TWI434952B - Method for surface treatment of stainless steel - Google Patents
Method for surface treatment of stainless steel Download PDFInfo
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- TWI434952B TWI434952B TW100133987A TW100133987A TWI434952B TW I434952 B TWI434952 B TW I434952B TW 100133987 A TW100133987 A TW 100133987A TW 100133987 A TW100133987 A TW 100133987A TW I434952 B TWI434952 B TW I434952B
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Description
本發明是有關於一種鋼鐵表面之處理方法,特別是有關於一種利用無機層狀雙層氫氧化物(layered double hydroxide;LDH)處理不銹鋼表面之方法。The present invention relates to a method for treating a steel surface, and more particularly to a method for treating a stainless steel surface using an inorganic layered double hydroxide (LDH).
不銹鋼具有獨特的強度、較高的耐磨性、優越的防腐性能及不易生銹等優良的特性,故廣泛應用於化工、食品機械、機電、環保、家用電器及家庭裝潢等行業。Stainless steel has excellent strength, high wear resistance, superior corrosion resistance and rust resistance. It is widely used in chemical, food machinery, electromechanical, environmental protection, household appliances and home decoration industries.
由於不銹鋼具有特殊的金相組織和表面鈍化膜,使其在一般情況下較難與介質發生化學反應而被腐蝕,但若在腐蝕介質和誘因(如劃傷、飛濺、割渣等)存在的條件下,不銹鋼還是會與腐蝕介質發生緩慢的化學和電化學反應而被腐蝕。Because stainless steel has a special metallographic structure and a surface passivation film, it is difficult to be corroded by chemical reaction with the medium under normal conditions, but if it exists in corrosive media and incentives (such as scratches, splashes, slag, etc.) Under the conditions, stainless steel will be corroded by slow chemical and electrochemical reactions with corrosive media.
在不銹鋼產品的加工作業過程中,可藉由表面處理的方法以減少腐蝕的情況產生。目前常見的不銹鋼表面處理方法有表面本色白化處理、表面鏡面光亮處理和表面著色處理等方法。其中,表面著色處理不僅賦予不銹鋼製品各種顏色,增加產品的花色品種,並可提高產品耐磨性和耐腐蝕性。In the processing of stainless steel products, it can be produced by surface treatment to reduce corrosion. At present, the common stainless steel surface treatment methods include surface whitening treatment, surface mirror brightening treatment and surface coloring treatment. Among them, the surface coloring treatment not only imparts various colors to the stainless steel products, increases the color variety of the products, and improves the wear resistance and corrosion resistance of the products.
不銹鋼著色方法有化學氧化著色法、電化學氧化著色法、離子沉積氧化物著色法、高溫氧化著色法和氣相裂解著色法等。化學氧化著色法係在特定溶液中,透過化學氧化形成膜的顏色,有重鉻酸鹽法、混合鈉鹽法、硫化法、酸性氧化法和鹼性氧化法。電化學著色法是在特定溶液中,透過電化學氧化形成膜的顏色。離子沉積氧化物著色法化學法是將不銹鋼工件放在真空鍍膜機中進行真空蒸發鍍,此種方法適用於大批量產品加工。高溫氧化著色法則是在特定的熔鹽中,浸入不銹鋼並保持一定的工藝參數,使工件形成一定厚度氧化膜,而呈現出各種不同色澤。氣相裂解著色法因較為複雜,在工業中的應用較少。The stainless steel coloring methods include chemical oxidation coloring method, electrochemical oxidation coloring method, ion deposition oxide coloring method, high temperature oxidation coloring method, and gas phase cracking coloring method. The chemical oxidation coloring method is a color of a film formed by chemical oxidation in a specific solution, and is a dichromate method, a mixed sodium salt method, a vulcanization method, an acidic oxidation method, and an alkaline oxidation method. Electrochemical coloring is the color of a film formed by electrochemical oxidation in a specific solution. Ion-deposited oxide coloring method is a method in which a stainless steel workpiece is placed in a vacuum coating machine for vacuum evaporation. This method is suitable for processing large quantities of products. The high temperature oxidation coloring method is to immerse the stainless steel in a specific molten salt and maintain certain process parameters, so that the workpiece forms a certain thickness of oxide film, and presents various colors. The gas phase cracking coloring method is less complicated and has less application in industry.
