201037302 六、發明說明 【發明所屬之技術領域】 本發明是有關於一種分析方法，特別是指一種電化學 分析方法。 【先前技術】 ❹ Ο 「熱浸鑛鋅鋼板」以製作方式區分可分為「熱浸鍍辞 鋼板」（Hop-dip galvanized，以下簡稱gi鋼板）和「熱浸鑛 鐵鋅鋼板」（Galvannealed，以下簡稱GA鋼板）二類，其製 作方法大抵是將冷軋後的板狀鋼材經過還原氣氛爐還原 後，浸到一高溫的熔融鋅液中，由於在高溫的熱浸辞液過 程中，液態的辞和固態的鐵會產生擴散作用而獲得冶金上 之接合，因此，當鋼材離開鋅液後即會彼覆一層鋅構成的 鑛層，接著再以風刀括除部分液態的鋅藉以控制錢層厚 度；而之後，如果直接冷卻即可得到GI鋼板，而如果先進 入到加熱爐内進行合金化反應後再冷卻，則得到ga鋼板。 在上述高溫的熱浸鑛鋅製程中，由於鐵和辞的反應激 烈，因此容易在鋼材和辞構成的鑛層間形成包括有鐵辞合 金組成的界面層，由於鐵鋅合金组成的性質為脆、硬且： 度較低，因此，料面層中包含大量的鐵鋅合金組成時， 則容易造成熱浸鍍鋅鋼板在後續的製程或產品應用時，沿 著界面層中的鐵鋅合金組成斷裂，從： 產品壽命的降低。 或 目前為了抑制界面層中鐵鋅合金組成的生成，通常舍 在鋅液中添加微量的鋁，刹 、节會 利用鋁在兩溫時跟鐵的擴散速率 3 201037302 較㈣’囚此’當將鋼材浸在添加㈣辞液時， 鐵紹D金、，，且成’此肋合金組成與碳鋼鋼材的密著性較 辞合金t錢，且可抑_料纽成_成，從而可以 調控熱次鍍辞鋼板界面層的結構’並提升熱浸 鍵層與碳鋼鋼材彼此的㈣強度，進㈣後續= 昇，以及維持產品應用時的穩定。 由述說月可知，在熱浸鑛鋅鋼板的製作過程中 18合金組成的形成與否’和熱浸鑛辞鋼板後續的性質與應 用息息相關，因此如何快速並準柄分析在熱浸鑛鋅的製 作過程中，鐵鋁合金组成的生成與否，以提供生產線製程 即時參考訊息’確保熱浸_鋼板生產品質的穩定，一直 是本技術領域者研究的方向之一。 舉例來說，美國專利第US6,342,31G號案，揭示一種以 穿透式電子顯微鏡（TEM)方法解析熱浸鍵辞鋼板之界面層的 微結構1外’電化學剝除法則是目前另—種用來分析敎 浸鑛鋅鋼板之界面層的方法，其主要是利用在—固定的外 加電流下’讓熱浸鑛鋅鋼板進行陽極溶解，藉由紀錄隨不 同時間溶解時相對於參考電極所得到的電位值進行分析。 而以牙透式電子顯微鏡分析熱浸鑛辞鋼板，不僅 需要昂貴的設備，且在試片的製作跟觀察上都相當費時’ 不符合生產鋼板的即時需要；而以電化學剝除法進行熱浸 鍍鋅鋼板結構的分析，雖然可從量測結果定義出各鍍層溶 解的¥間，進而得知熱浸鍍鋅鋼板的微組織結構，但是缺 ‘’占仍然疋實驗铯費的時間太長，且須精確的控制外加電源 201037302 的電流密度，同樣地無法滿足生產的即時需求。 因此’如何提供-種簡易、快速、省時且精確的方 法，有效的分析熱浸鑛辞鋼板的結構，進而控制生產执浸 鍍鋅鋼板的生產品質，-直是本技術領域者不斷改良的方 向之一。 【發明内容】 因此，本發明之目的，即在提供一種簡單且可快速的201037302 VI. Description of the Invention [Technical Field of the Invention] The present invention relates to an analytical method, and more particularly to an electrochemical analysis method. [Prior Art] ❹ 「 "Hot-dip galvanized steel sheet" can be classified into "Hop-dip galvanized" (hereinafter referred to as gi steel sheet) and "hot-dip iron-zinc steel sheet" (Galvannealed). The following is abbreviated as the second type of GA steel plate. The production method is generally that the cold rolled steel plate is reduced in a reducing atmosphere furnace and then immersed in a high-temperature molten zinc liquid. The words and solid iron will diffuse and get metallurgical joints. Therefore, when the steel leaves the zinc liquid, it will be covered with a layer of zinc, and then the air knife will be used to remove some liquid zinc to control the money. The layer thickness; and then, if directly cooled, the GI steel sheet can be obtained, and if it is first introduced into a heating furnace for alloying reaction and then cooled, a ga steel sheet is obtained. In the high-temperature hot-dip galvanizing process described above, due to the intense reaction between iron and rhodium, it is easy to form an interfacial layer composed of an iron-alloy alloy between the steel layer and the ore-contained layer, since the composition of the iron-zinc alloy is brittle, Hard and: low degree, therefore, when the material layer contains a large amount of iron-zinc alloy composition, it is easy to cause the hot-dip galvanized steel sheet to break along the iron-zinc alloy in the interface layer in the subsequent process or product application. From: Reduced product life. Or at present, in order to suppress the formation of iron-zinc alloy composition in the interface layer, a small amount of aluminum is usually added to the zinc solution, and the diffusion rate of aluminum with iron at two temperatures is used. When the steel is immersed in the addition (4) lexical liquid, the iron shovel D gold, and, into the rib alloy composition and the carbon steel steel, the adhesion of the alloy is more than the money, and can inhibit the _ material into a _ into, which can be regulated The thermal-polished steel plate interface layer structure 'and enhances the (four) strength of the hot dip bond layer and the carbon steel steel, the subsequent (four) subsequent = rise, and maintain the stability of the product application. It can be seen from the description of the month that the formation of the 18 alloy composition in the production process of hot-dip galvanized steel sheet is closely related to the subsequent properties and application of the hot-dip mining steel plate, so how to quickly and accurately analyze the production of hot-dip zinc In the process, the formation of iron-aluminum alloy composition to provide instant reference information for the production line process to ensure the stability of hot dip _ steel plate production quality has been one of the research directions of this technology. For example, U.S. Patent No. 6,342,31G discloses a method for analyzing the microstructure of an interface layer of a hot dip bond steel plate by a transmission electron microscope (TEM) method. The 'electrochemical stripping rule is currently another. a method for analyzing an interfacial layer of a strontium-zinc-zinc steel plate, which is mainly used for anodic dissolution of a hot-dip galvanized steel plate under a fixed impressed current, by recording with respect to a reference electrode when dissolving at different times The resulting potential values were analyzed. The analysis of hot-dip mining plates by a tooth-to-earth electron microscope requires not only expensive equipment, but also