1275665 玖、發明說明 【發明所屬之技術領域】 本發明係有關於一種鎂金屬之陽極氧化處理液，特別 是適用於鎮金屬表面處理的陽極氧化處理液。 【先前技術】 在輕量化的需求下，鎂及其合金已受到相當的重視。 鎂合金因其密度低（約1.7 g/cm2)、強度重量比高、電磁遮 蔽性佳等特性，在汽車工業、休閒設備、3C產品等方面 已大量的被使用，但是，在鎮合金的發展過程以及運用領 域中，耐蝕性不佳一直是鎂合金最大的致命傷，因此鎂合 金較少使用於結構性或腐餘性較高的環境中。為了改善鎂 合金之耐蝕性質、擴展鎂合金之應用領域及延長使用壽命 和安全性的考量，耐蝕處理是很重要的步驟，其中表面處 理為重要且有效的方法之一，各種與鎮及其合金相關之表 面耐蝕處理一直是學者研究的課題。其中，陽極氧化處理 所得之保護膜具有較佳的耐磨耗以及保護性，為相當適合 鎂合金之表面耐餘處理方式。 陽極氧化處理係利用火花放電（Sparking)時產生的局 部高溫’促使鎂合金表面形成一層類似燒結之陶瓷的氧^匕 層，即陽極膜，藉由陽極膜良好的保護性保護鎂合金基材 而達到增加耐蝕性的效果，較於其他表面處理，陽：氧 j理的耐磨耗性較佳，塗裝的时性㈣，相#適用於 、°金的表面耐蝕處理’為近年來相當受到重視的鎂合金 1275665 表面處理方法之一。 、一 f來說，陽極氧化處理技術主要是在鎂合金表面形 成層陽極膜，力陽極膜層必須肖勾的覆蓋於表面，以免 在陽極氧化處理後陽極膜的缺陷反而加速基材的破壞，同 時所成長之陽極膜也必須提供優良的保㈣，才能達到保 濩鎂合金基材的效果。所以陽極膜的均勻性、成分及結構 等，都是決定陽極膜保護性好壞的一個關鍵。進一步而 言，要成長性質佳且可以保護鎂合金的陽極膜層，使其不 受外在腐蝕環境影響，其關鍵在於陽極氧化處理時所使用 之電解液，而電解液的組成及其中之添加物，都會影響陽 極氧化處理之結果以及陽極膜的性質。 鎮及其合金之陽極氧化處理液原以鉻酸鹽類為主，但 近年來環保意識抬頭，鉻酸鹽類的陽極氧化處理液或化成 處理（Conversion Coating)電解液已漸漸被淘汰，低污染環 保型之陽極氧化處理液開始成為主流，這類的陽極氧化處 理液包含氟化物、磷酸鹽類、硫酸鹽類、氫氧化鉀（K〇H)、 風氧化納（NaOH)等。在陽極氧化處理液中加入麟酸鹽， 一般認為可以縮小陽極膜上因火花放電造成之孔洞，而陽 極氧化處理液中加入氟化物，可以增強陽極膜之耐刮傷磨 損性。 1¾極氧化處理所得之保護膜雖具較佳的耐磨耗以及 保δ蔓性’相當適用於鎂合金之表面耐敍處理，但因其技術 尚未成熟，應用在鎖合金產業上之陽極氧化處理仍然有 限。舉例而言，壓鑄（Die Casting)AZ91D鎂合金在含有氮 1275665 以及碟酸鈉之陽極氧化處理液進行陽極 氧化處理過程中’會產生火花放電集中之現象，而造成陽 極膜生長不均勻的情％。為符合未來鎖合金使用上的需 求，實有其必要改變電解液組成來改善火花放電集中之現 象以冀獲得均勻之陽極膜，並提升鎂及鎂合金之耐蝕能 【發明内容】 因此本發明的目的之一就是揭露一種鎖金屬之陽極 氧化處理液，此鎂金屬之陽極氧化處理液係至少包含矽酸 鹽及硝酸鹽，其中矽酸鹽可提升陽極膜對鎂金屬之保護 性，硝酸鹽則可使陽極膜均勻生長於鎂金屬之表面。 本發明之另一目的就是揭露一種鎂金屬之陽極氧化 處理方法’此陽極氧化處理方法係利用本發明之鎂金屬之 陽極氧化處理液，於此電解液中針對鎂金屬表面進行陽極 氧化處理。如此一來，可提昇鎂金屬之陽極膜之保護性， 更改善艤金屬在陽極氧化處理過程中火花放電引起陽極 膜不均勻的問題。 根據本發明上述之目的，提出一種鎂金屬之陽極氧化 處理液，至少包含：〇·01莫耳濃度（M)至2 Μ之矽酸鹽； 〇·〇1 Μ至2Μ之硝酸鹽；〇·1 Μ至5 Μ之氫氧化鉀；u Μ 至1 Μ之氟化鉀；〇」μ至1 Μ之磷酸鈉；以及去離子水。 依照本發明一較佳實施例，上述之矽酸鹽可例如為石夕 酸鈉（Na2Si03)、四砍酸納（Na2Si4〇9)或上述之組合。 1275665 依照本發明一較佳實施例，上述之硝酸鹽係選自於由 硝酸鋁、硝酸卸、硝酸納或上述之組合。 根據本發明上述之目的，再提出一種鎂金屬之陽極氧 化處理方法，至少包含：首先，提供鎂金屬，其中此鎂金 ‘ 屬可例如鎂或鎂合金；以及進行陽極氧化處理步驟，係在 陽極氧化處理液中對此鎂金屬依序施加定電流及定電 壓，藉以於鎂金屬之表面形成陽極膜；其中陽極氧化處理 液至少包含：〇.〇1]^至2]^之矽酸鹽；〇〇1]^至2]^之 籲） 硝酸鹽；0·1 Μ至5 Μ之氫氧化鉀；（Μ M至丨M之氟化 鉀’ 0.1M至1M之磷酸鈉；以及去離子水。 ，由於本發明之鎂金屬之陽極氧化處理液含有矽酸鹽 及硝酸鹽，其中矽酸鹽可提升陽極膜之保護性，硝酸鹽則 可以改善火化放電集中之現象，使陽極膜均勻生長於鎂金 屬之表面，並提升鎂金屬之耐蝕能力。 【貫施方式】 本發明揭露-種鎂金屬之陽極氧化處理液，此陽極氧 酸睡/係以去離子水溶解至少包含㈣以至2M之石夕 〇 ::1……酸鹽、。·1Μ至W 撥挑 、氟化鉀、以及0.1 Μ至1 Μ之磷酸鈉等， 化處理7成為水'合液，然後針對鎖金屬之表面進行陽極氧 〇·5 Μ為較'佳月較佳實施例中，矽酸鹽之濃度以Ο·1 Μ至 ^ ’硝酸鹽之濃度以〇·1 Μ至0.5 Μ為較佳， 10 1275665 氫氧化鉀之濃度以1 Μ至3 Μ為較佳，氟化鉀之濃度以 〇·5 Μ至1 μ為較佳，而磷酸鈉之濃度以〇·ι μ至〇.5 μ 為較佳。在本發明一更佳實施例中，氫氧化鉀之濃度以約 3 Μ為更佳，氟化鉀之濃度以約〇·6 %為更佳，而磷駿納 之濃度以約〇·21 Μ為更佳。 依照本發明一較佳實施例，上述之石夕酸鹽可例如為石夕 酸納、四石夕酸鈉或上述之組合。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anodizing treatment liquid for magnesium metal, particularly an anodizing treatment liquid suitable for surface treatment of a town metal. [Prior Art] Magnesium and its alloys have received considerable attention under the demand of light weight. Magnesium alloys have been widely used in the automotive industry, leisure equipment, and 3C products due to their low density (about 1.7 g/cm2), high strength-to-weight ratio, and good electromagnetic shielding. However, in the development of town alloys. In the process and in the field of application, poor corrosion resistance has been the biggest fatal injury to magnesium alloys, so magnesium alloys are less used in environments with high structural or rot. In order to improve the corrosion resistance of magnesium alloys, expand the application of magnesium alloys and extend the service life and safety considerations, corrosion resistance is an important step, in which surface treatment is one of the important and effective methods, various types and alloys Related surface corrosion treatment has always been the subject of scholars' research. Among them, the protective film obtained by the anodizing treatment has better wear resistance and protection, and is quite suitable for the surface residual treatment of the magnesium alloy. The anodizing treatment utilizes the local high temperature generated during sparking (Sparking) to promote the formation of a layer of oxygen-like ceramics similar to sintered ceramics on the surface of the magnesium alloy, that is, the anode film, which protects the magnesium alloy substrate by the good protection of the anode film. To achieve the effect of increasing corrosion resistance, compared with other surface treatments, the wear resistance of yang: oxygen is better, the timeliness of coating (4), phase # applies to, the surface corrosion treatment of gold is very similar in recent years. One of the surface treatment methods of magnesium alloy 1272665. In the case of f, the anodizing treatment technology mainly forms a layer of anodic film on the surface of the magnesium alloy, and the anodic film layer must be covered on the surface to avoid the defects of the anodic film after the anodizing treatment, thereby accelerating the destruction of the substrate. At the same time, the grown anode film must also provide excellent protection (4) in order to achieve the effect of the magnesium alloy substrate. Therefore, the uniformity, composition and structure of the anodic film are all key to determining the protective properties of the anodic film. Further, it is preferable to grow and protect the anode film layer of the magnesium alloy from the external corrosive environment, and the key is the electrolyte used in the anodizing