不銹鋼的表面處理技術發展可影響不銹鋼的應用,因此,發展良好的表面處理方法使不銹鋼具更佳的抗腐蝕性,可增長不銹鋼的使用時間,也可擴展其應用層面。The development of stainless steel surface treatment technology can affect the application of stainless steel. Therefore, the development of a good surface treatment method makes the stainless steel have better corrosion resistance, can increase the use time of stainless steel, and can also expand its application level.
因此,本發明之一態樣是在提供一種不銹鋼表面處理之方法。首先製備酸性混合溶液,酸性混合溶液之鎂離子與鐵離子([Mg2+ ]/[Fe3+ ])的莫耳比為40至70,再將不銹鋼樣品浸入酸性混合溶液中,之後持續通入二氧化碳氣體於酸性混合溶液中,於50℃至75℃反應0.5至3小時,以於不銹鋼樣品之表面形成微細結晶層。Accordingly, one aspect of the present invention is to provide a method of surface treatment of stainless steel. First, an acidic mixed solution is prepared. The molar ratio of magnesium ions to iron ions ([Mg 2+ ]/[Fe 3+ ]) in the acidic mixed solution is 40 to 70, and the stainless steel sample is immersed in the acidic mixed solution, and then continuously passed. The carbon dioxide gas is reacted in an acidic mixed solution at 50 ° C to 75 ° C for 0.5 to 3 hours to form a fine crystal layer on the surface of the stainless steel sample.
在反應的同時,製備鹼性碳酸水,其中鹼性碳酸水之pH值為8.0至10.0。接著,將形成微細結晶層之不銹鋼樣品浸入鹼性碳酸水中,於50℃至75℃反應10至22小時,使微細結晶層成長、增厚並緻密化。最終,於不銹鋼樣品之表面形成無機層狀雙層氫氧化物,其中此無機層狀雙層氫氧化物為鎂-鐵層狀雙層氫氧化物,且無機層狀雙層氫氧化物之中間層離子為碳酸根。At the same time as the reaction, alkaline carbonated water was prepared in which the pH of the alkaline carbonated water was 8.0 to 10.0. Next, the stainless steel sample forming the fine crystal layer is immersed in alkaline carbonated water, and reacted at 50 ° C to 75 ° C for 10 to 22 hours to grow, thicken, and densify the fine crystal layer. Finally, an inorganic layered double layer hydroxide is formed on the surface of the stainless steel sample, wherein the inorganic layered double layer hydroxide is a magnesium-iron layered double layer hydroxide, and the middle layer of the inorganic layered double layer hydroxide The layer ions are carbonate.
依照本發明之一實施方式,上述酸性混合溶液包括氫氧化鎂及三氯化鐵。According to an embodiment of the present invention, the acidic mixed solution includes magnesium hydroxide and ferric chloride.
依照本實施方式之一實施例,上述製備酸性混合溶液之步驟更包含利用鹽酸調整酸性混合溶液之pH值,使酸性混合溶液之pH值為0.2至1.5。According to an embodiment of the present embodiment, the step of preparing the acidic mixed solution further comprises adjusting the pH of the acidic mixed solution with hydrochloric acid so that the pH of the acidic mixed solution is 0.2 to 1.5.
依照本實施方式之一實施例,上述形成微細結晶層之步驟係使不銹鋼樣品在酸性混合溶液中於70℃反應2小時。According to an embodiment of the present embodiment, the step of forming the fine crystal layer is performed by reacting a stainless steel sample in an acidic mixed solution at 70 ° C for 2 hours.
依照本實施方式之一實施例,上述二氧化碳氣體係以2.0 kPa至4.5 kPa之壓力通入酸性混合溶液中。According to an embodiment of the present embodiment, the carbon dioxide gas system is introduced into the acidic mixed solution at a pressure of from 2.0 kPa to 4.5 kPa.
依照本實施方式之一實施例,上述製備鹼性碳酸水之步驟更包含通入二氧化碳氣體於去離子水中,以形成pH 4.0至4.5之碳酸水,再調整碳酸水之pH值達8.0至10.0,以形成鹼性碳酸水。According to an embodiment of the present embodiment, the step of preparing alkaline carbonated water further comprises introducing carbon dioxide gas into deionized water to form carbonated water having a pH of 4.0 to 4.5, and adjusting the pH of the carbonated water to 8.0 to 10.0. To form alkaline carbonated water.
依照本實施方式之一實施例,其中上述碳酸水係利用氫氧化鈉水溶液調整,以形成鹼性碳酸水。According to an embodiment of the present invention, the carbonated water is adjusted with an aqueous sodium hydroxide solution to form alkaline carbonated water.
