1353393 1 Λ 100年09月14日 梭正 八、發明說明： 【發明所屬之技術領域】 [0001]本發明涉及一種鎂合金工件及鎂合金磷化方法。 [先前技術3 [0002] 鎂合金輕材料因為比重低、強度高且適合回收使用而廣 泛應用於汽車及電器設備。惟’由於鎮合金化學性質較 為活潑，耐腐蝕性能較差’故鎮合金工件於使用前一般 需要於其表面形成抗腐蝕膜’該抗腐姓膜需具有良好之 耐鹽霧性能、較高之附著力及較小之表面阻抗。 [0003] 習知技術中，一般係藉由磷化方法於鎂合金工件表面形 成一層磷化膜，以提高其抗腐蝕性。惟，習知之磷化膜 一般由磷酸鎂、磷酸錳等複合磷酸鹽構成，其於後續之 塗裝過程中與油漆層之附著力較差，故會影響鎂合金工 件之使用。 【發明内容】 [0004] 鐾於上述狀泥，有必要提供一種鎮合金工件及鎮合金碟 化方法。該鎂合金磷化方法形成的磷化膜與後續塗裝的 油漆層具有較高的附著力。 [0005] —種鎂合金磷化方法，包括以下步驟：提供一鎂合金預 基材；酸洗，用酸洗溶液去除該鎂合金預基材表面之氧 化物與離型劑；驗洗，用驗以容液去除該鎂合金預基材 表面之黑灰；化成’用含有單寧酸之化成溶液於該錢合 金預基材表面形成磷化膜。 [_ -種鎖合金工件’該鎮合金卫件包括齡金預基材及一 096150093 表單編號Α0101 第3頁/共15頁 1003334214-0 1353393 100年0 形成於該錢σ金預基材表面之魏膜，該 含有單寧酸之化成溶液於該鎂合金預基材表面而形成。 _7]上述接合金鱗化方法中，化成溶液含有單寧酸，使生成 之磷化膜表面性能得以改善，從而易於使形成於鎂合金 工件表面之磷化膜與後續塗裝之油漆層具有較高之附著 力。 [實施方式】 [0008] 下麵將結合附圖及實施例對本發明鎂合金工件及鎂合金 磷化方法做進一步詳細說明。 [0009] 請參見圖1，所示為本發明較佳實施方式之鎂合金磷化方 法之流程圖，其包括以下步驟： [〇〇1〇] 步驟10，提供一鎂合金預基材； - [0011] 步驟20，脫脂，用除油溶液去除該鎂合金預基材表面之 油污ί [0012] 步驟30，酸洗，用酸洗溶液去除該鎂合金預基材表面之 氧化物與離型劑； [0013] 步驟40，鹼洗，用鹼洗溶液去除該鎂合金預基材表面之 黑灰； [0014] 步驟50，化成’用含有單寧酸之化成溶液於該鎂合金預 基材表面形成磷化膜。 [0015] 於步驟20中’脫脂時間可控制於4至8分鐘，脫脂溫度可 控制於55至65°C。該除油溶液可為氫氧化鈉（Na〇H)或填 酸鈉（Na3P〇4)之水溶液。脫脂過程主要係用於去除該鎂 096150093 表單编號A0101 第4頁/共15頁 1003334214-0 1353393 Λ 100年09月14日修正替換頁 合金預基材表面之機油、切削油等有機油。可以理解， 於該鎂合金預基材先經過喷砂等方式處理後，鎂合金預 基材表面沒有油污，則該步驟20可省略。 [0016] 於步驟30中，酸洗時間可控制於3至5分鐘，酸洗溫度可 控制於35至45°C。本實施例中，該酸洗溶液包括濃度為5 至30克/升之檸檬酸（工業級） (HOOCCH9C(OH)(COOH)CH9COOH)與濃度可為 1. 5至6克/ L· 升之無矽水溶性表面活性劑（工業級）。 [0017] 檸檬酸可與鎂合金預基材表面之氧化物及壓鑄成型時噴 塗之離型劑反應，以去除該氧化物及離型劑。其可除去 之氧化物包括氧化鎂（MgO)、氧化鋁（Al2〇3)以及氧化辞 (ZnO)等；其可除去之離型劑包括高矽脂有機物 ((CH9) -CH(Si) -C00R)，其中R為曱基等官能團。檸 2 m η 檬酸於該酸洗溶液中可同時避免或減少於該鎂合金預基 材表面形成黑灰物質（主要成分係鋁、鋅）。檸檬酸於該 酸洗溶液之濃度優選為8至15克/升。於酸洗步驟中，檸 檬酸主要發生以下化學反應： [0018] MgO + 2H + = Mg2 + + H2〇 ； [0019] A10 +6H + = 2A13 + + 3H90 ；1353393 1 09 September 14, 2014 Shuttle Zheng VIII. Invention: [Technical Field] [0001] The present invention relates to a magnesium alloy workpiece and a magnesium alloy phosphating method. [Prior Art 3 [0002] Magnesium alloy light materials are widely used in automobiles and electrical equipment because of their low specific gravity, high strength, and suitability for recycling. However, because the chemical properties of the alloy are relatively active and the corrosion resistance is poor, the alloy workpieces in the town generally need to form an anti-corrosion film on the surface before use. The anti-corrosion film needs to have good salt spray resistance and high adhesion. Force and small surface impedance. [0003] In the prior art, a phosphating film is generally formed on the surface of a magnesium alloy workpiece by a phosphating method to improve its corrosion resistance. However, the conventional phosphating film is generally composed of a composite phosphate such as magnesium phosphate or manganese phosphate, which has poor adhesion to the paint layer in the subsequent coating process, and thus affects the use of the magnesium alloy workpiece. SUMMARY OF THE INVENTION [0004] In view of the above-mentioned