而在表面形成的氧化膜，使鎂合金基體2〇表 面被活化。 [0019] 用植物油酸（亦稱順-9-十八碳烯酸）為成膜劑的溶液對 鎂合金基體20進行化學轉化處理，以於鎂合金基體20上 100100106 表單編號A0101 第5頁/共13頁 1002000188-0 201229285 形成植物油酸轉化膜3 0。 [0020] 該化學轉化處理所用溶液配方可為含10-30ml/L植物油 油酸及酮類化合物的水溶液’其中該酮類化合物用於促 進植物油酸的溶解’該植物油酸溶液的pH值為2- 5。較佳 地，該植物油酸溶液為含15ml/L及丙酮的水溶液，其pH 值為2.8。處理方法可將經上述鹼蝕處理的鎂合金基體2〇 浸泡於30-50°C的該植物油酸溶液中2-4分鐘，浸泡過程 中可授拌溶液。較佳地，浸泡過程中該植物油酸溶液的 溫度保持為35°C，浸泡時間為2. 5分鐘。 [0021] 然後，對形成有所述植物油酸轉化膜30的鎂合金基體20 進行真空鍍膜處理，以在植物油酸轉化膜30上形成由難 熔化合物組成的陶瓷塗層40。該陶瓷塗層40包括一層或 多層金屬難熔化合物層，該金屬難熔化合物可選自鈦、 鋁、鉻、錘及鈷的氮化物、氧化物、氮碳化物及氮氧化 物中的一種或幾種的組合。本實施例中，該陶瓷塗層40 包括一層氧化鋁（Akop錄42及一層氮氧化鉻（Cr0N) 層43，該氧化鋁層42直接#成妓該植物油酸轉化膜30上 ，該氮氧化鉻層43形成於該氧化鋁層42上。 [0022] 該真空鍍膜處理可採用磁控濺射或電弧離子鍍，下面以 磁控濺射製備該氧化鋁層42及該氮氧化鉻層43為例對該 真空鍍膜處理進行說明。 [0023] 請參閱圖2，提供一磁控濺射設備1，磁控濺射設備1包括 一真空室2、用以對真空室2抽真空的真空泵3以及與真空 室2相通的氣源通道7。該真空室2内設有轉架4及相對設 100100106 表單编號A0101 第6頁/共13頁 1〇〇20〇〇^88-0 201229285 [0024] ❹ [0025]❹ [0026] [0027] 置的鋁靶5和鉻靶6。轉架4帶動鎂合金基體20做圓周運行 ，且鎂合金基體2 0在隨轉架4運行的同時亦進行自轉。鍍 膜時，濺射氣體與反應氣體經由氣源通道7進入真空室2 〇 在該植物油酸轉化膜30上濺射該氧化鋁層42。將形成有 該植物油酸轉化膜30的鎂合金基體20放置於磁控濺射設 備1的轉架4上，對真空室2抽真空至6. 0x1 (Γ3~8. Ox 10_3Pa後通入濺射氣體氬氣，氬氣流量為150〜300sccm (標準狀態毫升/分鐘），同時通入反應氣體氧氣，氧氣 流量為50~90sccm，錢合金基體20施加偏Μ至-100~-300V，開啟鋁靶5，鋁靶5的功率為8〜10kw，調節 真空室2内溫度為100〜150°C，轉架4的轉速為 0. 5 〜1. Orpm (revolution per minute，轉/分鐘） ，濺射0. 5~1小時，以於植物油酸轉化膜30表面形成該氧 化銘層42。 在氧化鋁層42上濺射該氮氧化鉻層43。關閉鋁靶5，開啟 鉻靶6，鉻靶6的功率為8〜10kw，調節氧氣流量為 40~100sccm，氮氣流量為30〜60sccm，其它參數保持不 變，濺射0. 5〜2小時，以在該氧化鋁層42上沉積一層氮氧 化絡層43。 鍍膜結束後，關閉負偏壓及鉻靶6電源，停止通入氬氣和 反應氣體，待所述氮氧化鉻層43冷卻後，向真空室2内通 入空氣，打開真空室門，取出鍍覆好的鎂製品10。 請參閱圖1，由上述鎂合金表面防腐處理方法所獲得的鎂 100100106 表單編號A0101 第7頁/共13頁 1002000188-0 201229285 製品10，包括鎂合金基體20、形成於鎂合金基體20表面 的植物油酸轉化膜3 0及形成於該植物油酸轉化膜3 0上的 由難炫化合物組成的陶竞塗層4 0。該植物油酸轉化膜3 0 經用植物油酸為成膜劑的溶液對鎂合金基體2 0進行化學 轉化處理而形成。該陶究塗層40包括一層或多層金屬難 溶化合物層，該金屬難炫化合物可選自鈦、銘、鉻、錯 及钴的氮化物、氧化物、氮礙化物及氮氧化物中的一種 或幾種的組合。本實施例中，該陶瓷塗層4 0包括一層氧 化鋁（Al9〇q)層42及一層氮氧化鉻（CrON)，該氧化鋁 層42直接形成於該植物油酸轉化膜30上，該氮氧化鉻層 43形成於該氧化鋁層42上。 [0028] 對由本發明的防腐處理方法所製備的鎂製品10試樣進行 35°C中性鹽霧（NaCl濃度為5%)測試。結果發現，鎂製 品10試樣在72小時後才出現有腐蝕現象，具有良好的防 腐性能。 [0029] 本發明的鎂合金表面防腐處理方法先藉由化學轉化處理 於鎂合金基體20上製備一層植物油酸轉化膜30，然後於 該植物油酸轉化膜30上鍍覆耐磨陶瓷塗層40。其中該植 物油酸轉化膜30—方面將鎂合金基體20表面平整化，另 一方面植物油酸轉化膜30自身結構緻密，阻擋性好，化 學穩定性高，與鎂免金基體20結合力強，具有良好的防 腐功能。而外層耐磨的陶瓷塗層40，可保護植物油酸轉 化膜30不易受到機械損傷。故，經該方法處理的鎂製品 10具有良好的抗腐蝕性能。 【圖式簡單說明】 100100106 表單編號A0101 第8頁/共13頁 1002000188-0 201229285 [0030] 圖1為由本發明較佳實施例的鎂合金表面防腐處理方法所 [0031] 製得的鎂製品的剖視示意圖。 圖2為本發明較佳實施例的鎂合金表面防腐處理方法中所 用鍍膜設備示意圖。 [0032] 【主要元件符號說明】 鎂製品：10 [0033] 鎂合金基體：20 [0034] 〇 [0035] 植物油酸轉化膜：30 陶瓷塗層：40 [0036] 氧化鋁層：42 [0037] 氮氧化鉻層：43 [0038] 磁控濺射設備：1 [0039] 真空室：2 [0040] 〇 [0041] 真空泵：3 轉架：4 [0042] 鋁靶：5 [0043] 鉻靶：6 [0044] 氣源通道：7 100100106 表單編號A0101 第9頁/共13頁 1002000188-0Just now (four), it is necessary to provide a kind of effective treatment to improve the corrosion treatment of magnesium alloy A. For the performance of Gangke, it is also necessary to provide "(4) the money system made by the above branches. 100100106 Form No. A0101 Page 3 of 13 1〇〇2〇〇〇1 201229285 [0006] A magnesium alloy surface anticorrosive treatment method comprising the following steps: [0007] providing a magnesium alloy matrix; [0008] a magnesium alloy matrix Performing chemical degreasing; [0009] chemically converting a magnesium alloy substrate with a solution of a vegetable oleic acid as a film forming agent to form a vegetable oleic acid conversion film on the magnesium alloy substrate; [0010] the vegetable oil is applied by a vacuum coating method A Tauman coating composed of a refractory compound is formed on the acid conversion film. [0011] The magnesium product obtained by the above-mentioned magnesium alloy surface anti-corrosion treatment method comprises a magnesium alloy substrate, a vegetable oleic acid