treatment, and the composition of the electrolyte and the addition thereof The material will affect the results of the anodizing treatment and the properties of the anode film. The anodizing treatment liquid of the town and its alloys is mainly chromate. However, in recent years, the environmental awareness has risen, and the chromate anodizing treatment liquid or the conversion coating electrolyte has been gradually eliminated, and the pollution is low. Environmentally friendly anodizing treatment liquids have begun to become mainstream. Such anodizing treatment liquids include fluorides, phosphates, sulfates, potassium hydroxide (K〇H), and wind oxides (NaOH). The addition of the linoleic acid salt to the anodizing treatment liquid is generally considered to reduce the pores caused by the spark discharge on the anodic film, and the addition of fluoride to the anodic oxidation treatment liquid can enhance the scratch resistance of the anodic film. Although the protective film obtained by the 13⁄4 pole oxidation treatment has better wear resistance and the δ vine resistance is quite suitable for the surface treatment of the magnesium alloy, but because the technology is not mature, it is applied to the anodizing treatment of the lock alloy industry. Still limited. For example, Die Casting AZ91D magnesium alloy will cause spark discharge concentration during the anodizing process of anodizing treatment solution containing nitrogen 1272665 and sodium silicate, resulting in uneven growth of the anodic film. . In order to meet the requirements of the future use of the lock alloy, it is necessary to change the electrolyte composition to improve the phenomenon of concentrated spark discharge to obtain a uniform anode film and improve the corrosion resistance of magnesium and magnesium alloys. One of the purposes is to disclose a metal-locking anodizing treatment liquid containing at least a bismuth citrate and a nitrate salt, wherein the bismuth salt enhances the protection of the anodic film against magnesium metal, and the nitrate salt The anode film can be uniformly grown on the surface of the magnesium metal. Another object of the present invention is to disclose an anodizing treatment method for magnesium metal. This anodizing treatment method utilizes the anodizing treatment liquid of the magnesium metal of the present invention in which the surface of the magnesium metal is anodized. In this way, the protection of the anode film of the magnesium metal can be improved, and the problem that the anode film is uneven due to the spark discharge of the base metal during the anodizing treatment can be improved. According to the above object of the present invention, an anodizing treatment liquid for magnesium metal is provided, which comprises at least: a cerium salt having a concentration of 〇·01 mol (M) to 2 ;; a nitrate of 〇·〇1 Μ to 2Μ; 1 Μ to 5 氢氧化 of potassium hydroxide; u Μ to 1 Μ of potassium fluoride; 〇"μ to 1 Μ of sodium phosphate; and deionized water. According to a preferred embodiment of the present invention, the above citrate may be, for example, sodium alginate (Na2Si03), sodium tetradecanoate (Na2Si4?9) or a combination thereof. 1275665 In accordance with a preferred embodiment of the present invention, the nitrate salt is selected from the group consisting of aluminum nitrate, nitric acid, sodium nitrate or a combination thereof. According to the above object of the present invention, there is further provided a method for anodizing magnesium metal, comprising at least: firstly, providing a magnesium metal, wherein the magnesium metal is, for example, a magnesium or a magnesium alloy; and performing an anodizing treatment step at the anode The oxidizing treatment liquid sequentially applies a constant current and a constant voltage to the magnesium metal, thereby forming an anodic film on the surface of the magnesium metal; wherein the anodizing treatment liquid contains at least: bismuth 〇1]^ to 2]^; 〇〇1]^至2]^之))Nitrate; 0·1 Μ to 5 Μ of potassium hydroxide; (Μ M to 丨M potassium fluoride '0.1M to 1M sodium phosphate; and deionized water Since the anodizing treatment liquid of the magnesium metal of the present invention contains a niobate and a nitrate, wherein the niobate can improve the protection of the anode film, the nitrate can improve the concentration of the cremation discharge, and the anode film is uniformly grown. The surface of the magnesium metal improves the corrosion resistance of the magnesium metal. [Comprehensive application method] The present invention discloses an anodizing treatment liquid for magnesium metal, which is dissolved in deionized water and contains at least (four) or even 2M stone.夕〇::1 ... acid salt, .1 Μ to W pluck, potassium fluoride, and 0.1 Μ to 1 Μ of sodium phosphate, etc., chemical treatment 7 becomes water 'liquid mixture, and then anodic oxime on the surface of the metal lock · 5 Μ In the preferred embodiment of the preferred embodiment, the concentration of the citrate is preferably 〇·1 Μ to 0.5 硝酸, and the concentration of 10 1275665 potassium hydroxide is 1 Μ. Preferably, the concentration of potassium fluoride is preferably 〇·5 Μ to 1 μ, and the concentration of sodium phosphate is preferably 〇·ι μ to 〇5 μm. A better implementation of the present invention. In the example, the concentration of potassium hydroxide is preferably about 3 Torr, the concentration of potassium fluoride is preferably about 〇·6 %, and the concentration of phosphine is preferably about 〇·21 。. In a preferred embodiment, the above-mentioned alumite can be, for example, sodium alginate, sodium tetrasodium citrate or a combination thereof.