mud, it is necessary to provide a town alloy workpiece and a town alloy dishing method. The phosphating film formed by the magnesium alloy phosphating method has high adhesion to the subsequently applied paint layer. [0005] a magnesium alloy phosphating method, comprising the steps of: providing a magnesium alloy pre-substrate; pickling, removing the oxide and release agent on the surface of the magnesium alloy pre-substrate with an acid pickling solution; The black ash of the surface of the magnesium alloy pre-substrate is removed by liquid-capacity; and the phosphating film is formed on the surface of the pre-substrate of the carbon alloy by using a solution containing tannic acid. [_ - Kind of lock alloy workpieces] The town's alloy guards include age gold pre-substrate and a 096150093 Form No. 101 0101 Page 3 / Total 15 pages 1003334214-0 1353393 100 years 0 formed on the surface of the money σ gold pre-substrate Wei film, which is formed by forming a solution of tannic acid on the surface of the magnesium alloy pre-substrate. _7] In the above-mentioned bonding gold scaling method, the chemical conversion solution contains tannic acid, and the surface properties of the formed phosphating film are improved, so that the phosphating film formed on the surface of the magnesium alloy workpiece is easily compared with the subsequently painted paint layer. High adhesion. [Embodiment] Hereinafter, a magnesium alloy workpiece and a magnesium alloy phosphating method of the present invention will be further described in detail with reference to the accompanying drawings and examples. [0009] Referring to FIG. 1, a flow chart of a magnesium alloy phosphating method according to a preferred embodiment of the present invention includes the following steps: [〇〇1〇] Step 10, providing a magnesium alloy pre-substrate; [0011] Step 20, degreasing, removing the oil stain on the surface of the magnesium alloy pre-substrate with a degreasing solution [0012] Step 30, pickling, removing the oxide and release of the surface of the magnesium alloy pre-substrate with an acid pickling solution [0013] Step 40, caustic washing, removing the black ash on the surface of the magnesium alloy pre-substrate with an alkali washing solution; [0014] Step 50, turning into a 'preparation of the magnesium alloy pre-substrate with a solution containing tannic acid A phosphating film is formed on the surface. [0015] In step 20, the degreasing time can be controlled from 4 to 8 minutes, and the degreasing temperature can be controlled from 55 to 65 °C. The degreasing solution may be an aqueous solution of sodium hydroxide (Na〇H) or sodium acetate (Na3P〇4). The degreasing process is mainly used to remove the magnesium. 