conversion film formed on the surface of the magnesium alloy substrate, and a ceramic composed of a refractory compound formed on the vegetable oleic acid conversion film. coating. [0012] wherein the vegetable oleic acid conversion membrane is formed by chemically converting a magnesium alloy substrate with a solution of a vegetable oleic acid as a film former. [0013] The magnesium alloy surface anti-corrosion treatment method of the present invention first prepares a layer of vegetable oleic acid conversion film by chemical conversion treatment on a magnesium alloy substrate, and then plated the wear-resistant ceramic coating on the plant oleic acid conversion film. The vegetable oleic acid conversion film planarizes the surface of the magnesium alloy substrate on the one hand, and the vegetable oleic acid conversion film itself has a compact structure, good barrier property, high chemical stability, strong binding force with the magnesium alloy matrix, and good anti-corrosion function. The outer wear-resistant ceramic coating protects the vegetable oleic acid conversion film from mechanical damage. Therefore, the magnesium product treated by the method has good corrosion resistance 〇 [Embodiment] 100100106 Form No. A0101 Page 4 / Total 13 Page 1002000188-0 201229285 [〇_本发日顿佳 implemented wrapped alloy surface _ treatment method Including the steps: _ Please refer to Figure b to provide the town alloy matrix 2〇. [_ Pure learning to remove oil. Chemical removal of pure alloy base ^ 3G-6Gs in 6G_8GC deoiling solution. The degreasing solution used is an aqueous solution of 325 30g/L sodium carbonate (Na^oy, 2〇_25g/L phosphoric acid tris(a3p〇4'12H2〇) and Bu 3g/L emulsifier, wherein: (10) A heart emulsifier whose main component is a condensate of a sulfonyl group and a cyclohexane ethane. [The α α α to the base 20 is subjected to a residual treatment. The money processing step is to immerse the magnesium alloy substrate 20 in 40_5. (The lithographic etchant is 37. The etchant used is 40-70g/L sodium hydroxide (NaOH) ' 1〇2〇g/LNa3P04'12H2〇' 25-30g/LNa2€3^ 40 5〇g/L aqueous solution of sodium fluoride (NaF). The alkali etching treatment is used to reduce the protruding portion of the magnesium alloy matrix 2, so that the surface of the magnesium alloy substrate 2 tends to be flat. The oil stain on the surface of the magnesium alloy substrate 20 can be further removed. [0018] The magnesium alloy substrate 20 can then be subjected to an activation treatment. The activation treatment step is to impregnate the town alloy substrate 20 with a concentration percentage of 1% to 3% HF. 3-5 s in an aqueous solution to remove the oxide film formed on the surface of the magnesium alloy substrate 20 due to excessive exposure to air, so that the surface of the magnesium alloy substrate 2 is [0019] The magnesium alloy substrate 20 is chemically converted with a solution of vegetable oleic acid (also known as cis-9-octadecenoic acid) as a film former to the magnesium alloy substrate 20 100100106 Form No. A0101 No. 5 Page / Total 13 pages 1002000188-0 201229285 Forming vegetable oleic acid conversion membrane 30. [0020] The solution formulation used in the chemical conversion treatment may be an aqueous solution containing 10-30 ml/L of vegetable oleic acid and a ketone compound, wherein the ketone compound For promoting the dissolution of vegetable oleic acid, the pH of the vegetable oleic acid solution is 2 to 5. Preferably, the vegetable oleic acid solution is an aqueous solution containing 15 ml/L and acetone, and the pH is 2.8. The alkali-etched