TWI440745B - An etching solution for electrolytically removing chromium carbide films and method for removing the films - Google Patents
An etching solution for electrolytically removing chromium carbide films and method for removing the films Download PDFInfo
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本發明涉及一種電解退除基材表面碳化鉻膜層之退鍍液及利用該退鍍液電解退除碳化鉻膜層之方法。 The invention relates to a deplating solution for electrolytically removing a chromium carbide film layer on a surface of a substrate and a method for electrolytically removing the chromium carbide film layer by using the deplating solution.
鍍膜工藝在工業領域有著廣泛之應用。然，通常在以下兩種情況下需要對鍍膜進行退除：(1)經過長期使用後，工件表面之鍍膜已經被損傷或者嚴重老化，從而需要去除鍍層，重新鍍覆；(2)在生產中，所鍍覆之鍍層不符合品質要求，為減少損失，節約成本，需要退掉鍍層，讓工件返工重新鍍膜。故，如何在不損傷基材之情況下，將鍍層從基材表面完全除去係工業生產中一個重要問題。 The coating process has a wide range of applications in the industrial field. However, the coating is usually removed in the following two cases: (1) After long-term use, the coating on the surface of the workpiece has been damaged or severely aged, requiring removal of the coating and re-plating; (2) in production The plated coating does not meet the quality requirements. In order to reduce losses and save costs, it is necessary to retreat the coating and rework the workpiece. Therefore, how to completely remove the plating layer from the surface of the substrate without damaging the substrate is an important problem in industrial production.
碳化鉻(Cr3C2)膜係一種性能優良之鉻系鍍層，其與鉻系鍍層中最常用之氮化鉻(Cr2N)膜相比具有更強之抗氧化、抗腐蝕性，而且硬度更高，耐磨性能亦更好，在工業領域具有廣闊之前景。現有之對碳化鉻膜電解退鍍之方法係採用只含有單一之鹼金屬氫氧化物(如氫氧化鈉)之退鍍液，該單一成分之退鍍液穩定性差，採用該退鍍液不能穩定進行電解退鍍，使得碳化鉻膜不能有效地、完全地退除，而且，還容易損傷基材。 The chromium carbide (Cr 3 C 2 ) film is a chromium-based coating with excellent properties, which is more resistant to oxidation and corrosion than the most commonly used chromium-chromium (Cr 2 N) film in chromium-based coatings. It has higher hardness and better wear resistance, and has a broad prospect in the industrial field. The existing method for electrolytic deplating of chromium carbide film adopts a deplating solution containing only a single alkali metal hydroxide (such as sodium hydroxide), and the deplating solution of the single component has poor stability, and the deplating solution cannot be stabilized by using the deplating solution. Electrolytic deplating is performed, so that the chromium carbide film cannot be effectively and completely removed, and the substrate is easily damaged.
有鑒於此，有必要提供一種不損傷基材前提下，能穩定、有效地退除碳化鉻膜層之退鍍液。 In view of the above, it is necessary to provide a deplating solution capable of stably and efficiently removing the chromium carbide film layer without damaging the substrate.
另外，還有必要提供一種使用上述退鍍液電解退除碳化鉻膜層之方法。 In addition, it is also necessary to provide a method of electrolytically removing the chromium carbide film layer using the above-mentioned deplating solution.
一種碳化鉻膜層之退鍍液，該退鍍液由鹼、促進劑、輔助劑及水組成，其中所述鹼為可溶性鹼金屬氫氧化物，鹼之濃度為20~200g/L；該促進劑為與鉻離子有絡合作用之絡合劑，該促進劑之濃度為40~150g/L；該輔助劑為可溶性聚磷酸鹽類化合物，輔助劑之濃度為0.5~10g/L。 a deplating solution of a chromium carbide film layer, the deplating solution is composed of a base, a promoter, an auxiliary agent and water, wherein the alkali is a soluble alkali metal hydroxide, and the concentration of the alkali is 20 to 200 g/L; The agent is a complexing agent for complexing with chromium ions, and the concentration of the accelerator is 40-150 g/L; the auxiliary agent is a soluble polyphosphate compound, and the concentration of the auxiliary agent is 0.5-10 g/L.