依照本發明一較佳實施例，上述之硝酸鹽可例如為確 酸銘、硝酸鉀、硝酸鈉或上述之組合。 依照本發明一較佳實施例，上述之鎂金屬可例如為純 鎭或鎮合金，其中鎂合金可例如為鎂鋁鋅系列鎂合金，且 鎂金屬之形成方法可例如利用經由壓鑄、鑄造或鍛造之方 法0 與本發明之鎂金屬之陽極氧化處理液相較，於習知含 有氫氧化鉀、氟化鉀及磷酸鈉之陽極氧化處理液中添加矽 酸鹽，雖可增加陽極膜的耐蝕性，但仍有火花放電不均的 _ ) 現象發生。由於放電不均會使陽極膜無法均勻覆蓋鎂金屬 的表面，故僅添加矽酸鹽並無法大幅提昇陽極膜之保護 性。然而，在上述習知之陽極氧化處理液中添加硝酸鹽， 發現可以減緩陽極氧化處理過程因火花放電集中現象造 成陽極膜纟長不肖勻的5見象。目&，綜合以±兩種添加物 所得之結果，本發明之陽極氧化處理液同時添加硝酸鹽以 · 及矽酸鹽，兩者相辅相成，可大幅提昇鎂金屬之耐蝕性質。 ’ 承上所述’本發明更揭露一種鎂金屬之陽極氧化處理 11 1275665 方法’係適用於鎂金屬之表面處理。以下係以數個實施例 並配合第1圖至第11圖之圖示，對本發明之鎂金屬之陽 極氧化處理方法作更進一步的揭露，然其並非用以限定本 發明’任何熟習技術者，在不脫離本發明之精神範圍内， 當可作為些許之更動與潤飾。 本發明之第一實施例至第十一實施例所使用之鎂金 屬例如為壓鑄AZ91D鎂合金，係先以下述方式進行前處 理。首先，將壓鑄AZ91D鎂合金裁切成15 mm長、15 mm 寬、以及1 ·5 mm厚之大小後，將鎂合金連接至銅導線。 接耆’利用環氧樹酯（Epoxy)鑲埋成直徑30 mm之試片 後’以碳化砍砂紙研磨至# 1〇〇〇。然後，利用去離子水清 洗試片，再以超音波震盪洗清試片表面。之後，即進行陽 極氡化處理步驟。 在進行陽極氧化處理步驟時，係先以定電流方式升 壓，待電壓到達預設電壓後，再以定電壓方式進行陽極氧 化處理。根據本發明之一較佳實施例，係設定電流之電流 抢度介於每平方公分1至15毫安培（mA/cm2)之間，並設 定電壓介於80至1〇〇伏特（volt; v)之間。在本發明之第 一實施例至第四實施例中，其電流密度設定為5 mA/cm而電壓鼓疋為80 V。在本發明之第五實施例至 第十一實施例中，其電流密度設定為1〇mA/cm2,而電壓 設定為90 V。上述之第一實施例至第十一實施例進行陽 極氧化處理時間皆為20分鐘，而陽極氧化處理所使用之 陰極為不銹鋼片。 12 1275665According to a preferred embodiment of the present invention, the above nitrate may be, for example, a sour acid, potassium nitrate, sodium nitrate or a combination thereof. According to a preferred embodiment of the present invention, the magnesium metal may be, for example, a pure tantalum or a town alloy, wherein the magnesium alloy may be, for example, a magnesium aluminum zinc series magnesium alloy, and the magnesium metal forming method may be, for example, by die casting, casting or forging. Method 0 Compared with the anodizing liquid phase of the magnesium metal of the present invention, the ceric acid salt is added to the anodizing treatment liquid containing potassium hydroxide, potassium fluoride and sodium phosphate, which can increase the corrosion resistance of the anodic film. , but there is still uneven spark discharge _) phenomenon occurs. Since the uneven discharge causes the anode film to not uniformly cover the surface of the magnesium metal, the addition of the niobate does not greatly enhance the protection of the anode film. However, the addition of the nitrate to the above-mentioned anodizing treatment liquid has been found to be able to alleviate the 5 phenomenon in which the anode film is not uniform due to the concentration of the spark discharge during the anodizing treatment. The results are obtained by combining the two kinds of additives. The anodizing treatment liquid of the present invention simultaneously adds a nitrate to a tantalate, and the two mutually complement each other, thereby greatly improving the corrosion resistance of the magnesium metal. According to the above, the present invention further discloses an anodizing treatment of magnesium metal. 11 1275665 The method is applicable to the surface treatment of magnesium metal. The method for anodizing magnesium metal of the present invention is further disclosed in the following examples in conjunction with the drawings of Figures 1 through 11, but it is not intended to limit the invention to any skilled artisan. It can be used as a slight change and retouching without departing from the spirit of the invention. The magnesium metal used in the first to eleventh embodiments of the present invention is, for example, a die-cast AZ91D magnesium alloy which is pretreated in the following manner. First, the die-cast AZ91D magnesium alloy was cut into 15 mm long, 15 mm wide, and 1 · 5 mm thick, and the magnesium alloy was attached to the copper wire. The joint was polished with Epoxy into a test piece of 30 mm in diameter and polished to a #1〇〇〇 with carbonized chopped sandpaper. Then, the test piece was washed with deionized water, and the surface of the test piece was washed with ultrasonic vibration. Thereafter, the anode deuteration processing step is performed. When the anodizing treatment step is performed, the voltage is firstly boosted by a constant current method, and after the voltage reaches a preset voltage, the anode is oxidized by a constant voltage method. According to a preferred embodiment of the present invention, the current current of the set current is between 1 and 15 milliamperes (mA/cm2) per square centimeter, and the set voltage is between 80 and 1 volt (volt; v )between. In the first to fourth embodiments of the present invention, the current density was set to 5 mA/cm and the voltage drum was 80 V. In the fifth to eleventh embodiments of the present invention, the current density was set to 1 mA/cm2, and the voltage was set to 90 volts. The first to eleventh embodiments described above were subjected to the anodic oxidation treatment time of 20 minutes, and the cathode used for the anodizing treatment was a stainless steel sheet. 12 1275665
