201137190 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種電解退除基材表面碳化絡膜層之退鍵液 及利用該退鍍液電解退除碳化鉻膜層之方法。 【先前技術】 [0002] 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，為減少損氣，節钓成本，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徐去係工業生產中一個重要 問題。 [0003] 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、抗腐蚀性，而且硬度更高，耐磨性能亦更好，在工 Q 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。 【發明内容】 [0004] 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。 [0005] 另外，還有必要提供一種使用上述退鍍液電解退除碳化 099113801 表單編號A0101 第3頁/共11頁 〇 201137190 鉻膜層之方法。 [0006] —種碳化鉻膜層之退鍍液，該退鍍液為含有鹼、促進劑 和辅助劑之水溶液，其中所述驗為可溶性驗金屬氫氧化 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 〇.5〜l〇g/L。 [0007] —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°C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。 [0008] 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猶後基材表面沒有受到腐麵 ，且能穩定、有效地退除碳化鉻膜層。 【實施方式】 [0009] 本發明之退鍍液適用於退除形成於基材表面之碳化路_ 層。所述基材包括鐵基合金（如不銹鋼）' 銅、銅合金 及塑膠。 [0010] 本發明之退鍵液為含有鹼、促進劑和輔助劑之水溶液。 其中所述驗可為可溶性鹼金屬氫氧化物，例如，可為氣 氧化鈉和氫氧化鉀中之一種或其組合。該驗之濃度可為 20〜200g/L，優選為50~100g/L。所述鹼在退鑛液中起 099113801 表單編號A0101 第4頁/共11頁 0992024314- 201137190 [0011] 導電作用’同時提供鹼性環境，使碳化鉻膜層中之鉻能 夠溶解於退鍵液中。 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 ο (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。 [0012] 輔助劑可為可溶性聚磷酸鹽類化合物，例如可為三聚嶙 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〜l〇g/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蘇效果，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。 Ο [0013] >!>! ί：:ί:.. 該退艘液可以藉由將·上述驗、促進劑及輔助劑溶於水製 得。 [0014] 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°C，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，以不銹鋼板或碳板作為陰 極，用1〜lOA/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 099113801 表單編號A_1 第5頁/共11頁 0992024314-0 201137190 材進行洗滌及乾燥。 [0015] 下麵藉由實施例對本發明進一步詳細說明。 [0016] 實施例1 [0017] 1.配製退鍍液 [0018] 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。 [0019] 2.電解退除碳化鉻膜層 [0020] 將退鍍液加熱至60~70°C，將不錄鋼基材表面形成有厚度 為大約2//m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，以該形成有碳化鉻臈層之不銹鋼 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 銹鋼基材進行洗滌及乾燥。 [0021] 實施例2 [0022] 1.配製退鍍液 [0023] 將6〇g氫氧化鈉緩慢溶解於5〇〇ml去離子水中，然後加入 30g檸檬酸鈉、4〇g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几，得到退鍍液。 [0024] 2.退除膜層 _]㈣舰加熱㈣〜7(rc，將補鋼基材表㈣成有厚度 為大約2ym之碳化鉻膜層之樣品浸置於退鍍液中並以 099113801 表單編號A0101 第6頁/共π頁 0992024314-0 201137190 該退鍍液作為電解液，以該形成有碳化鉻膜層之不銹鋼 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 銹鋼基材進行洗滌及乾燥。 [0026] 實施例3 [0027] 1.配製退鍍液 [0028] 將氫氧化鈉緩慢溶解於5〇〇ml去離子水中，然後加入 2〇g乙一胺四乙酸（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。 [0029] 2.退除膜層 .. ；；,：! - ' V；：;' ·： 闕將退舰加熱細，。C，將不表㈣成有厚度 為大約之碳化鉻膜層之樣品浸置於退鍍液中並以 該退锻液作為電解液，^該㈣有碳化鉻膜層之不錄鋼 基材作為陽極，以碳板作陰極，用6A/dm2之電流密度電 解5勿鐘，使該碳化鉻骐層完_退除。電解退鍍後，將不 銹鋼基材進行洗滌及乾燥。 [0031] 實施例4-6 剛A麟照實_1-3巾所述之方法g&製退鍍液，不同之處 H將實施例1-3中之不錄鋼基材用碳素鋼代替，在分 別與實施例卜3相同之條件下進行電解退膜。 圆將上述實施例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’均未發現以元素存在，證明膜層完全退 099113801 表單編號A0101 第7頁/共11頁 0992024314-0 201137190 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#。 【圖式簡單說明】 【主要元件符號說明】 099113801 表單編號A0101 第8頁/共11頁 0992024314-0[Technical Field] [0001] The present invention relates to a de-bonding liquid for electrolytically removing a carbonized film layer on a surface of a substrate, and a method for electrolytically removing a chromium carbide film layer by using the stripping solution. [Prior Art] [0002] 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 the gas loss and the cost of fishing, it is necessary to retreat the coating and rework the workpiece. Therefore, how to completely remove the coating from the surface of the substrate is an important problem in industrial production without damaging the substrate. [0003] A chromium carbide (Cr3C2) film is a chromium-based coating with excellent properties, which is more resistant to oxidation and corrosion than the most commonly used chromium-chromium (Cr2N) film in chromium-based coatings, and has a higher hardness. High, wear resistance is also better, and has a broad prospect in the field of industrial Q industry. 