依照本實施方式之一實施例,其中上述酸性混合溶液之鎂離子與鐵離子([Mg2+ ]/[Fe3+ ])之莫耳比為51.78。According to an embodiment of the present embodiment, the molar ratio of magnesium ions to iron ions ([Mg 2+ ] / [Fe 3+ ]) of the acidic mixed solution is 51.78.
本發明之另一態樣是在提供一種具有無機層狀雙層氫氧化物之不銹鋼,其係利用上述方法所製得。Another aspect of the present invention is to provide a stainless steel having an inorganic layered double layer hydroxide which is obtained by the above method.
根據上述可知,本發明之特點在於利用鎂-鐵層狀雙層氫氧化物形成於不銹鋼之表面而產生保護層,使不銹鋼具有良好的抗腐蝕特性。According to the above, the present invention is characterized in that a magnesium-iron layered double layer hydroxide is formed on the surface of the stainless steel to form a protective layer, so that the stainless steel has good corrosion resistance.
本發明是以含鎂離子和鐵離子的酸性混合溶液作為使層狀雙層氫氧化物形成於不銹鋼之表面而產生耐腐蝕層的處理液;不銹鋼置入上述溶液後,再開始通入大量的二氧化碳氣體,增加不銹鋼表面所形成的層狀雙層氫氧化物,使得不銹鋼的抗腐蝕性提高。The present invention is an acidic mixed solution containing magnesium ions and iron ions as a treatment liquid for forming a layered double-layer hydroxide on the surface of a stainless steel to produce a corrosion-resistant layer; after the stainless steel is placed in the above solution, a large amount of the solution is introduced. The carbon dioxide gas increases the layered double layer hydroxide formed on the surface of the stainless steel, so that the corrosion resistance of the stainless steel is improved.
請參照第1圖,為依照本發明一實施例之不銹鋼表面之處理方法100的步驟流程圖。Referring to Figure 1, a flow chart of the steps of a method 100 for treating a stainless steel surface in accordance with an embodiment of the present invention is shown.
步驟110為製備酸性混合溶液,此酸性混合溶液之鎂離子與鐵離子([Mg2+ ]/[Fe3+ ])的莫耳比為40至70。Step 110 is to prepare an acidic mixed solution having a molar ratio of magnesium ions to iron ions ([Mg 2+ ] / [Fe 3+ ]) of 40 to 70.
根據本發明之一實施例,此酸性混合溶液包括氫氧化鎂及三氯化鐵,更包含添加鹽酸調整酸性混合溶液之pH值為0.2至1.5,可促進氫氧化鎂之溶解。According to an embodiment of the present invention, the acidic mixed solution comprises magnesium hydroxide and ferric chloride, and further comprises adding hydrochloric acid to adjust the pH of the acidic mixed solution to 0.2 to 1.5 to promote dissolution of magnesium hydroxide.
步驟120為將不銹鋼樣品浸入酸性混合溶液中之後,再開始通入二氧化碳氣體於此酸性混合溶液中以進行反應,使不銹鋼樣品之表面形成微細結晶層。In step 120, after the stainless steel sample is immersed in the acidic mixed solution, carbon dioxide gas is introduced into the acidic mixed solution to carry out a reaction to form a fine crystal layer on the surface of the stainless steel sample.
根據本發明之一實施例,二氧化碳氣體係以2.0 kPa至4.5 kPa之壓力通入酸性混合溶液中,使不銹鋼樣品於50℃至75℃反應0.5至3小時,以在不銹鋼樣品的表面形成微細結晶層。According to an embodiment of the present invention, the carbon dioxide gas system is introduced into the acidic mixed solution at a pressure of 2.0 kPa to 4.5 kPa, and the stainless steel sample is reacted at 50 ° C to 75 ° C for 0.5 to 3 hours to form fine crystals on the surface of the stainless steel sample. Floor.
二氧化碳氣體可提供碳酸根離子(CO3 2- ),此時所形成之微細結晶層包含鎂離子(Mg2+ )、鐵離子(Fe3+ )和碳酸根離子,其形成於不銹鋼樣品之表面,而為一層黑色的表面膜,可參照第2圖,其為依照本發明一實施例之不銹鋼表面形成微細結晶層圖。Carbon dioxide gas provides carbonate ions (CO 3 2- ), and the fine crystal layer formed at this time contains magnesium ions (Mg 2+ ), iron ions (Fe 3+ ), and carbonate ions, which are formed on the surface of the stainless steel sample. As a black surface film, reference can be made to Fig. 2, which is a diagram showing the formation of a fine crystal layer on the surface of a stainless steel according to an embodiment of the present invention.