習知陽極氧化處理液係含有氫氧化鉀、氟化鉀、磷酸 鈉，而本發明則於習知陽極氧化處理液中，再利用不同添 加物分別形成三種陽極氧化處理液，其中第一種陽極氧化 處理液係於習知陽極氧化處理液中再添加0 01 M至2 M 之硝酸鋁，第二種陽極氧化處理液係於習知陽極氧化處理 液中再添加0.01 Μ至2M之矽酸鈉，第三種陽極氧化處 理液係於習知陽極氧化處理液中再同時添加〇〇1訄至2 Μ之梦酸納及0·15 Μ之确酸铭。上述之實施例中，此三 種陽極氧化處理液之陽極氧化處理條件皆相同，其中第三 種陽極氧化處理液僅於石夕酸納濃度有所變化。 本發明之第一實施例至第^--實施例之表面顯微結 構’係利用光學顯微鏡（Optical Microscope ; ΟΜ)以及掃 瞒式電子顯微鏡（Scanning Electron Microscope ; SEM)進 行觀察。電化學性質測試則於3·5重量百分比（Weight Percent ; wt%)之氣化鈉（NaCl)水溶液中進行。The conventional anodizing treatment liquid contains potassium hydroxide, potassium fluoride and sodium phosphate, and the present invention is used in a conventional anodizing treatment liquid, and three kinds of anodizing treatment liquids are respectively formed by using different additives, wherein the first anode is formed. The oxidizing treatment liquid is added to a conventional anodizing treatment liquid and further added with 0 01 M to 2 M of aluminum nitrate, and the second anodizing treatment liquid is added to a conventional anodizing treatment liquid and then adding 0.01 Μ to 2 M sodium citrate. The third anodizing treatment liquid is added to the conventional anodizing treatment liquid and then added with 〇〇1訄 to 2 Μ 梦 酸 及 and 0·15 Μ 确 酸 酸. In the above embodiments, the anodizing treatment conditions of the three anodizing treatment liquids are the same, and the third anodizing treatment liquid only changes in the concentration of the sodium oxalate. The surface microstructures of the first to the second embodiments of the present invention were observed by an optical microscope (Optical Microscope; ΟΜ) and a Scanning Electron Microscope (SEM). The electrochemical property test was carried out in an aqueous solution of sodium percarbonate (NaCl) of 3.5% by weight (wt%).
請參照第1(a)圖至第1(1>)圖，其係顯示壓鑄AZ91D 鎂合金之表面顯微結構。本發明之一較佳實施例係使用壓 鑄AZ91D鎂合金，壓鑄AZ91D鎂合金為兩相合金，包含 鎂固溶體（Solid Solution)之α相以及鎮铭合金之/5相，如 第1(b)圖中之α及泠所示。 請參照第2(a)圖至第2(e)圖，其係顯示經研磨處理之 壓鑄AZ91D鎂合金（第2(a)圖）與根據本發明之第一實施 例至第四實施例（第2(b)圖至第2(e)圖）之經陽極氧化處理 之壓鑄AZ91D鎂合金之表面巨觀照片。其中，本發明之 13 1275665 组’即利用習知陽極氧化處理液進行陽 陽搞备&南第—實施例至第四實施例係利用上述第一種 %極氧化處理液進行陽極氧化處理，其中第一種陽極氧化 處理液分別含右…， U㈣極氧化 有0.1 Μ、0.15 M以及0.25 M之硝酸鋁， 藉以了解硝酸鋁減少集中放電之效果。 、第2(a)圖，壓鑄AZ91D鎮合金經# 1〇〇〇砂紙 研磨後’試片表面有明顯之到痕。 、、’ 」而备壓鑄AZ91D鎂合金於習知陽極氧化處理液 中進行陽極氧化處理後，表面會有—層陽極膜覆蓋，同 時’因為火花放電集中的結果’所形成之陽極膜結構不均 勻’且保護性較差，如第2(b)圖所示之型態，其中第2⑻ 圖中之白色區域即為集中放電的區域，相料自色區域之 其他範圍，則形成較薄之陽極膜。這是由於電流集中現象 造成陽極膜之均勻性不佳，表面之白色區域所形成之陽極 膜較厚，其餘區域所形成之陽極膜較薄，腐蝕容易由較薄 之區域發生，因此無法有效保護鎂合金基材。 請參照第2(c)圖，相較於第一實施例之陽極膜的結 構，第二實施例之陽極膜已較為均勻，故其保護性較佳。 請參照帛2(d)圖’第三實施例之集中放電的現象明顯減 少，且經由本發明之陽極氧化處理後，陽極臈較為均勻， 且第三實施例之陽極膜比第二實施例之陽極膜更厚，因此 保護性更佳。請參照第2(e)圖，第三實施例之集中放電的 現象已經很少’因此所生成之陽極膜非常均勻。 、 簡言之，由第一實施例至第四實施例之觀察結果可 1275665 知’隨著硝酸鋁濃度增加，集中放電造成的陽極膜生長不 均勻現象越少，亦即集中放電之區域減少，如第2(b)圖至 第2(e)圖所示之型態。 請參照第3(a)圖至第3(c)圖，其係顯示根據本發明之 ‘ 第一實施例、第四實施例、以及第一實施例至第四實施例 之陽極氧化處理步驟中電流密度與時間之相對關係圖。請 參照第3(a)圖，其係顯示於陽極氧化處理期間電流會有震 盪的現象，這是火花放電過程之正常現象。在第一實施例 ❿） 中於未添加硝酸鋁的情況下，電流密度並不會隨著陽極氧 化處理進行而有減小的趨勢，顯示陽極膜並未成長得十分 完整，如第3(a)圖所示。請參照第3〇3)圖，其係顯示第四 實施例之電流密度以及時間之關係圖，圖中可明顯發現電 流震盪的震幅明顯減小，而電流密度會有顯著下降的趨 勢，此時因為火花放電集中現象減少，陽極膜較完整覆蓋 於基材表面。請參照第3(〇圖，其係顯示根據本發明之第 一實施例至第四實施例之陽極氧化處理步驟中電流密度 _ ) 與時間之相對關係圖，為避免混淆，圖中震盪部分以平均 值來表示。由圖中可知在添加適量的硝酸鋁，例如第三實 施例及第四實施例時，電流密度值明顯降低，顯示此時 AZ91D鎂合金表面形成一層較均勻的陽極膜。根據簡單 之電學原S:由於陽極膜造成纟面電阻增加，且在定電位 的情況下，電流值才會有下降的趨勢。而第3⑷圖中亦_ . 示各組之最終電流值隨著确酸紹含量增加而下降，最低彳 達約 0.3 mA/cm2。 15 1275665 請參照第4(a)圖至第4(c)圖，其係顯示根據本發明之 第五實施例至第七實施例之經陽極氧化處理之壓鑄 AZ91D鎮合金之表面巨觀照片。其中，第五實施例至第 七實施例係利用上述第二種陽極氧化處理液進行陽極氧 化處理，其中第二種陽極氧化處理液分別含有〇〇5 M、 〇·1 Μ以及0.15 M之㈣鈉，藉以了解㈣納對陽極膜 耐餘性提昇之效果。Μ 4刚至第4(e)@之表面巨觀照 片可知#添加石夕@^納之第二種陽極氧化處理液所形成陽 極膜的均勻性並不佳，仍有集中放電的現象發生。而且不 論添加之矽酸鈉濃度為何，於陽極氧化過程中，還是會發 生火花放電集中的情形。 請參照第5(a)圖至帛5⑷圖，其係顯示根據本發明之 第八實施例至第十一實施例之經陽極氧化處理之壓鑄 AZ91D鎂合金之表面巨觀照片。其中，第八實施例至第 十一實施例則利用上述第三種陽極氧化處理液進行陽極 氧化處理，其中第三種陽極氧化處理液含有〇15M硝酸 鋁並分別含有0·05 Μ、〇·ΐ M、〇 15 M以及〇 2 M之矽酸 鈉，藉以了解同時添加g酸紹及石夕酸㈣陽極氧化處理成 效之影響。相較於第4(a)圖至第4((：)圖之結果，於相同矽 酸納濃度時，添加G.15 Μ之魏㈣對;^陽極膜的均勻 性有明顯改善的效果。不論添加的石夕酸㈣度為何，試片 表面集中放電的現象係顯著減少，且陽極膜可均句覆蓋於 鎂合金表面，如第5(a)圖至第5(d)圖所示。 請參照第6⑷圖至第6(d)圖，其係顯示根據本發明之 1275665 第八實施例至第十一實施例之經陽極氧化處理之壓鑄 AZ91D鎂合金之表面顯微結構。由第6(a)圖至第6(d)圖 可知，陽極膜為多孔狀結構，此為火花放電的特徵。請參 照第7(a)圖至第7(d)圖，其係顯示根據本發明之第八實施 例至第十一實施例之經陽極氧化處理之壓鑄AZ91D鎂合 金之橫截面結構。由第7(a)圖至第7(d)圖可知，陽極膜厚 度為約6/zm至9/zm。 陽極膜的成分亦為決定陽極膜之耐蝕效果之關鍵之 一’一般而言，陽極膜是由氧化物所組成的氧化膜。請參 照第8圖，其係繪示根據本發明之第八實施例至第十一實 施例之X射線繞射（X-Ray Diffraction ; XRD)圖譜。由第 8圖可知，氧化鎂（Mg〇)為陽極膜之主要成分，如圖中之 繞射峰Ο所示’並包含少量之Al2(Si04)0如圖中之A所 示，陽極氧化處理即藉由此陽極膜阻絕外部腐蝕物質，達 到保護基材減低腐餘發生的效果。圖中並包含有鎮固溶體 以及介金屬化合物（MgnAl12)，分別如圖中之α以及沒所 示0 請參照第9圖，其係繪示根據本發明之第一實施例至 第四實施例之電化學交流阻抗測試結果。由第9圖中可 見，隨著硝酸鋁濃度增加，阻抗值亦增加。這是由於集中 放電的現象減少’陽極膜會均勻的覆蓋於鎂合金表面，對 於鎮合金基材之保護性更好，其極化阻抗亦佳，其中第一 實施例至第四實施例之電化學交流阻抗值則如第1表所 示0 17 1275665 第1表Refer to Figures 1(a) through 1(1>) for the surface microstructure of the die-cast AZ91D magnesium alloy. A preferred embodiment of the present invention uses a die-cast AZ91D magnesium alloy, and the die-cast AZ91D magnesium alloy is a two-phase alloy comprising an alpha phase of a magnesium solid solution (Solid Solution) and a phase 5 of a Zhenming alloy, such as a first phase (b). ) α and 泠 in the figure. Please refer to FIGS. 2(a) to 2(e), which show the die-cast AZ91D magnesium alloy (Fig. 2(a)) and the first to fourth embodiments according to the present invention ( 2(b) to 2(e)) A superficial photograph of the surface of an anodized die-cast AZ91D magnesium alloy. Wherein, the 13 1275665 group of the present