time-consuming and time-consuming production and observation of the test pieces, which does not meet the immediate needs of the production of steel plates, and hot-dip by electrochemical stripping. The analysis of the structure of the galvanized steel sheet, although the measurement results can be used to define the dissolution of each coating, and then the microstructure of the hot-dip galvanized steel sheet is known, but the lack of time is too long. The current density of the external power supply 201037302 must be precisely controlled, which cannot meet the immediate needs of production. Therefore, 'how to provide a simple, fast, time-saving and accurate method, effectively analyze the structure of the hot-dip mine steel plate, and then control the production quality of the production of immersed galvanized steel sheet, which is directly improved by the technical field. One of the directions. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a simple and fast
得知生產之熱錢辞鋼板結構的_料鋼㈣分析方 法。 為了簡化分析方法，以快速且有效的分析熱浸鐘辞鋼 板之界面層的結構’發明人以溶財式，藉由將熱浸鑛辞 鋼板置於-預定濃度的酸性純液中，將熱浸鑛辞鋼板由 最外層逐步向内㈣’並在溶㈣過程中同時量測不同溶 姓時間之開路電位，得到__溶㈣間·開路電位e(v，相對 餘和甘汞電極 ’ saturated calomel electr〇de(scE))曲線並 再將該溶蝕時間_開路電位曲線進行二次微分，藉由該二次 微 77曲線圖的曲率變化gp可,决；、 J坤千雙化即j厌迷且有效的分析熱浸鍍鋅鋼 板之界面層的結構。 於是，本發明一種熱浸鍍辞鋼板的分析方法，用於即 時得知熱浸鑛辞鋼板的結構，該熱浸鑛鋅鋼板具有一碳鋼 基材卩鋅構成的鑛層’及—在該碳鋼基材形成該鑛層 的過程中形成在該碳鋼基材與該鍍層之間的界面層，該分 析方法包含一溶蝕量測步驟、一微分步驟，及一判讀步 5 201037302 該溶蝕量測步驟，將一熱浸鍍鋅鋼板浸置在—酸性溶 蝕液中進行溶蝕，並在溶蝕的同時，量測該熱浸鍍鋅鋼板 對應於溶蝕時間的開路電位值，得到一條以溶蝕時間-開路 電位為X-y座標軸的對應曲線。 該微分步驟，是將該量測步驟得到的對應曲線進行二 次微分，得到一條二次微分曲線 該判讀步驟，是判讀該二次微分曲線，若該二次微分 曲線是由正值達到一最終為零之穩定值範圍時，判斷該界 面層具有鐵鋁合金組成，若該二次微分曲線是由負值達到 該最終為零之穩定值範圍，判斷該界面層不具有鐵鋁合金 組成。 本發明之功效在於：利用判讀開路電位與溶蝕時間的 二次微分曲線變化，即可快速正確地判斷該熱浸鍍鋅鋼板 之界面層疋否具有鐵鋁合金組成，進而可即時控制熱浸鍍 鋅鋼板的製程以生產出品質合於生產規格的熱浸鍍鋅鋼 板0 【實施方式】 有關本發明之前述及其他技術内容、特點與功效，在 以下配合參考圖式之一個較佳實施例的詳細說明中，將可 清楚的呈現。 <實施例> 參閱圖1，本發明熱浸鍍鋅鋼板的分析方法的一較佳實 施例，用於分析以熱浸鍍辞的生產製程所生產的熱浸鍍鋅 鋼板’該熱浸鍍辞鋼板具有一碳鋼基材、一以鋅構成的鑛 201037302 層，及一在該碳鋼基材形成該鍍層的過程中形成在該碳鋼 基材與該鍍層之間的界面層，具體的說，該熱浸鍍辞鋼板 是先將高溫的含碳鋼板，捲浸通過高溫且添加有重量百分 比為0.1〜0.2wt%之鋁的熔融鋅液後，即可得到該熱浸鍍辞 鋼板。 該熱浸鍍鋅鋼板的分析方法的較佳實施例是包含一溶 蝕量測步驟21、一微分步驟22，及一判讀步驟23。 首先是進行該溶蝕量測步驟21，將取樣自熱浸鍍鋅的 ¢) 生產製程所生產的熱浸鍍鋅鋼板，將其浸置在溫度是20〜80 °C，且重量百分比濃度為卜l〇wt%的酸性溶蝕液中進行溶 蝕，並在溶蝕的同時，量測該熱浸鍍鋅鋼板在不同溶蝕時 . 間下之開路電位，得到一以溶蝕時間-開路電位為x-y座標 . 軸的對應曲線。 具體的說，該步驟是先將該熱浸鍍鋅鋼板清洗後裁切 成邊長為10-50mm的方形試片，在90°C的烘烤中烘烤5分 鐘後，將試片以鐵氟龍載台套住露出固定面積，浸置於該 〇 溶蝕液中進行該熱浸鍍鋅鋼板的溶蝕，並同時量測於不同 溶蝕時間下的表面電位，該表面電位即為開路電位（Open Circuit Potential，OCP);於本實施例中，是以飽和甘汞電 極（SCE)為參考電極，以恆電位儀（型號：EG&G263A，製造 廠商：Princeton Applied Research)量測該熱浸鍍鋅鋼板在不 同溶蝕時間下相對於該參考電極之開路電位，並在量測得 到該基材之標準開路電位時即可停止該溶蝕量測步驟，得 到一溶蝕時間-開路電位的對應曲線。 7 201037302 進v地說a月，當該溶钱液的濃度或溫度太高時，溶 蝕速度較快，而因界面層的厚度通常極薄（<1μηι)，因此較 不：觀測到表面電位轉折處，而當溶蝕液的濃度或溫度太 :、’則所耗費的製程時間會較長，適用於本發明的酸性 ::蝕液可選自鹽酸、硝酸、硫酸或該等酸的組合，由於 六液僅在於以適當的溶钱速率自熱浸鑛辞鋼板外層向内 ，合姓，所以其種類、濃度等並非本發明創作重點所在，故 八★再夕作闡述’於本實施例中使用的溶姓液是重量百 分比濃度為4wt%的鹽酸，且溶钱溫度為25t。 接著進行該微分步驟22，將由該純量測步驟2ι得到 時間·開路電㈣線進行：讀分，得到—溶姓時間· 開路電位的二次微分曲線。 最終進仃t是該判讀步冑23 ’由該二次微分曲線達到 、‘,、、-之穩疋值範圍前的正、負值即可判斷該界面層是 否具有鐵鋁合金組成。 :體的5兑’當該二次微分曲線是由正值達到最終為零 :穩疋值範圍時’則判斷該熱浸鍍鋅鋼板之鑛層與碳鋼基 ^界面層具有鐵紹合金組成’若該二次微分曲線是由 負值達到最終為零之穩定值_，則_該 :鑛層與碳鋼基材間的界面層不具有仙合金組成，= 了由鐵紹合金組成的存在與否，判定該熱浸鑛辞鋼板的界 ==是否合於生產規格’依前述可知，當界面層存在 金组成時’代表其鑛層、界面層與碳鋼基材彼此 、者f佳纟就疋合於生產規格所需的熱浸鍍鋅鋼板， 201037302 月^ ρ時調整、控制生產的熱浸鍍辞鋼板，進而 製程的良率。 屋 ❹ 〇 、夺另外，值得一提的是，當由該判讀步驟23中判斷該熱 讀鋅鋼板之鑛層與碳鋼基材間的界面層具有鐵銘合金組 成時’則由該二次微分曲線達到最終為零之穩定值範圍前 的兩個相鄰零點的距離，即可判斷為該界面層之鐵紹合金 組成的溶餘時間，再與具不同標準膜厚之鐵紹合金組成在 同樣酸性溶钱液尹量得的厚度_溶钱時間時標準曲線進行内 插法運算，即可求得該界面層中鐵紹合金組成的厚度，進 而可以明確得知該界面層的微觀結構組織。 由上述說明可知’本發明主要是利用適當的酸性溶蝕 =行㈣並進行開路電位的量測，以快速地取得溶= ^開路電位對應曲線，之後再將溶料間·開路電位對應曲 续進:一次微分’而得到溶餘時間-開路電位的二次微分曲 估’藉由二次微分曲線達到最終為零之穩定值前的正、負 二即：快速判斷熱浸鍍辞鋼板之界面層中是否具有鐵銘合 不僅不需像習知以電化學剥除法，必須精確控制 抓的電流控度以逐步剝除熱浸鑛辞鋼板的層層結 二雜=不需要如穿透式電子顯微鏡觀察法一般，必須經過 試片準備過程才能得知界面層的微觀結構，確實具 ^速且正確地即時得知生產之熱浸錢鋅鋼板的品質的優 i述本發明熱祕鋅鋼板的分析方法㈣佳實施例， -口以下具體例的說明後，t可更加清楚的明白。 9 201037302 <具體例> 由於熱浸鍍鋅鋼板之界面層的組成結構會因為熱浸鍍 鋅製程的處理條件’例如：碳鋼基材的人溫鋅液的溫 度鋅液中之链含篁與鋼材於辞液中的浸锻時間而有所不 同’因此，本發明具❹"〜5使用之熱浸鍍鋅鋼板，是以 不同紹含量之鋅液、鋅液溫度、鋼材人溫，及浸鍍時間達 行…、’又鑛鋅製程所製得之五組熱浸鑛鋅鋼板，接著再分別 以本發明的分析方法進行分析判讀，兹將該五個具體例之 熱浸鍍辞鋼板簡單整理於表一。I learned the method of analysis of the steel sheet (4) of the steel sheet structure of the production. In order to simplify the analysis method, the structure of the interface layer of the hot-dip steel plate is analyzed quickly and efficiently. The inventor uses the solvent-saving formula to heat the hot-dip mine plate by placing it in a predetermined concentration of acidic pure liquid. The leaching of the plate from the outermost layer gradually inward (four) 'and in the process of dissolution (four) simultaneously measure the open circuit potential of different dissolution time, get __ dissolved (four) open circuit potential e (v, relative residual and calomel electrode 'saturated The calomel electr〇de(scE)) curve and then the second time of the dissolution time_open circuit potential curve, by which the curvature change gp of the second micro 77 curve can be determined, J J Kun Qian double or j The structure of the interface layer of the hot dip galvanized steel sheet is analyzed and effectively analyzed. Therefore, the present invention relates to a method for analyzing a hot dip plated steel plate for instantly knowing the structure of a