一種電解退除碳化鉻膜層之方法，包括：將形成有碳化鉻膜層之基材浸置於50~95℃之退鍍液中，並以該退鍍液作為電解液，以該形成有碳化鉻膜層之基材作為陽極，用1~10A/dm2之電流密度進行電解，使該碳化鉻膜層退除；將退鍍後之基材進行洗滌及乾燥；其中該退鍍液為本發明所述之退鍍液。 A method for electrolytically removing a chromium carbide film layer, comprising: immersing a substrate formed with a chromium carbide film layer in a deplating solution at 50 to 95 ° C, and using the deplating solution as an electrolyte; The substrate of the chromium carbide film layer is used as an anode, and is electrolyzed with a current density of 1 to 10 A/dm 2 to remove the chromium carbide film layer; the substrate after deplating is washed and dried; wherein the deplating solution is The deplating solution described in the present invention.
相較於習知技術，所述碳化鉻膜層之退鍍液及電解退除碳化鉻膜層之退除方法使退膜後基材表面沒有受到腐蝕，且能穩定、有效地退除碳化鉻膜層。 Compared with the prior art, the stripping solution of the chromium carbide film layer and the method for removing the chromium carbide film by electrolysis remove the surface of the substrate after the film is not corroded, and can stably and effectively remove the chromium carbide. Membrane layer.
本發明之退鍍液適用於退除形成於基材表面之碳化鉻膜層。所述基材包括鐵基合金(如不鏽鋼)、銅、銅合金及塑膠。 The stripping solution of the present invention is suitable for removing a chromium carbide film layer formed on the surface of a substrate. The substrate includes an iron-based alloy such as stainless steel, copper, a copper alloy, and a plastic.
本發明之退鍍液為含有鹼、促進劑和輔助劑之水溶液。其中所述鹼可為可溶性鹼金屬氫氧化物，例如，可為氫氧化鈉和氫氧化鉀中之一種或其組合。該鹼之濃度可為20~200g/L，優選為50~100g/L。所述鹼在退鍍液中起導電作用，同時提供鹼性環境，使碳化鉻膜層中之鉻能夠溶解於退鍍液中。 The deplating solution of the present invention is an aqueous solution containing a base, an accelerator, and an adjuvant. Wherein the base may be a soluble alkali metal hydroxide, for example, one of sodium hydroxide and potassium hydroxide or a combination thereof. The concentration of the base may be 20 to 200 g/L, preferably 50 to 100 g/L. The base acts as a conductive agent in the stripping solution while providing an alkaline environment to enable the chromium in the chromium carbide film layer to be dissolved in the stripping solution.
該促進劑為可以與鉻離子有絡合作用之絡合劑，如可為酒石酸鉀鈉、葡萄糖酸鈉、檸檬酸鈉及乙二胺四乙酸(EDTA)等化合物中之一種或幾種之混合物，優選為葡萄糖酸鈉與檸檬酸鈉或者葡萄糖酸鈉與乙二胺四乙酸(EDTA)之混合物。促進劑之濃度為20~150g/L，優選為40~100g/L。碳化鉻膜層中之鉻溶解於退鍍液後，與促進劑發生絡合作用形成絡合物，因此有利於碳化鉻膜層中之鉻之持續溶解。 The accelerator is a complexing agent which can be complexed with chromium ions, such as a mixture of one or more of potassium potassium tartrate, sodium gluconate, sodium citrate and ethylenediaminetetraacetic acid (EDTA). Preferred is sodium gluconate with sodium citrate or a mixture of sodium gluconate and ethylenediaminetetraacetic acid (EDTA). The concentration of the accelerator is 20 to 150 g/L, preferably 40 to 100 g/L. After the chromium in the chromium carbide film layer is dissolved in the deplating solution, it forms a complex with the accelerator to form a complex, thereby facilitating the continuous dissolution of chromium in the chromium carbide film layer.