invention is subjected to anodizing treatment by using the above-mentioned first type of extreme oxidation treatment liquid, that is, using a conventional anodizing treatment liquid for performing Yangyang preparation & Nandi - the fourth to fourth embodiments. The first anodizing treatment liquid contains right ..., U (four) pole oxidation has 0.1 Μ, 0.15 M and 0.25 M aluminum nitrate, in order to understand the effect of aluminum nitrate to reduce concentrated discharge. , Figure 2 (a), die-casting AZ91D town alloy after # 1〇〇〇 sandpaper grinding, the surface of the test piece has obvious marks. After the anodizing treatment of the AZ91D magnesium alloy in the conventional anodizing treatment liquid, the surface will be covered with an anodic film, and the anodic film structure formed by the result of the concentration of the spark discharge is uneven. 'And the protection is poor, as shown in Figure 2(b), where the white area in Figure 2(8) is the concentrated discharge area, and the other areas of the phase self-color area form a thinner anodic film. . This is due to the current concentration phenomenon, the uniformity of the anode film is not good, the anode film formed by the white area of the surface is thick, the anode film formed in the remaining areas is thin, and the corrosion is easily caused by the thinner region, so it cannot be effectively protected. Magnesium alloy substrate. Referring to Fig. 2(c), the anode film of the second embodiment is relatively uniform compared to the structure of the anode film of the first embodiment, so that the protective property is preferred. Referring to FIG. 2(d), the phenomenon of concentrated discharge in the third embodiment is significantly reduced, and after the anodizing treatment of the present invention, the anode crucible is relatively uniform, and the anode film of the third embodiment is more than that of the second embodiment. The anodic film is thicker and therefore more protective. Referring to Figure 2(e), the phenomenon of concentrated discharge in the third embodiment has been very small. Therefore, the anodic film formed is very uniform. In short, the observation results from the first embodiment to the fourth embodiment can be 1272565. 'As the concentration of aluminum nitrate increases, the uneven growth of the anodic film caused by concentrated discharge is less, that is, the area of concentrated discharge is reduced. The pattern shown in Figures 2(b) to 2(e). Please refer to FIGS. 3(a) to 3(c), which show the anodizing treatment steps of the first embodiment, the fourth embodiment, and the first to fourth embodiments according to the present invention. A plot of the relative relationship between current density and time. Please refer to Figure 3(a), which shows that the current will oscillate during the anodizing process, which is a normal phenomenon in the spark discharge process. In the first embodiment, in the case where aluminum nitrate is not added, the current density does not decrease as the anodizing treatment proceeds, indicating that the anodic film does not grow very completely, as in the third (a) ) shown in the picture. Please refer to the figure 3第3), which shows the relationship between the current density and the time of the fourth embodiment. It can be clearly found that the amplitude of the current oscillation is significantly reduced, and the current density tends to decrease significantly. When the concentration of the spark discharge is reduced, the anode film is completely covered on the surface of the substrate. Please refer to FIG. 3 (a diagram showing the relationship between current density _ in the anodizing treatment step according to the first to fourth embodiments of the present invention) and time. To avoid confusion, the oscillating portion in the figure is The average value is expressed. It can be seen from the figure that when an appropriate amount of aluminum nitrate is added, for example, in the third embodiment and the fourth embodiment, the current density value is remarkably lowered, indicating that a relatively uniform anode film is formed on the surface of the AZ91D magnesium alloy. According to the simple electric original S: the resistance of the surface is increased due to the anodic film, and the current value will decrease when the potential is fixed. In the third (4) chart, the final current value of each group decreases with the increase of the acid content, and the minimum enthalpy reaches about 0.3 mA/cm2. 