hot dip slag steel plate having a carbon steel substrate bismuth zinc and a deposit layer and An interface layer formed between the carbon steel substrate and the plating layer during formation of the carbon steel substrate, the analysis method comprising a corrosion measurement step, a differential step, and a reading step 5 201037302 In the measuring step, a hot dip galvanized steel sheet is immersed in an acidic etching solution for dissolution, and at the same time of dissolution, the open circuit potential value corresponding to the dissolution time of the hot dip galvanized steel sheet is measured, and a dissolution time is obtained - The open circuit potential is the corresponding curve of the Xy coordinate axis. The differentiating step is to secondarily differentiate the corresponding curve obtained by the measuring step to obtain a second differential curve. The reading step is to read the second differential curve, and if the second differential curve is positive, the final value is reached. When the range of the stable value is zero, it is judged that the interface layer has an iron-aluminum alloy composition, and if the second differential curve is from a negative value to the final zero stable range, it is judged that the interface layer does not have an iron-aluminum alloy composition. The effect of the invention is that the boundary layer of the hot dip galvanized steel sheet can be quickly and correctly determined by using the change of the second differential curve of the open circuit potential and the dissolution time to have the composition of the iron aluminum alloy, and the hot dip coating can be controlled immediately. The process of the zinc steel plate is to produce a hot-dip galvanized steel sheet having a quality in accordance with the production specifications. [Embodiment] The foregoing and other technical contents, features and effects of the present invention are related to a preferred embodiment of the following reference drawings. In the detailed description, it will be clearly presented. <Embodiment> Referring to Fig. 1, a preferred embodiment of the analysis method of the hot dip galvanized steel sheet of the present invention is for analyzing a hot dip galvanized steel sheet produced by a hot dip plating process. The plated steel plate has a carbon steel substrate, a 201037302 layer of zinc, and an interface layer formed between the carbon steel substrate and the plating layer during the formation of the carbon steel substrate. The hot dip plated steel sheet is obtained by first immersing a high temperature carbon-containing steel sheet through a molten zinc liquid having a high temperature and adding 0.1 to 0.2% by weight of aluminum by weight. . A preferred embodiment of the method for analyzing a hot dip galvanized steel sheet includes an erosion measurement step 21, a differential step 22, and an interpretation step 23. First, the corrosion measurement step 21 is performed, and the hot-dip galvanized steel sheet produced by the hot-dip galvanizing process is immersed at a temperature of 20 to 80 ° C, and the weight percentage is L〇wt% of the acidic dissolution solution is dissolved, and while the corrosion is being measured, the open-circuit potential of the hot-dip galvanized steel sheet under different dissolution is measured, and a dissolution time-open circuit potential is obtained as the xy coordinate. Corresponding curve. Specifically, in this step, the hot-dip galvanized steel sheet is first cleaned and cut into square test pieces having a side length of 10-50 mm, and baked in a baking at 90 ° C for 5 minutes, and then the test piece is iron-treated. The fluorocarbon carrier covers the exposed fixed area, is immersed in the bismuth dissolution liquid to dissolve the hot dip galvanized steel sheet, and simultaneously measures the surface potential under different etching time, and the surface potential is an open circuit potential (Open Circuit Potential (OCP); In this embodiment, the hot-dip galvanizing is measured by a potentiostat (model: EG&G263A, manufacturer: Princeton Applied Research) using a saturated calomel electrode (SCE) as a reference electrode. The open circuit potential of the steel plate relative to the reference electrode at different dissolution times, and the measurement of the standard open circuit potential of the substrate can be stopped to obtain the corresponding curve of the dissolution time-open circuit potential. 