步驟130為製備鹼性碳酸水,此鹼性碳酸水之pH值為8.0至10.0。Step 130 is to prepare alkaline carbonated water having a pH of 8.0 to 10.0.
根據本發明之一實施例,製備鹼性碳酸水之步驟更包含通入二氧化碳氣體於去離子水中,以形成pH 4.0至4.5之碳酸水。之後,再調整此碳酸水之pH值達8.0至10.0,而形成鹼性碳酸水。在一例示中,係利用氫氧化鈉水溶液調整碳酸水,以形成鹼性碳酸水。According to an embodiment of the invention, the step of preparing the alkaline carbonated water further comprises passing carbon dioxide gas in deionized water to form carbonated water having a pH of 4.0 to 4.5. Thereafter, the pH of the carbonated water was adjusted to 8.0 to 10.0 to form alkaline carbonated water. In an example, the carbonated water is adjusted with an aqueous sodium hydroxide solution to form alkaline carbonated water.
步驟140為將形成微細結晶層之不銹鋼樣品浸入鹼性碳酸水中,使微細結晶層成長、增厚,而成為具備抗腐蝕能力的保護層。此保護層為無機層狀雙層氫氧化物。In step 140, the stainless steel sample forming the fine crystal layer is immersed in alkaline carbonated water to grow and thicken the fine crystal layer to form a protective layer having corrosion resistance. This protective layer is an inorganic layered double layer hydroxide.
根據本發明之一實施例,將上述不銹鋼樣品浸入鹼性碳酸水中,於50℃至75℃反應10至22小時,其中上述無機層狀雙層氫氧化物為透明的鎂-鐵層狀雙層氫氧化物,且此無機層狀雙層氫氧化物之中間層離子為碳酸根。According to an embodiment of the present invention, the stainless steel sample is immersed in alkaline carbonated water and reacted at 50 ° C to 75 ° C for 10 to 22 hours, wherein the inorganic layered double layer hydroxide is a transparent magnesium-iron layer double layer. a hydroxide, and the intermediate layer ion of the inorganic layered double layer hydroxide is carbonate.
根據本發明之不銹鋼表面處理方法,持續通入二氧化碳氣體於酸性混合溶液,二氧化碳氣體所提供的碳酸根離子會影響其後於不銹鋼表面所形成之無機層狀雙層氫氧化物的保護層,進而影響不銹鋼的抗腐蝕性。According to the stainless steel surface treatment method of the present invention, carbon dioxide gas is continuously supplied to the acidic mixed solution, and the carbonate ions provided by the carbon dioxide gas affect the protective layer of the inorganic layered double-layer hydroxide formed on the surface of the stainless steel, and further Affects the corrosion resistance of stainless steel.
請參照表一,為經表面處理前後之不銹鋼極化測試結果。其係利用動電位極化法測試不銹鋼的抗腐蝕性,此技術為習知評估材料抗腐蝕性的方法,故在此不另加贅述。Please refer to Table 1 for the results of stainless steel polarization test before and after surface treatment. It uses the potentiodynamic polarization method to test the corrosion resistance of stainless steel. This technique is a conventional method for evaluating the corrosion resistance of materials, and therefore will not be further described herein.
以SUS-316L型不銹鋼為樣品,0.5M硫酸水溶液為極化溶液,掃描速率為0.5 mV/sec進行抗腐蝕性的測試。表一中不銹鋼樣品的表面處理流程為先溶解14克的氫氧化鎂及1.26克的三氯化鐵於350毫升的去離子水中,並添加鹽酸調整pH值至0.5以促進氫氧化鎂溶解,而形成酸性混合溶液,其中鎂離子與鐵離子([Mg2+ ]/[Fe3+ ])之莫耳比為51.78。接著,將不銹鋼樣品浸入酸性混合溶液,分別持續通入不同壓力(例如0 kPa、2.5 kPa、3.5 kPa和4.0 kPa)之二氧化碳氣體,於70℃反應2小時,以於不銹鋼樣品之表面形成微細結晶層。The SUS-316L type stainless steel was used as a sample, the 0.5 M sulfuric acid aqueous solution was used as a polarizing solution, and the scanning rate was 0.5 mV/sec for corrosion resistance test. The surface treatment process of the stainless steel sample in Table 1 is to first dissolve 14 grams of magnesium hydroxide and 1.26 grams of ferric chloride in 350 ml of deionized water, and add hydrochloric acid to adjust the pH to 0.5 to promote the dissolution of magnesium hydroxide. An acidic mixed solution was formed in which the molar ratio of magnesium ions to iron ions ([Mg 2+ ] / [Fe 3+ ]) was 51.78. Next, the stainless steel sample is immersed in the acidic mixed solution, and carbon dioxide gas at different pressures (for example, 0 kPa, 2.5 kPa, 3.5 kPa, and 4.0 kPa) is continuously supplied, and reacted at 70 ° C for 2 hours to form fine crystals on the surface of the stainless steel sample. Floor.