15 1275665 Referring to Figures 4(a) to 4(c), there are shown superficial photographs of the surface of the anodized AZ91D town alloy according to the fifth to seventh embodiments of the present invention. The fifth embodiment to the seventh embodiment are anodized by using the second anodizing treatment liquid, wherein the second anodizing treatment liquid contains 〇〇5 M, 〇·1 Μ and 0.15 M (4), respectively. Sodium, in order to understand the effect of (4) nano-adhesion to the anode film. Μ 4 to the 4th (e) @ surface of the giant Guanzhao film, we can see that the uniformity of the anode film formed by the addition of the second anodizing treatment solution of Shi Xi@^Na is not good, and there is still a phenomenon of concentrated discharge. Moreover, regardless of the concentration of sodium citrate added, a concentration of spark discharge will occur during the anodization process. Referring to Figures 5(a) to 5(4), there are shown superficial photographs of the surface of the anodized AZ91D magnesium alloy according to the eighth to eleventh embodiments of the present invention. The eighth embodiment to the eleventh embodiment are anodized by using the third anodizing treatment liquid, wherein the third anodizing treatment liquid contains 〇15M aluminum nitrate and contains 0·05 Μ, 〇· ΐ M, 〇15 M and 〇2 M sodium citrate, in order to understand the effect of adding gacid and oxalic acid (4) anodizing treatment. Compared with the results of Fig. 4(a) to Fig. 4((:), when the same sodium citrate concentration is added, the addition of G.15 Μ Wei (4) pairs; ^ anodic film uniformity has a significant improvement effect. Regardless of the degree of tetracycline (four) added, the phenomenon of concentrated discharge on the surface of the test piece is significantly reduced, and the anodic film can be uniformly covered on the surface of the magnesium alloy, as shown in Figs. 5(a) to 5(d). Please refer to FIGS. 6(4) to 6(d), which show the surface microstructure of the anodized AZ91D magnesium alloy according to the eighth embodiment to the eleventh embodiment of the present invention. (a) FIG. 6(d) shows that the anode film has a porous structure, which is a feature of spark discharge. Please refer to FIGS. 7(a) to 7(d), which show according to the present invention. The cross-sectional structure of the anodized AZ91D magnesium alloy of the eighth embodiment to the eleventh embodiment. From the 7th to 7th (d), the thickness of the anodic film is about 6/zm to 9/zm. The composition of the anodic film is also one of the key factors determining the corrosion resistance of the anodic film. In general, the anodic film is an oxide film composed of oxides. 8 is a view showing an X-ray diffraction (XRD) pattern according to eighth to eleventh embodiments of the present invention. From Fig. 8, magnesium oxide (Mg〇) is an anode. The main component of the film, as shown by the diffraction peak in the figure, and contains a small amount of Al2(Si04)0, as shown in A of the figure, the anodizing treatment is to block the external corrosive substance by the anodic film to reach the protective group. The material has the effect of reducing the occurrence of corrosion. The figure also contains the municipal solid solution and the intermetallic compound (MgnAl12), respectively, as shown in the figure, and not shown in the figure. Referring to Figure 9, it is shown in accordance with the present invention. The results of the electrochemical alternating current impedance test of the first to fourth embodiments. It can be seen from Fig. 9 that as the concentration of aluminum nitrate increases, the impedance value also increases. This is because the phenomenon of concentrated discharge is reduced, and the anode film is uniform. Covering the surface of the magnesium alloy, the protection is better for the town alloy substrate, and the polarization resistance is also good. The electrochemical impedance values of the first embodiment to the fourth embodiment are as shown in Table 1 0 17 1275665. Table 1
由第1表之電化學交流阻抗測試莊要- 气…果顯不，隨著硝酸 銘濃度增加，阻抗值亦提高，顯示陽極膜夕仏 徑膘之均勻性對於陽 極膜之耐蝕性有極大之影響。至於第四膏施加4 — 布Θ頁％例之交流阻抗 值略微下降，這是由於添加硝酸鋁可有效去除集中放電現 象’但疋放電日ΤΓ間反而縮短’此時陽極膜的厚度會略微減 少，因此石肖酸紹的添加量亦存在有極限濃度。 請參照第10圖，其係繪示根據本發明之第五實施例 至第七實施例之電化學交流阻抗測試結果。由第1〇圖可 見，隨著矽酸鈉濃度增加，阻抗值亦增加，顯示矽酸鈉的 添加有助於增加陽極膜之保護性，鎂合金基材不易受到外 在腐蝕物質侵襲。第五實施例至第七實施例之電化學交流 阻抗值則如第2表所示。 第2表 實施例編號 第五實施例 第六實施例 第七實施土1_ 極化阻抗 (Ω -cm2) 6755 11952 21056 18 I275665 由第2表t電化學交、流阻抗測試結果顯示，隨著添加 之矽酸鈉濃度增加，交流阻抗值亦增加，陽極膜之阻抗^ 可較第一例提昇三倍之多。 ^ 請參照第11圖，其係繪示根據本發明之第八實施例 至第十一實施例之電化學交流阻抗測試結果。由上述第一 實施例至第四實施例之結果可知，硝酸鋁的添加可以使集 中放電效應減少，而由上述第五實施例至第七實施例則顯 示矽酸鈉可以提昇陽極膜之保護性，因此在第八實施例至 第十一實施例中同時添加矽酸鈉以及硝酸鋁的情形下，試 片之極化阻抗值大幅增加，約為鎂合金基材之2〇〇倍，也 較單獨添加石夕酸納或是硝酸鋁之p且抗值增加約十倍。因 此，在本發明之陽極氧化處理液中，硝酸鋁以及矽酸納實 相輔相成，使得陽極膜之均勻性以及耐蝕性大幅提昇。第 八實施例至第十一實施例之電化學交流阻抗值則如第3 表所示。 第3表 實施例編號 第八 實施例 第九 實施例 第十 實施例 第十一 實施例 極化阻抗 (Ω -cm2) 58480 119840 ί 88690 93670 由第3表之電化學交流阻抗測試結果顯示，添加硝酸 鋁減少火花放電集中的情形’使得陽極膜生長均勻，而石夕 19 1275665 酸鈉 >辰度增加更增加陽極膜之耐钱性，且大幅提昇交流阻 抗值，其中第九實施例之極化阻抗值約為第一實施例之 17倍，相較於單獨加入硝酸鋁或是矽酸鈉，對於陽極膜 耐钱性的提昇更加顯著。由結果得知，同時添加矽酸鈉以 及頌酸紹對於改善陽極膜耐钱效果有很大的助益。然而在 第十實施例中極化阻抗值有略為下降的趨勢，此因陽極氧 化溶液中之配方互相發生反應，溶液中有透明的反應生成From the electrochemical impedance impedance test of the first table, it is necessary to show the gas resistance. As the concentration of nitric acid increases, the impedance value also increases, indicating that the uniformity of the anode film is extremely large for the corrosion resistance of the anode film. influences. As for the fourth paste application, the AC impedance value of the sample is slightly decreased. This is because the addition of aluminum nitrate can effectively remove the concentrated discharge phenomenon, but the discharge time of the discharge is shortened, and the thickness of the anode film is slightly reduced. Therefore, there is also a limit concentration in the amount of the addition of succinic acid. Referring to Fig. 10, there are shown electrochemical impedance resistance test