7 201037302 Into a month, when the concentration or temperature of the solution is too high, the dissolution rate is faster, and the thickness of the interface layer is usually very thin (<1μηι), so less: surface potential is observed At the turning point, when the concentration or temperature of the dissolution solution is too: ', the process time taken may be longer, and the acidity suitable for the present invention: the etching liquid may be selected from hydrochloric acid, nitric acid, sulfuric acid or a combination of such acids. Since the six liquids only lie in the outer layer of the outer layer of the hot-dip smelting steel at the appropriate rate of dissolution, the type and concentration of the steel are not the focus of the present invention, so the description is made in this embodiment. The solution used was a hydrochloric acid having a concentration by weight of 4% by weight and a solvent temperature of 25t. Then, the differentiation step 22 is performed, and the time-and-open circuit (four) line is obtained from the pure measurement step 2: the reading is performed to obtain a second differential curve of the time of the solution and the open circuit potential. The final step t is that the interpretation step 23' determines whether the interface layer has an iron-aluminum alloy composition by the positive and negative values before the second differential curve reaches the range of the stability values of ',,, -. : When the secondary differential curve is from the positive value to the final zero: stable value range, then it is judged that the hot-dip galvanized steel sheet and the carbon steel base interface layer have the composition of the iron-sand alloy 'If the secondary differential curve is a stable value from a negative value to a final zero, then the interface layer between the mineral layer and the carbon steel substrate does not have a fairy alloy composition, = the presence of a composition consisting of iron-smelting alloy Whether or not it is determined whether the boundary of the hot dip ore plate == is in conformity with the production specification. As can be seen from the foregoing, when the interface layer has a gold composition, it represents the mineral layer, the interface layer and the carbon steel substrate. The hot-dip galvanized steel sheet required for the production specifications is adjusted and controlled to produce the hot-dip galvanized steel sheet at 201037302. It is worth mentioning that when it is judged from the interpretation step 23 that the interface layer between the mineral layer of the hot-read zinc steel sheet and the carbon steel substrate has the composition of the iron alloy, then the second The distance between the two adjacent zero points before the differential curve reaches the range of the final zero stable value can be judged as the residual time of the composition of the iron-sand alloy of the interface layer, and then composed of the iron-sand alloy with different standard film thicknesses. Similarly, the thickness of the acidic solvent solution Yin _ the time of the solvent curve is interpolated, the thickness of the composition of the iron-sand alloy in the interface layer can be obtained, and the microstructure of the interface layer can be clearly known. . It can be seen from the above description that the present invention mainly uses appropriate acid dissolution = row (four) and measures the open circuit potential to quickly obtain the corresponding curve of the dissolution = ^ open circuit potential, and then continues the interaction between the melt and the open circuit potential. : One time differential 'and get the remnant time - the second derivative of the open circuit potential'. The positive and negative two before the stable value of the final zero is obtained by the second differential curve: quickly determine the interface layer of the hot dip plated steel plate Whether or not there is iron in the joint does not need to be electrochemically stripped as in the prior art, and the current control of the grasping must be precisely controlled to gradually remove the layered knot of the hot-dip mining steel plate. In the observation method, the microstructure of the interface layer must be known through the preparation process of the test piece. It is true that the quality of the hot-dip zinc steel plate produced by the instant is known and accurately. Method (4) A good example, after the description of the specific example below, the t can be more clearly understood. 9 201037302 <Specific Example> Since the composition of the interface layer of the hot dip galvanized steel sheet is due to the processing conditions of the hot dip galvanizing process, for example, the temperature of the zinc liquid of the carbon steel substrate is in the chain of the zinc liquid.篁 and steel immersion time in the liquid is different. Therefore, the hot-dip galvanized steel sheet used in the present invention has a different content of zinc liquid, zinc liquid temperature, and steel temperature. And the immersion plating time reaches..., and the five sets of hot-dip galvanized steel sheets obtained by the smelting process of zinc and zinc are then analyzed and interpreted by the analysis method of the present invention, respectively. The steel plates are simply arranged in Table 1.
表一 鋅液中銘含量 (wt%) T ——---- _ 鋅液溫度 (°c ) 鋼材入溫 (°C) 浸鍍時間 (S) 具體例1 0.12 500 具體例2 0.2 460 520 5 具體例3 0 16 520 3 具體例4 0.16 460 dfkO _ 490 5 ' 具體例5 0.2 460 • ----------」 480 480 3Table 1 Zinc liquid content (wt%) T —————— _ Zinc liquid temperature (°c) Steel temperature (°C) Dip plating time (S) Specific example 1 0.12 500 Specific example 2 0.2 460 520 5 Specific example 3 0 16 520 3 Concrete example 4 0.16 460 dfkO _ 490 5 'Specific example 5 0.2 460 • ----------” 480 480 3