096150093 Form No. A0101 Page 4 of 15 1003334214-0 1353393 09 September 14, 2014 Correction Replacement Page Organic oil such as engine oil and cutting oil on the surface of the alloy pre-substrate. It can be understood that the step 20 can be omitted after the magnesium alloy pre-substrate is treated by sand blasting or the like, and the surface of the magnesium alloy pre-substrate is free of oil. [0016] In step 30, the pickling time can be controlled from 3 to 5 minutes, and the pickling temperature can be controlled from 35 to 45 °C. 5至六克/L·升升。 In this embodiment, the sulphuric acid solution (industrial grade) (HOOCCH9C (OH) (COOH) CH9COOH) and the concentration may be 1. 5 to 6 g / L · liter A flawless water-soluble surfactant (industrial grade). [0017] The citric acid may be reacted with an oxide of the surface of the magnesium alloy pre-substrate and a release agent sprayed during die-casting to remove the oxide and the release agent. The removable oxides include magnesium oxide (MgO), aluminum oxide (Al2〇3), and oxidized (ZnO), etc.; the removable release agent includes sorghum organic ((CH9)-CH(Si)- C00R), wherein R is a functional group such as a thiol group. Lime 2 m η citric acid can simultaneously avoid or reduce the formation of black ash material (main component aluminum, zinc) on the surface of the magnesium alloy pre-base. The concentration of citric acid in the pickling solution is preferably from 8 to 15 g/l. In the pickling step, citric acid mainly undergoes the following chemical reaction: [0018] MgO + 2H + = Mg2 + + H2 〇 ; [0019] A10 + 6H + = 2A13 + + 3H90 ;
L ό LL ό L
[0020] ΖηΟ + 2Η + = Ζη2 + + Η2〇 ； [0021] Mg + 2H+ = Mg2 + + H9 ; u[0020] ΖηΟ + 2Η + = Ζη2 + + Η2〇; [0021] Mg + 2H+ = Mg2 + + H9 ; u
[0022] (CHJ -CH(Si) -C00R + H+ = R + +(CH0) -CH(Si) -C00H 2 m n 2 m n 096150093 表單編號A0101 第5頁/共15頁 1003334214-0 1353393 [0023] 1100年09月14日修正替換頁 無砂水溶性表面雜用於使鎂合金預基材表面反應更 加均句，避免酸洗過程中鎂合金預基材表面產生過度腐 蝕現象。1¾無石夕水溶性表面活性劑為低泡無石夕水溶性非 離子型表面活性劑，其親水基主要係羥基。該無矽水溶 性表面活性劑可為多元醇，例如聚乙二醇、甘油、季戊 四醇H、葡萄糖、山梨醇等。為使反應更均勻及避 免浪費，無矽水溶性表面活性劑於酸洗溶液中之濃度優 選為3至4克/升。 [0024] [0025] 於步驟40中，鹼洗之時間可為3至5分鐘，鹼洗之溫度可 為60至80°C。該鹼洗溶液中之鹼可為氫氧化鉀（K〇H)或 氫氧化鈉（NaOH)。 鹼洗用於與鎂合金預基材表面之黑灰物質（主要成分為鋁 與鋅）反應，用以除去黑灰，使錢合金基材暴露出來。若 採用工業級之虱氧化斜’其於該驗洗溶液中之濃度可為 60至180克/升，為使黑灰完全除去及避免後續碌化膜表 面局部發黑及避免後續生成之磷化膜之表面阻抗偏大， 氫氧化鉀於該鹼洗溶液中之濃度優選為1〇〇至15〇克/升。 氫氧化鉀主要發生以下化學反應： [0026] [0027] [0028] 6K0H+2A1=2K,A10 +3H0 ; ό O c 2ΚΟΗ+Ζη=Κ2Ζη〇2+Η2 。 於步驟50中，化成之時間可為30至50秒，化成之溫度可 為35至45 C。化成形成於遠鎂合金預基材表面之填化膜 厚度可為5至30微米，該鎂合金預基材之表面阻抗可小於 2歐姆。該化成溶液可包括2. 89至8. 67克/升之磷酸 096150093 表單编號Α0101 1003334214-0 1353393 [0029] [0030] [0031] 100年09月14日修正替换頁 PO )(工業级）、〇· 3至1克/升之尿素（分析純）、〇. 39 4 J 至1. 56克/升之确酸（ΗΝΟ」（工業級）、6至30克/升之 • ό 磷酸二氫猛（Μη(Η2Ρ04)2)(工業級）及0. 2至〇. 6克/升 之單寧酸（c76H52〇46)(分析純）。 磷酸之主要作用係提供形成磷化膜所需要之磷酸根離子 。碟酸於該化成溶液中之濃度優選為4. 34至6.5克/升。 尿素之主要作用係使形成之磷化膜更均勻。尿素於該化 成溶液中濃度優選為至0.6克/升。 硝酸之主要作用係提供遊離氫離子，以調整化成溶液之 PH值，使該化成溶液之PH值於6. 5至9. 5之間。為使碟化 膜具有較佳之抗鹽霧性能及較低之表面阻抗，硝酸於該 化成溶液中濃度優選為〇. 62至0. 94克/升。 [0032] 磷酸二氫錳之主要作用係提供錳離子、磷酸根離子及遊 離氫離子。磷酸二氫锰於該化成溶液中濃度優選為10至 [0033] 18克/升。 單寧酸之主要作用係增加鱗化臈與後續塗裝於磷化膜上 之油漆層之間之附著力。由於單寧酸係一極性高分子酸 ，其可與後續塗裝於填化膜上之油漆層中之樹脂如環氧 樹脂等物質相互吸引，從而使得碟化膜與油漆層之間之 附著力增強。單寧酸於該化成溶液中優選為至0.55克 /升。 