在形成微細結晶層的同時,製備鹼性碳酸水,其係通入二氧化碳氣體於去離子水中,直至形成pH值為4.3的碳酸水。接著,加入氫氧化鈉水溶液,調整碳酸水的pH值達9.5,而形成鹼性碳酸水。While forming a fine crystal layer, alkaline carbonated water was prepared which was passed through a carbon dioxide gas in deionized water until a carbonated water having a pH of 4.3 was formed. Next, an aqueous sodium hydroxide solution was added to adjust the pH of the carbonated water to 9.5 to form alkaline carbonated water.
將形成微細結晶層之不銹鋼樣品浸入鹼性碳酸水中,於70℃反應20小時後,晾乾即完成表面處理。The stainless steel sample forming the fine crystal layer was immersed in alkaline carbonated water, reacted at 70 ° C for 20 hours, and dried to complete the surface treatment.
表一中腐蝕電流的大小表示不銹鋼腐蝕速率的快慢。由表一可知,二氧化碳通氣量增高,會使經表面處理後的不銹鋼樣品於0.5M硫酸溶液中的腐蝕速率明顯降低。其中,通入4.0 kPa二氧化碳的不銹鋼樣品,其腐蝕速率較未經表面處理之SUS-316L不銹鋼低約1個數量級。The magnitude of the corrosion current in Table 1 indicates the rate of corrosion of the stainless steel. It can be seen from Table 1 that the increase in carbon dioxide aeration results in a significant decrease in the corrosion rate of the surface treated stainless steel sample in a 0.5 M sulfuric acid solution. Among them, stainless steel samples with 4.0 kPa carbon dioxide have a corrosion rate about one order of magnitude lower than that of SUS-316L stainless steel without surface treatment.
由本發明上述實施方式可知,應用本發明的不銹鋼表面處理方法,其優點在於利用鎂-鐵層狀雙層氫氧化物形成於不銹鋼之表面,而產生一保護層,使不銹鋼在嚴苛的環境下,仍具有良好的抗腐蝕特性。According to the above embodiment of the present invention, the stainless steel surface treatment method of the present invention has the advantage that the magnesium-iron layered double layer hydroxide is formed on the surface of the stainless steel to produce a protective layer, so that the stainless steel is in a severe environment. , still has good corrosion resistance.
雖然本發明已以實施方式揭露如上,然其並非用以限定本發明,在本發明所屬技術領域中任何具有通常知識者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。The present invention has been disclosed in the above embodiments, and is not intended to limit the present invention. Any one of ordinary skill in the art to which the present invention pertains can make various changes without departing from the spirit and scope of the invention. The scope of protection of the present invention is therefore defined by the scope of the appended claims.
100...不銹鋼表面之處理方法100. . . Stainless steel surface treatment method
110...步驟110. . . step
120...步驟120. . . step
130...步驟130. . . step
140...步驟140. . . step
為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂,所附圖式之說明如下:The above and other objects, features, advantages and embodiments of the present invention will become more apparent and understood.
第1圖為依照本發明一實施例之不銹鋼表面之處理方法100的步驟流程圖。1 is a flow chart showing the steps of a method 100 for treating a stainless steel surface in accordance with an embodiment of the present invention.
第2圖為依照本發明一實施例之不銹鋼表面形成微細結晶層圖。Fig. 2 is a view showing the formation of a fine crystal layer on the surface of a stainless steel according to an embodiment of the present invention.
100...不銹鋼表面之處理方法100. . . Stainless steel surface treatment method
110...步驟110. . . step
120...步驟120. . . step
130...步驟130. . . step
140...步驟140. . . step
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