參閱圖2〜圖6 ’ Η 2〜圖6分別是該五個具體例的開路 -位-溶料㈣應㈣（以實線表㈡，及開 間的二次微分曲虛線料）。 4時 座參閱圖2,圖2是該具體例1的開路電位·溶钱時， ‘曲線（以實線表示），及開路電位·溶料 線（以虛線標繪）。 刀f ……π %#汾挪呷間二次微分曲線可看出， 2次微分曲線是從二次微分值為負值（即圖示中箭^所 ‘處）達到最終為零之穩定值範圍，因此判斷此具體例】的 10 201037302 熱浸鑛辞鋼板之界面層不具有鐵㈣金組成。 =斷結果，可由圖2中之開路電位 (實線標不)，再經過與各材質(即碳 J曲線 鋁合金組成、辞..等）之_。金組成、鐵 、 寻）之料開路電位比對後確認，圖2 之-1.04伙特處為純鋅錄層之開路電位、仙伏特對應 =合=成之標準開路電位，最後·〇 5伏特對應處::鋼 層/界面^可知該具體例1之熱浸錄辞鋼板結構為純鋅鍍 ❹Referring to Fig. 2 to Fig. 6' Η 2 to Fig. 6 are the open circuit-position-dissolving materials (4) of the five specific examples, respectively (four) (in the solid line table (2), and the second differential curved line material in the open). Referring to Fig. 2 at the time of 4 o'clock, Fig. 2 is a graph showing a curve (indicated by a solid line) and an open circuit potential and a solvent line (shown by a broken line) when the open circuit potential and the money are dissolved in the specific example 1. The knife f ...... π %# 汾 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次 二次The range, therefore, judges this specific example] 10 201037302 The interface layer of the hot dip mine steel plate does not have an iron (qua) gold composition. = The result of the break can be determined by the open circuit potential in Figure 2 (the solid line is not specified), and then passed through with each material (ie, carbon J curve aluminum alloy, word, etc.). The composition of the gold composition, iron, and finder is confirmed by the open circuit potential. The -1.04 gang of Figure 2 is the open circuit potential of the pure zinc recording layer, the equivalent of the volts corresponding to the = open = the standard open circuit potential, and finally 〇 5 volts Corresponding place:: steel layer/interface ^ It can be seen that the hot dip recording steel plate structure of the specific example 1 is pure zinc rhodium plating.
、 料合金組成）/碳鋼基材，該界面層為鐵辞合金 組成構成，不且：έ* /dfc > . 八有鐵鋁合金組成，驗證本發明的判 果0 口 參閱圖3’圖3是該具體例2的開路電位·溶料間對 應曲線（以實線表示），及開路電位·溶料間的二次微分曲 線（以虛線標繪）。 ，圖3之開路電位_溶敍時間二次微分曲線可看出該 —人微分曲線是從二次微分值為正值（圖3中箭頭1所指處） 達到最终為零之穩定值範圍（圖3中箭頭4所指處），因此判 斷此具體例的熱浸錢鋅鋼板之界面層具有鐵銘合金組成， 而再由圖3中之開路電位-溶蝕時間曲線（實線標示），與各 材質（¼鋼、鐵鋁合金組成、鋅等）之標準開路電位比對後 確認，圖3 Φ夕Λ,π Τ之-0.65伏特對應處為鐵鋁合金組成之標準開 >ffr Mr, ’ 此可知該具體例2之熱浸鍍鋅鋼板結構為純鋅 錢層/界面層（鐵紹合金組成）/碳鋼基材，可進一步驗證本發 明的判斷結果。 由上述判讀結果得知該具體例2之熱浸鍍鋅鋼板的界 11 201037302 H鐵銘合金組成，因此再由該：次微分曲線達到, 終為零之穩定值範圍前的兩個;3 1最 指位置）的距離，對岸得到^ (圖3中箭頭2、3所 時間；由圖m 層之鐵紹合金組成的溶餘 中該一次微分曲線可知該具 層的溶蝕時間為37·2秒。 "中之界面 雷/參閱圖4〜圖6’圖4〜圖6分別是該具體例3〜5的開路 電位-溶韻時間對Α曲续 路 門的- 線表示），及開路電位-溶敍時 間的一_人微分曲線（以虛線標繪）。 由圖4〜圖6 Φ夕-a 、 〇 中之一二人微分曲線看出，該每一圖 從，微分值為正值(圖4〜”箭頭1所;) 3 5之心值如此料得知該具體例 二：：板的界面層均分別具有鐵銘合金組成，且 零之穩定亥圖4〜6中之二次微分曲線達到最終為 零〜疋值範圍别的兩個相鄭 位置）的距離，可對計H零點（圖4〜6中箭頭2 ' 3所指 邮，由Λ 界面層之鐵銘合金組成的溶敍 夺間由圖4〜6中可得知該具體例3〜5之 33.6 秒、30.2 秒、31 3 职、甘 β ± 、馬 不同人 該具體例3〜5為具有_ Ρ又、呂5金組成’且可初步判斷該具體例2〜5之 =合金^成的厚度由大到小為：具體例2>具體例3>具體 例5>具體例4。 為更進—步驗證本發明該熱浸鑛辞鋼板的分析方法的 準確性’因此針對上述該具體例i及具體例2配合光學顯 微鏡（以下簡稱〇M)、掃描式電子顯微鏡（以下簡稱SEM)、 穿透式f子顯㈣（以下簡稱TEM)、能量散佈分析儀（以下 12 201037302 簡稱EDS)，及低掠角X-射線光譜（Glancing-Angle XRD， 以下簡稱GA-XRD)進行熱浸鍍鋅鋼板的結構觀測分析。 以下為各分析方法進行前試片之製備及分析條件之一 簡單說明。 OM(型號·· Microphot-fxa，Nikon)試片製備： 先將欲觀察之熱浸鑛鋅鋼板裁切出四片2mmx20mm大 小之試片，於丙酮中以超音波洗淨、吹乾後，將四片試片 以 M-Bond 膠（M-Bond 610, Vishay Micro-measurement)對黏 〇 之後，於90°c溫度下加熱40分鐘，接著將對黏好之試片材 切成1.5mm之大小，並以晶體膠包埋固定在載台上，進行 試片表面研磨至平整後（研磨用砂紙號數:No.600，800)，再 以凹窩減薄機（dimpler)減薄拋光，以得到試片表面平整、無 刮痕且無倒角的橫截面試片後，再接著以25ml picric acid(96ml ethanol+4g picric acid)、25ml 2wt% nitric acid(98ml H20+2ml HN03)、150ml 無水酒精及 0.3ml 的殺菌 劑（Zephrin chloride 17%)所配製之腐蚀液進行彩色化學腐 Ο 蝕，腐蝕時間約為2秒，接著以去離子水清洗並用氣槍吹 乾後，即可進行觀察。 TEM(型號：Tecnai G2 F20, FEI Company)試片製備： 將欲觀察之熱浸鍍辞鋼板裁切出四片2mmx20mm大小 之試片，於丙酮中以超音波洗淨、吹乾後，將四片試片以 M-bond 膠（M-Bond 610, Vishay Micro-measurement)對黏之 後於90°C溫度下加熱40分鐘，接著將對黏好之試片裁切成 1.5mm之大小，並以晶體膠包埋固定在載台上，進行試片 13 201037302 表面研磨至平整後（研磨用砂紙號數：No.600，800)，再以凹 窩減薄機（dimpler)減薄拋光，接著即可上銅環（銅環孔徑： 0. 6mm)，上完銅環後再將試片力口熱40分鐘以使M-bond膠 獲得充分加熱，之後再將試片翻面將第二表面進行與前述 相同之研磨、減薄步驟後，最後再以機械離子減薄機（ion miller)打出薄區，直到薄區出現後即可將試片進行TEM觀 察，該離子減薄機是在電壓為4.Okv、角度為10°的參數條 件下操作實施。 GA-XRD (型號：D8SSS，廠牌：Bruker)試片製備： 進行熱浸鍵辞鋼板之界面層的GA-XRD分析前，需先 將熱浸鍍鋅鋼板之辞外層移除，移除方式可由前述之酸性 溶蝕液將鋅鍍層進行移除，以清水洗淨、乾燥後，在特定 掃描角度下對試片進行GA-XRD光譜分析。於本具體例 1、 2中之GA-XRD光譜分析是針對界面層之鐵鋅合金組成 和鐵銘合金組成進行鑑定分析。茲將GA-XRD對各合金組 成之掃描條件整理如表三。 