形成磷化膜之時間^為3〇秒至5〇秒。形成之鱗化膜之主 要成分為磷酸鎮（Mg3(P〇4)2)、磷酸锰（Mn3(P〇4)2)等複 合磷酸鹽，其中主要化學反應方程式如下： 096150093 表單编號A0101 第 1003334214-0 [0034] 1353393 100年09月14日梭正替換頁 [0035] Mg+2H+=Mg2+ + Η2； [0036] 3Mg2++2P〇43 _=Mg3 丨(Ρ〇< 丨V [0037] 3Μη2 + + 2Ρ〇/ =Μη. ,(ΡΟ; _ )〇。 [0038] 複合磷酸鹽其化學代表式可為： (Mg2 + )A(Mn2 + )B(N03_)c(Zn2 + )D(P043_)f。 [0039] 由於形成磷化膜之化成溶液中含有單寧酸與尿素，故， 磷化膜中含有碳（C)、氧（0)、鎂（Mg)、鋁（A1)、磷 (P)、锰（Μη)等元素。 [0040] 可以理解，於步驟20 '步驟30、步驟40及步驟50後還可 分別進行至少一次水洗步驟，以及於步驟50後還可還進 一步對該鎂合金工件進行烘烤處理，其中烘烤之時間為 30至70分鐘，烘烤之溫度為110至150°C。 [0041] 為進一步對上述鎂合金磷化方法進行說明，以下將以具 體實施例說明。 [0042] 提供三組（第一組、第二組與第三組）鎂合金預基材，該 鎂合金預基材之材質均為AZ91D型鎂合金，採用如圖2所 示之工藝流程及參數，對該三組鎂合金預基材進行磷化 處理；且於磷化處理過程中，第一組、第二組與第三組 鎂合金預基材於脫脂、酸洗、鹼洗及化成工藝中所採用 之溶液相應之組分濃度分別如圖3中之A組、B組、C組所 在列所示。 [0043] 磷化處理後之三組鎂合金工件，各抽樣檢測三個樣品， 測試結果如圖4所示。其中，鹽霧測試於鹽霧箱中進行， 096150093 表單編號A0101 第8頁/共15頁 1003334214-0 93 100年09月14日修正巷;換i 使用5%之氯化鈉溶液；表面阻抗測試使用微歐姆計與探 針；附著力係於鎂合金工件表面塗裝油漆層後，使用百 格刀測試。 [〇〇44] 從圖4中可以看出，三組樣品之鹽霧測試均超過8級，表 面阻抗均小於2歐姆，附著力均大於3B。可見，採用本發 明之鎂合金磷化方法處理之鎂合金工件具有良好之耐鹽 霧性能、較高之附著力及較小之表面阻抗。當該鎂合金 工件應用於可檇式電子裝置時，可確保該可檇式電子裝 置具有較強之電磁波遮罩能力。 °45〕综上所述，本發明符合發明專利要件，爰依法提出專利 申凊》惟，以上所述者僅為本發明之較佳實施方式，本 發明之範圍並不以上述實施方式為限，舉凡熟悉本案技 藝之人士’於援依本案發明精神所作之等效修飾或變化 ，皆應包含於以下之申請專利範圍内。 【圖式簡單說明】 [_] m係本發明較佳實施方式之錤合金魏方法之流程圖。 [〇〇47]圖2鎂合金磷化工藝流程及參數圖。 [_]則磷㈣程帽脂、酸洗、驗Μ化成步驟之溶液配方 [0049] 圖4樣品測試結果圖。 【主要元件符號說明】 [0050] 無 096150093 表單編號Α0101 第9頁/共15頁 1003334214-0(CHJ -CH(Si) -C00R + H+ = R + +(CH0) -CH(Si) -C00H 2 mn 2 mn 096150093 Form No. A0101 Page 5 of 15 1003334214-0 1353393 [0023] Modified on September 14, 1100, the water-free surface of the replacement page is used to make the surface reaction of the magnesium alloy pre-substrate more uniform, avoiding the excessive corrosion of the surface of the magnesium alloy pre-substrate during the pickling process. The surfactant is a low-foaming, non-ionic surfactant, and the hydrophilic group is mainly a hydroxyl group. The water-free surfactant can be a polyhydric alcohol, such as polyethylene glycol, glycerin, pentaerythritol H, Glucose, sorbitol, etc. In order to make the reaction more uniform and avoid waste, the concentration of the water-free surfactant in the pickling solution is preferably 3 to 4 g / liter. [0025] In step 40, the base The washing time may be 3 to 5 minutes, and the alkali washing temperature may be 60 to 80° C. The alkali in the alkali washing solution may be potassium hydroxide (K〇H) or sodium hydroxide (NaOH). Reacting with black ash material (mainly composed of aluminum and zinc) on the surface of the magnesium alloy pre-base to remove black ash The alloy substrate is exposed. If the industrial grade is used, the concentration of the alloy may be 60 to 180 g/liter in order to completely remove the black ash and avoid partial blackening of the surface of the subsequent film. The surface resistance of the subsequently formed phosphating film is prevented from being excessively large, and the concentration of potassium hydroxide in the alkali washing solution is preferably from 1 Torr to 15 gram per liter. The main chemical reaction occurs in potassium hydroxide: [0026] [0027] [0028] 6K0H+2A1=2K, A10 +3H0; ό O c 2ΚΟΗ+Ζη=Κ2Ζη〇2+Η2. In step 50, the formation time may be 30 to 50 seconds, and the formation temperature may be 35 to 45 I. The formation of the solution may be 2. 