magnesium alloy substrate 2 is immersed in the vegetable oleic acid solution at 30-50 ° C for 2-4 minutes, and the solution can be mixed during the soaking process. Preferably, the temperature of the vegetable oleic acid solution during the soaking process is maintained as Then, the magnesium alloy substrate 20 on which the vegetable oleic acid conversion film 30 is formed is subjected to vacuum coating treatment to form a refractory compound on the vegetable oleic acid conversion film 30 at 35 ° C. Composition of ceramic coating 40. The ceramic coating 40 comprises one or more layers of a metal refractory compound which may be selected from the group consisting of titanium, aluminum, chromium, hammer and cobalt nitrides, oxides, nitrogen carbides and oxynitrides. In one embodiment, the ceramic coating 40 comprises a layer of aluminum oxide (Akop recorded 42 and a layer of chromium oxynitride (Cr0N) layer 43 which directly forms the vegetable oleic acid conversion coating film. At 30, the chromium oxynitride layer 43 is formed on the aluminum oxide layer 42. [0022] The vacuum coating treatment may be performed by magnetron sputtering or arc ion plating, and the vacuum coating treatment will be described by taking the alumina layer 42 and the chromium oxynitride layer 43 by magnetron sputtering as an example. Referring to FIG. 2, a magnetron sputtering apparatus 1 is provided. The magnetron sputtering apparatus 1 includes a vacuum chamber 2, a vacuum pump 3 for evacuating the vacuum chamber 2, and a gas source passage communicating with the vacuum chamber 2. 7. The vacuum chamber 2 is provided with a turret 4 and a relative setting 100100106. Form No. A0101 Page 6 / Total 13 Page 1 〇〇 20 〇〇 ^ 88-0 201229285 [0024] ❹ [0025] 0026 [0026] [0027] The aluminum target 5 and the chromium target 6 are placed. The turret 4 drives the magnesium alloy substrate 20 to perform circumferential operation, and the magnesium alloy substrate 20 also rotates while running along with the turret 4. At the time of plating, the sputtering gas and the reaction gas enter the vacuum chamber 2 via the gas source passage 7, and the alumina layer 42 is sputtered on the vegetable oleic acid conversion film 30. The magnesium alloy substrate 20 on which the vegetable oleic acid conversion film 30 is formed is placed on the turret 4 of the magnetron sputtering apparatus 1, and the vacuum chamber 2 is evacuated to 6. 0x1 (Γ3~8. Ox 10_3Pa and then sputtered) Gas argon gas, argon gas flow rate is 150~300sccm (standard state cc/min), and oxygen gas is introduced into the reaction gas, the oxygen flow rate is 50~90sccm, and the carbon alloy substrate 20 is biased to -100~-300V to open the aluminum target. 5〜1. Orpm (revolution per minute, rpm), sputtering, the power of the aluminum target 5 is 8~10kw, the temperature in the vacuum chamber 2 is adjusted to 100~150°C, and the rotation speed of the turret 4 is 0. 5 〜1. 0.5 to 1 hour, the oxide layer 42 is formed on the surface of the vegetable oleic acid conversion film 30. The chromium oxynitride layer 43 is sputtered on the aluminum oxide layer 42. The aluminum target 5 is turned off, the chromium target 6 is turned on, and the chromium target 6 is opened. The power is 8~10kw, the oxygen flow rate is 40~100sccm, the nitrogen flow rate is 30~60sccm, the other parameters are kept unchanged, and the sputtering is 0.5~2 hours to deposit a layer of nitrogen oxide on the aluminum oxide layer 42. Layer 43. After the coating is completed, the negative bias voltage and the chromium target 6 power supply are turned off, and the