表三, alloy composition / carbon steel substrate, the interface layer is composed of iron alloy composition, not: έ * / dfc > . Eight iron alloy composition, verify the judgment of the invention 0 see Figure 3 ' Fig. 3 is a graph showing the open circuit potential/solubility curve (shown by a solid line) and the second differential curve between the open circuit potential and the solution (depicted by a broken line) in the specific example 2. The open circuit potential of Figure 3_the second differential curve of the dissolution time can be seen that the human differential curve is a stable value range from the second differential value to the positive value (pointed by the arrow 1 in Fig. 3) to the final zero ( As indicated by the arrow 4 in Fig. 3, it is judged that the interface layer of the hot dip zinc steel plate of this specific example has the composition of the iron alloy, and the open circuit potential-dissolution time curve (indicated by the solid line) in Fig. 3, The standard open circuit potential of each material (1⁄4 steel, iron-aluminum alloy composition, zinc, etc.) is confirmed after comparison. Figure 3 Φ Λ, π Τ -0.65 volt corresponds to the standard of iron-aluminum alloy composition >ffr Mr, It can be seen that the hot dip galvanized steel sheet structure of the specific example 2 is a pure zinc layer/interfacial layer (iron-smelting alloy composition)/carbon steel substrate, and the judgment result of the present invention can be further verified. From the above-mentioned interpretation results, it is known that the hot-dip galvanized steel sheet of the specific example 2 is composed of the boundary of the 2010-11302 H-Mei alloy, and thus is obtained by the sub-differential curve, and finally two of the stable value ranges of zero; 3 1 The distance from the most pointed position) is obtained on the opposite bank (the time of arrows 2 and 3 in Fig. 3; the first differential curve in the composition composed of the iron-sand alloy of the m layer of the figure shows that the dissolution time of the layer is 37·2 seconds. "Intermediate interface mine / see Fig. 4 to Fig. 6' Fig. 4 to Fig. 6 are the open circuit potential of the specific examples 3 to 5 - the time of the dissolution time is indicated by the - line of the meandering gate, and the open circuit potential - A human differential curve of the lysing time (plotted with a dotted line). It can be seen from the differential curves of one of the two figures in Fig. 4 to Fig. 6 that the differential value is positive (Fig. 4~" arrow 1;) It is known that the specific example 2: the interface layers of the plates are respectively composed of the iron alloy, and the second differential curve in the stable of the zero maps 4 to 6 reaches the two phase positions of the final zero to the range of the threshold value. The distance of the H can be calculated from the zero point of the H (the arrow 2 ' 3 in Figure 4 to 6), which is composed of the iron alloy of the interface layer. The specific example 3 can be seen from Figures 4 to 6. ~5 of 33.6 seconds, 30.2 seconds, 31 3 jobs, Gan β ±, horses different people, the specific examples 3 to 5 are composed of _ Ρ 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The thickness of the composition is as follows: Specific Example 2 > Specific Example 3 > Specific Example 5 > Specific Example 4. To further verify the accuracy of the analysis method of the hot dip mine steel plate of the present invention The specific example i and the specific example 2 are combined with an optical microscope (hereinafter referred to as 〇M), a scanning electron microscope (hereinafter referred to as SEM), and a transmissive f sub-display (four) (hereinafter simply TEM), energy dispersive analyzer (hereinafter referred to as 12 201037302 for EDS), and low-grazing angle X-ray spectroscopy (Glancing-Angle XRD, hereinafter referred to as GA-XRD) for structural observation analysis of hot dip galvanized steel sheets. The method of preparation and analysis of the pre-test piece is briefly described. OM (Model··Microphot-fxa, Nikon) test piece preparation: Firstly, the hot-dip galvanized zinc steel plate to be observed is cut out into four pieces of 2mm×20mm size test pieces. After being ultrasonically washed and dried in acetone, the four test pieces were adhered to M-Bond 610 (Vishay Micro-measurement), and then heated at 90 ° C for 40 minutes. Next, the adhered test piece is cut into a size of 1.5 mm, and embedded on a stage with a crystal glue, and the surface of the test piece is ground to a flat shape (grinding sandpaper number: No. 600, 800). Then thin the polishing with a dimple to obtain a flat, scratch-free and chamfer-free cross-section interview piece of the test piece, followed by 25 ml picric acid (96 ml ethanol + 4 g picric acid), 25ml 2wt% nitric acid (98ml H20+2ml HN03), 150ml anhydrous alcohol and 0.3ml The etching solution prepared by the sterilizing agent (Zephrin chloride 17%) was subjected to color chemical etching, and the etching time was about 2 seconds, and then it was observed by washing with deionized water and drying with an air gun. TEM (Model: Tecnai G2) F20, FEI Company) Preparation of test piece: Cut the hot-dip plated steel plate to be observed into four pieces of 2mm x 20mm test pieces, wash them in acetone and dry them in acetone, then take four test pieces as M- Bond glue (M-Bond 610, Vishay Micro-measurement) is heated at 90 ° C for 40 minutes, then the bonded test piece is cut into 1.5 mm size and embedded in crystal glue. On the stage, the test piece 13 201037302 is ground to a flat surface (grinding sandpaper number: No. 600, 800), and then thinned and polished with a dimpler, then the copper ring (copper) Ring aperture: 0. 