輔助劑可為可溶性聚磷酸鹽類化合物，例如可為三聚磷酸鈉及五聚磷酸鈉中之一種或其組合，優選為五聚磷酸鈉。輔助劑之濃度為0.5~10g/L，優選為2~8g/L。輔助劑有利於加強電解完成後對基材之洗滌效果，可使附著於基材上之退鍍液更快、更完全地被清洗乾淨，以避免殘留退鍍液對基材之腐蝕。 The adjuvant may be a soluble polyphosphate compound, such as one or a combination of sodium tripolyphosphate and sodium pentapolyphosphate, preferably sodium pentapolyphosphate. The concentration of the adjuvant is 0.5 to 10 g/L, preferably 2 to 8 g/L. The auxiliary agent is beneficial to enhance the washing effect on the substrate after the completion of the electrolysis, and the deplating solution adhered to the substrate can be cleaned more quickly and completely to avoid corrosion of the residual deplating solution on the substrate.
該退鍍液可以藉由將上述鹼、促進劑及輔助劑溶於水製得。 The stripping solution can be prepared by dissolving the above base, accelerator and adjuvant in water.
利用上述退鍍液退除基材上之碳化鉻膜層之方法包括，將退鍍液加熱至50~95℃，將形成有碳化鉻膜層之基材浸置於退鍍液中，並以該退鍍液作為電解液，以該形成有碳化鉻膜層之基材作為陽極，以不鏽鋼板或碳板作為陰極，用1~10A/dm2之電流密度進行電解，使該碳化鉻膜層完全退除。所述電流密度優選4~7A/dm2。退鍍後，將基材進行洗滌及乾燥。 The method for removing the chromium carbide film layer on the substrate by using the deplating solution comprises: heating the deplating solution to 50 to 95 ° C, immersing the substrate formed with the chromium carbide film layer in the deplating solution, and The deplating solution is used as an electrolyte, and the substrate on which the chromium carbide film layer is formed is used as an anode, and a stainless steel plate or a carbon plate is used as a cathode, and electrolysis is performed at a current density of 1 to 10 A/dm 2 to form the chromium carbide film layer. Completely withdrawn. The current density is preferably 4 to 7 A/dm 2 . After deplating, the substrate is washed and dried.
下面藉由實施例對本發明進一步詳細說明。 The invention will now be described in further detail by way of examples.
將70g氫氧化鈉緩慢溶解於500ml去離子水中，然後加入50g檸檬酸鈉、30g葡萄糖酸鈉、2g五聚磷酸鈉，完全溶解後補去離子水使溶液體積為1L，得到退鍍液。 70 g of sodium hydroxide was slowly dissolved in 500 ml of deionized water, and then 50 g of sodium citrate, 30 g of sodium gluconate, and 2 g of sodium pentapolyphosphate were added, and after completely dissolving, deionized water was added to make the volume of the solution 1 L to obtain a deplating solution.
將退鍍液加熱至60~70℃，將不鏽鋼基材表面形成有厚度為大約2μm之碳化鉻膜層之樣品浸置於退鍍液中，並以該退鍍液作為電解液，以該形成有碳化鉻膜層之不鏽鋼基材作為陽極，以碳板作陰極，用5A/dm2之電流密度電解6分鐘，使該碳化鉻膜層完全退除。電解退鍍後，將不鏽鋼基材進行洗滌及乾燥。 The deplating solution is heated to 60 to 70 ° C, and a sample having a chromium carbide film layer having a thickness of about 2 μm formed on the surface of the stainless steel substrate is immersed in the deplating solution, and the deplating solution is used as an electrolyte to form the deplating solution. A stainless steel substrate having a chromium carbide film layer was used as an anode, and a carbon plate was used as a cathode, and electrolysis was performed for 6 minutes at a current density of 5 A/dm 2 to completely remove the chromium carbide film layer. After electrolytic deplating, the stainless steel substrate is washed and dried.