results according to fifth to seventh embodiments of the present invention. As can be seen from the first graph, as the concentration of sodium citrate increases, the impedance value also increases, indicating that the addition of sodium citrate helps to increase the protective properties of the anodic film, and the magnesium alloy substrate is less susceptible to external corrosive substances. The electrochemical alternating current impedance values of the fifth to seventh embodiments are as shown in the second table. Table 2 Embodiment No. Fifth Embodiment Sixth Embodiment Seventh Embodiment Soil 1_ Polarization Impedance (Ω - cm2) 6755 11952 21056 18 I275665 The electrochemical impedance and flow impedance test results of the second table t show that with the addition As the concentration of sodium citrate increases, the value of the AC impedance increases, and the impedance of the anodic film can be increased by a factor of three compared with the first case. ^ Referring to Fig. 11, there are shown electrochemical impedance resistance test results according to eighth to eleventh embodiments of the present invention. From the results of the above-described first to fourth embodiments, it is understood that the addition of aluminum nitrate can reduce the concentrated discharge effect, and the fifth to seventh embodiments show that sodium citrate can improve the protection of the anodic film. Therefore, in the case where sodium citrate and aluminum nitrate are simultaneously added in the eighth embodiment to the eleventh embodiment, the polarization resistance value of the test piece is greatly increased, which is about 2 times that of the magnesium alloy substrate, and is also Separation of sodium sulphate or aluminum nitrate was added separately and the resistance increased by about ten times. Therefore, in the anodizing treatment liquid of the present invention, aluminum nitrate and sodium niobate are mutually complementary, so that the uniformity and corrosion resistance of the anode film are greatly improved. The electrochemical AC impedance values of the eighth embodiment to the eleventh embodiment are as shown in Table 3. Third Table Embodiment No. Eighth Embodiment Ninth Embodiment Tenth Embodiment Eleventh Embodiment Polarization Impedance (Ω - cm2) 58480 119840 ί 88690 93670 The electrochemical impedance impedance test result of the third table is shown, added Aluminum nitrate reduces the concentration of spark discharges to make the anodic film grow evenly, while the increase of the sodium sulphate 19 1275665 > increase the anodic film's durability, and greatly increase the AC impedance value, the ninth embodiment The resistance value is about 17 times that of the first embodiment, and the increase in the durability of the anode film is more remarkable than the addition of aluminum nitrate or sodium citrate alone. It is known from the results that the addition of sodium citrate and bismuth citrate are of great benefit to improving the anodic membrane resistance. However, in the tenth embodiment, the polarization resistance value tends to decrease slightly, because the formulations in the anodic oxidation solution react with each other, and a transparent reaction is formed in the solution.
物’而造成陽極氧化處理後試片之極化阻抗下降。第^-- 實施例之極化阻抗值與第十實施例相當接近，其中陽極氧 化處理液之反應增加，生成物亦變多。 由上述本發明較佳實施例可知，應用本發明之鎂金屬 之暢極氧化處理液之一優點，在於此鎂金屬之陽極氧化處 理液係至少包含矽酸鹽及硝酸鹽，其中矽酸鹽可提升陽極 膜對鎂金屬之保護性’硝酸鹽則可使陽極膜均勻生長於鎂 金屬之表面。The polarization resistance of the test piece after the anodizing treatment was lowered. The polarization resistance value of the first embodiment is quite close to that of the tenth embodiment, in which the reaction of the anodic oxidation treatment liquid is increased and the amount of the product is also increased. According to the preferred embodiment of the present invention, one of the advantages of applying the magnesium metal sulphur oxidation treatment liquid of the present invention is that the anodic oxidation treatment liquid of the magnesium metal contains at least a citrate and a nitrate. Enhancing the protection of the anodic film against magnesium metal 'Nitrate salt allows the anodic film to grow uniformly on the surface of the magnesium metal.
由上述本發明較佳實施例可知，應用本發明之鎂金屬 之陽極氧化處理方法之另一優點，在於此鎂金屬之陽極氧 化處理方法係利用本發明之鎂金屬之陽極氧化處理液，對 鎖金屬之表面進行陽極氧化處理。如此一來，可提昇鎂金 屬之陽極膜之保護性，更改善鎂金屬在陽極氧化處理過程 中火花放電引起陽極膜不均勻的問題。 雖然本發明已以較佳實施例揭露如上，然其並非用以 限定本發明，任何熟習此技藝者，在不脫離本發明之精神 和範圍内，當可作各種之更動與潤飾，因此本發明之保護 20 1275665 範圍田視後附 < 中請專利範圍所界定者為準。 【圖式簡單說明1 第i(a)圖至第1(b)圖係顯示壓鑄AZ91D鎂合金之表 面顯微結構； 第2(a)圖係顯示經研磨處理之壓鑄AZ91D鎂合金之 表面巨觀照片； ()目至第2(e)圖係顯示根據本發明之第一實施 例至第四實施例之經陽極氧化處理之壓鑄AZ91D鎂合金 之表面巨觀照片； 第3(a)圖係顯示根據本發明之第一實施例之陽極氧 化處理步驟中電流密度與時間之相對關係圖； 第3(b)圖係顯示根據本發明之第四實施例之陽極氧 化處理步驟中電流密度與時間之相對關係圖； 第3(c)圖係顯示根據本發明之第一實施例至第四實 施例之陽極氧化處理步驟中電流密度與時間之相對關係 圖； 第4(a)圖係顯示根據本發明之第五實施例之經陽極 氧化處理之壓鑄AZ91D鎂合金之表面巨觀照片； 第4(b)圖係顯示根據本發明之第六實施例之經陽極 氧化處理之壓鑄AZ91D鎂合金之表面巨觀照片； 第4(c)圖係顯示根據本發明之第七實施例之經陽極 氧化處理之壓鑄AZ91D鎂合金之表面巨觀照片； 第5(a)圖係顯示根據本發明之第八實施例之經陽極 21 1275665 氧化處理之壓鱗AZ91D鎂合金之表面巨觀照片； 第5(b)圖係顯示根據本發明之第九實施例之經陽極 氧化處理之壓鑄AZ91D鎂合金之表面巨觀照片； 第5(c)圖係顯示根據本發明之第十實施例之經陽極 氧化處理之壓鑄AZ91D鎂合金之表面巨觀照片； 第5 (d)圖係顯示根據本發明之第^--實施例之經陽 極氧化處理之壓鑄AZ91D鎂合金之表面巨觀照片； 第6(a)圖係顯示根據本發明之第八實施例之經陽極 氧化處理之壓鑄AZ91D鎂合金之表面顯微結構； 第6(_係顯示根據本發明之第九實施例之經陽極 氧化處M_AZ91D鎂合金之表面顯微結構； 第6(c)圖係顯示根據本發明之第十實施例之經陽極 氧化處理之展鑄AZ91D鎂合金之表面顯微結構； 第6剛㈣隸據本發明之第十—實施例之經陽 極氧化處理之壓鑄AZ91D鎖合金之表面顯微結構； 第7⑷圖係顯*根據本發明之第人實施例之經陽極 氧化處理之壓鑄AZ91D鎂合金之撗戴面結構； 第7(b)圖係顯示根據本發明之第九實施例之經陽極 氧化處理之壓鑄AZ91D鎂合金之橫截面結構； &第7⑷圖係顯示根據本發明之第十實施例之經陽極 乳化處理之壓鑄AZ91D鎂合金之橫截面結構； 第7剛_示根據本發明之第十—實施例之經陽 極乳化處理之壓鑄AZ91DM合金之橫戴面結構； 第8圖係繪示根據本發明之第人實施例至第十-實 22 1275665 施例之x射線繞射圖譜； 第9圖係繪示根據本發明之第一實施例至第四實施 例之電化學交流阻抗測試結果； 第10圖係繪示根據本發明之第五實施例至第七實施 例之電化學交流阻抗測試結果；以及 第11圖係繪示根據本發明之第八實施例至第十一實 施例之電化學交流阻抗測試結果。 