6mm), after the copper ring is finished, the test piece is heated for 40 minutes to fully heat the M-bond glue, and then the test piece is turned over to make the second surface be polished as described above. After the thinning step, the thin zone is finally punched with a mechanical ionizer (ion miller). Thin region occurs after the test piece to a TEM observation, the ion milling machine operating parameters in the embodiment of voltage conditions 4.Okv, an angle of 10 °. GA-XRD (Model: D8SSS, Brand: Bruker) Preparation of test strips: Before performing GA-XRD analysis of the interface layer of the hot dip bond steel plate, the outer layer of the hot dip galvanized steel plate must be removed first. The zinc plating layer may be removed by the above-mentioned acidic etching solution, washed with water, dried, and subjected to GA-XRD spectrum analysis at a specific scanning angle. The GA-XRD spectral analysis in the specific examples 1 and 2 is for the identification analysis of the composition of the iron-zinc alloy and the composition of the iron alloy of the interface layer. The scanning conditions of GA-XRD for each alloy composition are summarized in Table 3. Table 3
Angle Scan rate Step size Scan angle (Degree) (Sec./step) (Degree) (Degree) 鐵辞合金組成 1 1 0.05 10 〜80 鐵鋅合金組成 5 1.5 0.05 20 〜80 參閱圖7、圖8，圖7為該具體例1之截面光學金相 圖，圖8為該具體例1之界面層的GA-XRD光譜圖。 14 201037302 由圖7中可看出該熱浸鍍鋅鋼板之碳鋼基材（圖7中 steel標示處）、鍍層（圖7中ο標示處）與界面層，且該界面 層為兩相（ζ相和δ相）結構（圖7中ζ和δ標示處）；而由 GA-XRD光譜圖之鐘定結果得知該界面層的兩相結構均是 由鐵辞合金所構成，且因該具體例1之鐵鋅合金過度成 長，因此厚度較大（約為5〜7μιη)，而由前述說明可知，該鐵 辞合金組成將會影響熱浸鍍鋅鋼板後續的加工性和成型 性。 ❹ 參閱圖9、圖10，圖9為該具體例2之光學金相圖， 圖10為該具體例2之界面層的GA-XRD光譜圖。 由圖9中發現，在碳鋼基材（圖9中steel標示處）和純 • 鋅鍍層（圖9中β標示處）之間，並無觀測到如上述二次微分 曲線所判斷之界面層組成結構，但是由圖1〇的ga xrd光 譜圖之鑑定結果得知，在碳鋼基材和純鋅鍍層之間應有一 由鐵鋁合金組成構成之界面層存在，然而由圖1〇中並無法 看出該鐵銘合金組成，此因為該鐵銘合金組成的厚度極 Ο 薄，而受限於OM的解析能力’因此無法直接觀測，為更 確認該界面層的存在因此將該具體例2進行tem裁面觀 測。 參閱圖11、圖圖U為該具體例2之橫截面的 麗影像，圖12為圖u巾DP1、贈、㈣標示處之擇區 電子繞射圖譜。 由圖11顯示出之影像得知，在該碳鋼基材與純鋅鍍層 間有該界面層存在，且由圖12測得之電子繞射圖譜可知 15 201037302 DPI DP2 DP3處皆為鐵銘合金組成㈣叫，此結果與經 由上述該圖4中之—次微分曲線的判斷結果相同，且與標 準開路電位比較結果亦符合。 圖13、14分別為圖3中該具體例2的二次微分曲線在 達到最終為零之穩定值範圍前的兩個相鄰零點的SEM影像 圖，圖13是圖3中箭頭2所指位置，圖Μ是圖3中箭頭3 所指位置。 由圖13可知，在薪通1 ， 頭所私位置為該鐵鋁合金組成的 初溶钱時間，因此可看屮矣 有出表面具有大量的鐵鋁合金組成； :由圖14則可清楚看出，到箭頭3所指之位置時，該鐵銘 :金組成已幾乎完全移除，因此由影像中幾乎只可觀測到 =鋼基材，此結果與本發明以二次微分曲線在達到最終為 =之穩定值範圍前㈣個相鄰零點戟義出之溶糾間一 :二此，可更加證實由本發明由該溶料間與表面電位 時間的準確度。析所件之界面層組成及界面層溶蚀 用將：亡：述’本發明該熱浸鑛辞鋼板的分析方法，是利 鑛辞鋼板浸置在一酸性溶姑液令，經由量測不同 :=熱浸鑛辞鋼板的表面電位，得到-㈣時間 到表的對應曲線後，並將該曲線圖進行二次微分得 曲線圖’藉由該二次微分曲線圖之曲率變化， p可快速分析該界面層的組 相對厘择該界面層之溶蝕時間及 •厚度，故確實可達到本發明之目的。 惟以上所述者，僅為本發明之較佳實施例而已，當不 16 201037302 能以此限定本發明實施之範圍，即大凡依本發明申請專利 範圍及發明說明内容所作之簡單的等效變化與修飾皆仍 屬本發明專利涵蓋之範圍内。 【圖式簡單說明】 圖1是一流程圖，說明本發明熱浸鍍辞鋼板的分析方 法的較佳實施例； 圖2是一曲線圖，說明具體例丨之溶蝕時間與表面電 位之對應曲線圖及二次微分曲線圖； 〇 圖3是一曲線圖，說明具體例2之溶蝕時間與表面電 位之對應曲線圖及二次微分曲線圖； 圖4是一曲線圖，說明具體例3之溶蝕時間與表面電 位之對應曲線圖及二次微分曲線圖； 圖5是一曲線圖，說明具體例4之溶蝕時間與表面電 位之對應曲線圖及二次微分曲線圖； 圖6是一曲線圖，說明具體例5之溶蝕時間與表面電 位之對應曲線圖及二次微分曲線圖； 〇 圖7疋一金相圖’說明該具體例1之截面結構； 圖8是一 GA-XRD光譜圖，說明該具體例i截面結構 的GA-XRD分析結果； 圖9是一金相圖，說明具體例2之截面結構； 圖10是一 GA-XRD光譜圖，說明該具體例2之截面結 構的GA-XRD分析結果； 圖11是一 TEM影像圖，說明該具體2之橫截面的 TEM影像； 17 201037302 圖12是一電子繞射圖譜，為圖11中DPI、DP2、DP3 標示處之擇區電子繞射分析結果； 圖13是一 SEM影像圖，說明圖3中箭頭2所指位置的 SEM影像；及 圖14是一 SEM影像圖，說明圖3中箭頭3所指位置的 SEM影像。 18 201037302 【主要元件符號說明】 21 溶蝕量測步驟 22 微分步驟 23 判讀步驟 Ο 19Angle Scan rate Step size Scan angle (Degree) (Sec./step) (Degree) (Degree) Iron alloy composition 1 1 0.05 10 ~ 80 Iron-zinc alloy composition 5 1.5 0.05 20 ~ 80 See Figure 7, Figure 8, Figure 7 is a cross-sectional optical metallographic diagram of the specific example 1, and FIG. 8 is a GA-XRD spectrum diagram of the interface layer of the specific example 1. 14 201037302 It can be seen from Fig. 7 that the hot-dip galvanized steel sheet has a carbon steel substrate (steel mark in Fig. 7), a plating layer (marked in Fig. 7) and an interface layer, and the interface layer is two-phase ( ζ phase and δ phase) structure (marked by ζ and δ in Fig. 7); and the results of the GA-XRD spectrum show that the two-phase structure of the interface layer is composed of iron alloy, and The iron-zinc alloy of Specific Example 1 is excessively grown, and therefore has a large thickness (about 5 to 7 μm). From the above description, it is understood that the composition of the iron-based alloy affects the subsequent workability and formability of the hot-dip galvanized steel sheet. 9 Referring to FIG. 9 and FIG. 10, FIG. 9 is an optical metal phase diagram of the specific example 2, and FIG. 10 is a GA-XRD spectrum diagram of the interface layer of the specific example 2. It is found from Fig. 9 that no interface layer as judged by the above secondary differential curve is observed between the carbon steel substrate (the steel mark in Fig. 9) and the pure zinc coating (the β mark in Fig. 9). The composition is composed, but it is known from the identification of the ga xrd spectrum of Fig. 1 that there should be an interfacial layer composed of an iron-aluminum alloy between the carbon steel substrate and the pure zinc coating, but It is impossible to see the composition of the iron alloy, because the thickness of the composition of the iron alloy is extremely thin, and it is limited by