89 to 8. 67. The formation of the solution may be less than 2 ohms.克/升的磷酸096150093 Form No. 1010101 1003334214-0 1353393 [0030] [0031] Correction replacement page PO of September 14, 100 (industrial grade), 〇·3 to 1 gram/liter of urea ( Analytically pure, 〇. 39 4 J to 1. 56 g / liter of acid (ΗΝΟ) (industrial grade), 6 to 30 g / liter • ό phosphoric acid Hydrogen (Μη(Η2Ρ04)2) (industrial grade) and 0.2 to 〇. 6 g/l of tannic acid (c76H52〇46) (analytical grade). The main role of phosphoric acid is to provide the formation of a phosphate film. Phosphate ion. The concentration of the acid in the solution is preferably from 4.34 to 6.5 g / liter. The main function of urea is to make the formed phosphating film more uniform. The concentration of urea in the formation solution is preferably from 0.6 g/liter. 5之间之间。 The pH is between 6.5 and 9.5. The concentration of the nitric acid in the solution is preferably 6262 to 0.94 g/liter, so that the concentration of the nitric acid in the solution is preferably 〇62. [0032] The main action of manganese dihydrogen phosphate is to provide manganese ions, phosphate ions, and free hydrogen ions. The concentration of manganese dihydrogen phosphate in the chemical conversion solution is preferably from 10 to 18 g/liter. The main function of tannic acid is to increase the adhesion between the squamous sputum and the subsequent paint layer applied to the phosphating film. Since the tannic acid is a polar polymer acid, it can be attracted to a resin such as an epoxy resin which is subsequently applied to the paint layer on the filling film, thereby causing adhesion between the disc film and the paint layer. Enhanced. The tannic acid is preferably in the formation solution to 0.55 g / liter. The time for forming the phosphating film is from 3 sec to 5 sec. The main components of the formed scaled film are phosphate phosphate (Mg3 (P〇4) 2), manganese phosphate (Mn3 (P〇4) 2) and other complex phosphates, the main chemical reaction equation is as follows: 096150093 Form No. A0101 1003334214-0 [0034] 1353393 September 14th, 2014 Shuttle replacement page [0035] Mg+2H+=Mg2+ + Η2; [0036] 3Mg2++2P〇43 _=Mg3 丨(Ρ〇< 丨V [0037] 3Μη2 + + 2Ρ〇/ =Μη. ,(ΡΟ; _ )〇. [0038] The chemical formula of the complex phosphate can be: (Mg2 + ) A(Mn2 + )B(N03_)c(Zn2 + )D (P043_)f. [0039] Since the formation of the phosphating film contains tannic acid and urea, the phosphating film contains carbon (C), oxygen (0), magnesium (Mg), and aluminum (A1). , such as phosphorus (P), manganese (Μη), etc. [0040] It can be understood that at least one water washing step may