introduction of argon gas and the reaction gas is stopped, and the chromium oxynitride is to be replaced. After cooling 43, air is introduced into the vacuum chamber 2, the vacuum chamber door is opened, and the plated magnesium product 10 is taken out. Referring to Fig. 1, the magnesium 100100106 obtained by the above-mentioned magnesium alloy surface anticorrosive treatment method is shown in Form No. A0101. Page 10/13 of 1002000188-0 201229285 Article 10 includes a magnesium alloy substrate 20, a vegetable oleic acid conversion film 30 formed on the surface of the magnesium alloy substrate 20, and a hard-to-dark compound formed on the vegetable oleic acid conversion film 30. Tao Jing Coating 40. The vegetable oleic acid conversion film 30 is formed by chemically converting a magnesium alloy substrate 20 with a solution of vegetable oleic acid as a film former. The ceramic coating 40 comprises one or more layers of metal insoluble. a compound layer, the metal refractory compound may be selected from one or a combination of titanium, indium, chromium, cobalt and oxides, oxides, nitrogen compounds and nitrogen oxides. In this embodiment, the ceramic The coating 40 includes a layer of aluminum oxide (Al9〇q) 42 and a layer of chromium oxynitride (CrON) formed directly on the vegetable oleic acid conversion film 30, and the chromium oxynitride layer 43 is formed in the oxidation. On the aluminum layer 42. [002 8] The magnesium product 10 sample prepared by the anticorrosive treatment method of the present invention was subjected to a 35 ° C neutral salt spray (NaCl concentration of 5%) test, and it was found that the magnesium product 10 sample showed corrosion after 72 hours. Phenomenon, having good anticorrosive properties. [0029] The magnesium alloy surface anticorrosive treatment method of the present invention first prepares a layer of vegetable oleic acid conversion film 30 on the magnesium alloy substrate 20 by chemical conversion treatment, and then plated on the vegetable oleic acid conversion film 30. Wear-resistant ceramic coating 40. The vegetable oleic acid conversion film 30-flatizes the surface of the magnesium alloy substrate 20, and on the other hand, the vegetable oleic acid conversion film 30 has a compact structure, good barrier property, high chemical stability, and strong binding force with the magnesium-free gold matrix 20, Good anti-corrosion function. The outer layer of the wear-resistant ceramic coating 40 protects the vegetable oleic acid conversion film 30 from mechanical damage. Therefore, the magnesium product 10 treated by this method has good corrosion resistance. BRIEF DESCRIPTION OF THE DRAWINGS 100100106 Form No. A0101 Page 8 of 13 1002000188-0 201229285 [0030] FIG. 1 is a magnesium product prepared by the surface treatment method for magnesium alloy according to a preferred embodiment of the present invention [0031] A schematic cross-sectional view. Fig. 2 is a schematic view showing a coating apparatus used in a method for preserving a surface of a magnesium alloy according to a preferred embodiment of the present invention. [Main component symbol description] Magnesium product: 10 [0033] Magnesium alloy substrate: 20 [0034] Vegetable oleic acid conversion film: 30 Ceramic coating: 40 [0036] Alumina layer: 42 [0037] Chromium oxynitride layer: 43 [0038] Magnetron sputtering equipment: 1 [0039] Vacuum chamber: 2 [0040] 〇 [0041] Vacuum pump: 3 turret: 4 [0042] Aluminum target: 5 [0043] Chromium target: 6 [0044] Air source channel: 7 100100106 Form number A0101 Page 9 / Total 13 pages 1002000188-0