the analytical ability of the OM', so it cannot be directly observed, so the specific example 2 is confirmed to confirm the existence of the interface layer. Perform tem face observation. Referring to Fig. 11, Fig. U is a photographic image of the cross section of the specific example 2, and Fig. 12 is a selected electron diffraction pattern of the masks of the masks DP1, 赠, and (4). It can be seen from the image shown in FIG. 11 that the interface layer exists between the carbon steel substrate and the pure zinc plating layer, and the electron diffraction pattern measured by FIG. 12 can be seen that 15 201037302 DPI DP2 DP3 are all iron alloys. The composition (4) is called, and the result is the same as the judgment result of the sub-differential curve in the above-mentioned FIG. 4, and the result is also in agreement with the standard open circuit potential. 13 and 14 are SEM images of two adjacent zero points of the second differential curve of the specific example 2 in FIG. 3 before reaching a final stable value range, and FIG. 13 is the position indicated by the arrow 2 in FIG. , Figure Μ is the position indicated by arrow 3 in Figure 3. It can be seen from Fig. 13 that in the salary pass 1, the private position of the head is the initial dissolved time of the iron-aluminum alloy composition, so it can be seen that the surface has a large amount of iron-aluminum alloy composition; : It can be clearly seen from Fig. 14. Out, at the position indicated by the arrow 3, the iron name: the gold composition has been almost completely removed, so almost only the steel substrate can be observed from the image, and the result is in the final with the second differential curve of the present invention. For the range of the stable value range of = (four) adjacent zero points, the correctness of the solution is one: two, the accuracy of the time between the solution and the surface potential of the present invention can be further confirmed. The interfacial layer composition and the interfacial layer dissolution of the device will be: Death: The analysis method of the hot dip ore plate of the present invention is that the slag plate is immersed in an acidic liquefied liquid order, and the measurement is different: = The surface potential of the hot-dip mine plate, after - (four) time to the corresponding curve of the table, and the curve is secondarily differentiated to obtain a curve 'by the curvature change of the second differential curve, p can be quickly analyzed The group of the interface layer can determine the dissolution time and thickness of the interface layer relatively, so that the object of the present invention can be achieved. However, the above is only the preferred embodiment of the present invention, and the scope of the present invention is limited to the extent that the invention is based on the scope of the invention and the simple equivalent changes made by the scope of the invention and the description of the invention. And modifications are still within the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a preferred embodiment of the analysis method of the hot dip plated steel sheet of the present invention; Fig. 2 is a graph showing the corresponding curve of the dissolution time and the surface potential of the specific example FIG. 3 is a graph illustrating a corresponding graph of the dissolution time and the surface potential of the specific example 2 and a second differential curve; FIG. 4 is a graph illustrating the dissolution of the specific example 3. Corresponding graph of time and surface potential and quadratic differential graph; FIG. 5 is a graph illustrating the corresponding graph of the dissolution time and surface potential of the specific example 4 and the second differential graph; FIG. 6 is a graph. A corresponding graph and a second differential curve of the dissolution time and the surface potential of the specific example 5 will be described; FIG. 7 is a metallographic diagram' illustrating the cross-sectional structure of the specific example 1; FIG. 8 is a GA-XRD spectrum diagram illustrating The results of the GA-XRD analysis of the cross-sectional structure of this specific example i; FIG. 9 is a metallographic diagram illustrating the cross-sectional structure of the specific example 2; and FIG. 10 is a GA-XRD spectrum diagram illustrating the GA- of the cross-sectional structure of the specific example 2. XRD analysis results; Figure 1 1 is a TEM image showing the TEM image of the cross section of the specific 2; 17 201037302 FIG. 12 is an electron diffraction pattern, which is the result of the selective electron diffraction analysis of the DPI, DP2, and DP3 marks in FIG. 11; 13 is an SEM image showing the SEM image of the position indicated by the arrow 2 in FIG. 3; and FIG. 14 is an SEM image showing the SEM image of the position indicated by the arrow 3 in FIG. 18 201037302 [Explanation of main component symbols] 21 Corrosion measurement procedure 22 Derivative step 23 Interpretation step Ο 19