be performed after step 20 'step 30, step 40 and step 50, and further may be further after step 50 The magnesium alloy workpiece is subjected to a baking treatment, wherein the baking time is 30 to 70 minutes, and the baking temperature is 110 to 150 ° C. [0041] To further describe the above magnesium alloy phosphating method, the following will With Description of Embodiments [0042] Three sets (first group, second group and third group) of magnesium alloy pre-substrate are provided, and the material of the magnesium alloy pre-substrate is AZ91D type magnesium alloy, as shown in FIG. The process and parameters of the three groups of magnesium alloy pre-base materials are phosphating; and in the phosphating process, the first group, the second group and the third group of magnesium alloy pre-base materials are degreased, pickled, The corresponding component concentrations of the solutions used in the alkaline washing and chemical formation process are shown in the columns of Group A, Group B, and Group C in Figure 3. [0043] Three sets of magnesium alloy workpieces after phosphating, each sample Three samples were tested and the test results are shown in Figure 4. Among them, the salt spray test was carried out in a salt spray box, 096150093 Form No. A0101 Page 8 / Total 15 Page 1003334214-0 93 Corrected Lane on September 14, 100 i Use a 5% sodium chloride solution; the surface impedance test uses a micro-ohmmeter and a probe; the adhesion is applied to the surface of the magnesium alloy workpiece after the paint layer is applied, and the test is performed using a hundred-square knife. [〇〇44] From Figure 4 It can be seen that the salt spray test of the three groups of samples exceeds 8 grades, and the surface impedance is less than 2 ohms. The force is greater than 3B. It can be seen that the magnesium alloy workpiece treated by the magnesium alloy phosphating method of the invention has good salt spray resistance, high adhesion and small surface resistance. When the magnesium alloy workpiece is applied to the crucible In the case of an electronic device, it is ensured that the portable electronic device has a strong electromagnetic wave shielding capability. The above is a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above embodiment. Equivalent modifications or changes made by those who are familiar with the skill of the case in the spirit of the invention shall be included in the scope of the following patent application. BRIEF DESCRIPTION OF THE DRAWINGS [_] m is a flow chart of a method for forming a niobium alloy according to a preferred embodiment of the present invention. [〇〇47] Figure 2 Magnesium alloy phosphating process and parameter map. [_] The formula of the solution of the phosphorus (four) cap, the pickling, and the step of chemical conversion [0049] FIG. [Main component symbol description] [0050] None 096150093 Form number Α0101 Page 9 of 15 1003334214-0