將60g氫氧化鈉緩慢溶解於500ml去離子水中，然後加入30g檸檬酸鈉、40g葡萄糖酸鈉、6g五聚磷酸鈉，完全溶解後補去離子水使溶液體積為1L，得到退鍍液。 60 g of sodium hydroxide was slowly dissolved in 500 ml of deionized water, and then 30 g of sodium citrate, 40 g of sodium gluconate, and 6 g of sodium pentapolyphosphate were added, and after completely dissolving, deionized water was added to make the volume of the solution 1 L to obtain a deplating solution.
將退鍍液加熱至60~70℃，將不鏽鋼基材表面形成有厚度為大約2μm之碳化鉻膜層之樣品浸置於退鍍液中，並以該退鍍液作為電解液，以該形成有碳化鉻膜層之不鏽鋼基材作為陽極，以碳板作陰極，用5A/dm2之電流密度電解6分鐘，使該碳化鉻膜層完全退 除。電解退鍍後，將不鏽鋼基材進行洗滌及乾燥。 The deplating solution is heated to 60 to 70 ° C, and a sample having a chromium carbide film layer having a thickness of about 2 μm formed on the surface of the stainless steel substrate is immersed in the deplating solution, and the deplating solution is used as an electrolyte to form the deplating solution. A stainless steel substrate having a chromium carbide film layer was used as an anode, and a carbon plate was used as a cathode, and electrolysis was performed for 6 minutes at a current density of 5 A/dm 2 to completely remove the chromium carbide film layer. After electrolytic deplating, the stainless steel substrate is washed and dried.
將50g氫氧化鈉緩慢溶解於500ml去離子水中，然後加入20g乙二胺四乙酸(EDTA)、40g葡萄糖酸鈉、4g五聚磷酸鈉，完全溶解後補去離子水使溶液體積為1L，得到退鍍液。 Slowly dissolve 50g of sodium hydroxide in 500ml of deionized water, then add 20g of ethylenediaminetetraacetic acid (EDTA), 40g of sodium gluconate, 4g of sodium pentapolyphosphate, completely dissolve and add deionized water to make the volume of the solution 1L. Deplating solution.
將退鍍液加熱至60~70℃，將不鏽鋼基材表面形成有厚度為大約3μm之碳化鉻膜層之樣品浸置於退鍍液中，並以該退鍍液作為電解液，以該形成有碳化鉻膜層之不鏽鋼基材作為陽極，以碳板作陰極，用6A/dm2之電流密度電解5分鐘，使該碳化鉻膜層完全退除。電解退鍍後，將不鏽鋼基材進行洗滌及乾燥。 The deplating solution is heated to 60 to 70 ° C, and a sample having a chromium carbide film layer having a thickness of about 3 μm formed on the surface of the stainless steel substrate is immersed in the deplating solution, and the deplating solution is used as an electrolyte to form the deplating solution. A stainless steel substrate having a chromium carbide film layer was used as an anode, and a carbon plate was used as a cathode, and electrolysis was carried out for 5 minutes at a current density of 6 A/dm 2 to completely remove the chromium carbide film layer. After electrolytic deplating, the stainless steel substrate is washed and dried.
分別按照實施例1-3中所述之方法配製退鍍液，不同之處在於，將實施例1-3中之不鏽鋼基材用碳素鋼代替，在分別與實施例1-3相同之條件下進行電解退膜。 The deplating solution was prepared in the same manner as in Example 1-3 except that the stainless steel substrate of Example 1-3 was replaced with carbon steel, and the same conditions as in Example 1-3, respectively. Electrolysis is carried out under the film.
將上述實施例1至實施例6中退除膜層後之樣品作X射線繞射(X-RD)分析，均未發現Cr元素存在，證明膜層完全退除；將退除膜層後之樣品進行掃描電鏡(SEM)試驗，發現基材均沒有受到腐蝕。 The X-ray diffraction (X-RD) analysis of the samples obtained by removing the film layers in the above Examples 1 to 6 did not reveal the presence of Cr, indicating that the film layer was completely removed; the sample after the film layer was removed Scanning electron microscopy (SEM) tests were conducted and it was found that the substrates were not corroded.
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