23According to the preferred embodiment of the present invention, another advantage of the method for anodizing magnesium metal according to the present invention is that the anodizing treatment method of magnesium metal utilizes the anodizing treatment liquid of magnesium metal of the present invention to lock The surface of the metal is anodized. In this way, the protection of the anodic film of the magnesium metal can be improved, and the problem that the anodic film is uneven due to the spark discharge of the magnesium metal during the anodizing process is improved. While the present invention has been described above by way of a preferred embodiment, it is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. Protection 20 1275665 The scope of the field is attached to the < [Simple diagram of the diagram 1 The i(a) to 1(b) shows the surface microstructure of the die-cast AZ91D magnesium alloy; the 2 (a) shows the surface of the die-cast AZ91D magnesium alloy Viewing the photograph; () to the second (e) diagram showing the superficial photograph of the surface of the anodized AZ91D magnesium alloy according to the first to fourth embodiments of the present invention; Fig. 3(a) The graph shows the relationship between the current density and the time in the anodizing treatment step according to the first embodiment of the present invention; and the third graph (b) shows the current density in the anodizing treatment step according to the fourth embodiment of the present invention. Fig. 3(c) is a diagram showing the relationship between current density and time in the anodizing treatment steps according to the first to fourth embodiments of the present invention; Fig. 4(a) shows the relationship A superficial photograph of the surface of an anodized die-cast AZ91D magnesium alloy according to a fifth embodiment of the present invention; and Fig. 4(b) is a graph showing an anodized die-cast AZ91D magnesium alloy according to a sixth embodiment of the present invention. Superficial photo of the surface; Figure 4(c) shows A superficial photograph of the surface of the anodized AZ91D magnesium alloy according to the seventh embodiment of the present invention; and Fig. 5(a) shows the scale of the oxidation treatment of the anode 21 1275665 according to the eighth embodiment of the present invention. A superficial photograph of the surface of the AZ91D magnesium alloy; the fifth (b) is a superficial photograph of the surface of the anodized AZ91D magnesium alloy according to the ninth embodiment of the present invention; and the fifth (c) diagram is based on A superficial photograph of the surface of an anodized AZ91D magnesium alloy according to a tenth embodiment of the present invention; and a fifth (d) diagram showing an anodized die-cast AZ91D magnesium according to the first embodiment of the present invention. a superficial photograph of the surface of the alloy; Fig. 6(a) is a view showing the surface microstructure of the anodized AZ91D magnesium alloy according to the eighth embodiment of the present invention; The surface microstructure of the M_AZ91D magnesium alloy at the anodization of the nine embodiment; and the sixth (c) diagram shows the surface microstructure of the anodized AZ91D magnesium alloy according to the tenth embodiment of the present invention; The sixth (four) is based on this The surface microstructure of the anodized AZ91D lock alloy subjected to anodization according to the tenth embodiment of the invention; Figure 7(4) shows the anodic oxidation of the die-cast AZ91D magnesium alloy according to the first embodiment of the present invention Fig. 7(b) shows a cross-sectional structure of an anodized die-cast AZ91D magnesium alloy according to a ninth embodiment of the present invention; & 7(4) shows a tenth embodiment according to the present invention The cross-sectional structure of the die-cast AZ91D magnesium alloy subjected to anodic emulsification treatment; the seventh embodiment shows the cross-face structure of the die-cast AZ91DM alloy subjected to the anodic emulsification treatment according to the tenth embodiment of the present invention; The x-ray diffraction pattern of the first embodiment to the tenth embodiment of the present invention to the tenth embodiment of the present invention; and the nineth embodiment show the electrochemical impedance resistance test results according to the first to fourth embodiments of the present invention; 10 is a graph showing electrochemical impedance resistance test results according to fifth to seventh embodiments of the present invention; and FIG. 11 is an illustration showing electrification according to eighth to eleventh embodiments of the present invention. Learn to pay Flow impedance test results. twenty three