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. SUMMARY OF THE INVENTION [0004] In view of the above, it is necessary to provide a deplating solution capable of stably and effectively removing a chromium carbide film layer without damaging a substrate. [0005] In addition, it is also necessary to provide a method for electrolytically removing carbonized 099113801 Form No. A0101 Page 3 of 11 〇 201137190 chrome film layer using the above-mentioned deplating solution. [0006] A decarburizing solution of a chromium carbide film layer, the deplating solution is an aqueous solution containing a base, a promoter and an auxiliary agent, wherein the test is a soluble metal hydroxide, and the concentration of the alkali is 20 to 200 g / L; the accelerator is a complexing agent complexed with chromium ions, the accelerator concentration is 40~150g / L; the adjuvant is a soluble polyphosphate compound, the concentration of the adjuvant is 〇.5~l 〇g/L. [0007] 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 having the chromium carbide film layer formed thereon is used as an anode, and electrolysis is performed at 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; The deplating solution is the deplating solution described in the present invention. [0008] Compared with the prior art, the method for removing the stripping solution of the chromium carbide film layer and the electrolytic chromium stripping layer removes the surface of the substrate after the backing, and the surface of the substrate is not subjected to corrosion, and can be stably and effectively Remove the chromium carbide film layer. [Embodiment] The deplating solution of the present invention is suitable for removing a carbonization path layer formed on the surface of a substrate. The substrate comprises an iron-based alloy (such as stainless steel) 'copper, copper alloy and plastic. [0010] The debonding liquid of the present invention is an aqueous solution containing a base, an accelerator, and an adjuvant. The test may be a soluble alkali metal hydroxide, for example, one of sodium oxyhydroxide and potassium hydroxide or a combination thereof. The concentration of the test may be 20 to 200 g/L, preferably 50 to 100 g/L. The base is in the demineralizing liquid from 099113801 Form No. A0101 Page 4 / Total 11 Page 0992024314- 201137190 [0011] Conductive action also provides an alkaline environment, so that the chromium in the chromium carbide film layer can be dissolved in the key solution . 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). Preference is given to sodium gluconate and sodium citrate or a mixture of sodium gluconate and ethylenediaminetetraacetic acid ο (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 is dissolved in the deplating solution, it forms a complex with the promoter to form a complex, which is advantageous for the continuous dissolution of chromium in the chromium carbide film layer. The adjuvant may be a soluble polyphosphate compound, such as one or a combination of sodium tripolysodium citrate and sodium pentapolyphosphate, preferably sodium pentapolyphosphate. 5〜一〇g/L, preferably 2~8g/L. The auxiliary agent is beneficial to enhance the effect of washing the substrate on the substrate after the completion of the electrolysis, so that the deplating solution adhering to the substrate can be cleaned more quickly and completely to avoid corrosion of the residual deplating solution on the substrate. Ο [0013] >!>! ί:: ί:.. The effluent can be prepared by dissolving the above test, accelerator and adjuvant in water. [0014] 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, and immersing the substrate formed with the chromium carbide film layer in the deplating solution In the middle, 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 OA/dm 2 to carbonize the substrate. The chrome layer is completely removed. The current density is preferably 4 to 7 A/dm2. After deplating, the base 099113801 Form No. A_1 Page 5 of 11 0992024314-0 201137190 is washed and dried. [0015] The present invention will now be described in further detail by way of examples. Example 1 [0017] 1. Preparation of deplating solution [0018] 70 g of sodium hydroxide was slowly dissolved in 500 ml of deionized water, then 50 g of sodium citrate, 30 g of sodium gluconate, 2 g of sodium pentapolyphosphate, completely After dissolving, the deionized water was added to make the volume of the solution 1 L, and a deplating solution was obtained. [0019] 2. Electrolytic removal of chromium carbide film layer [0020] The deplating solution is heated to 60-70 ° C, and a sample of a chromium carbide film layer having a thickness of about 2 / / m is formed on the surface of the non-recorded steel substrate Immersed in the deplating solution, and using the deplating solution as an electrolyte, using the stainless steel substrate having the chrome carbide layer formed thereon as an anode, using a carbon plate as a cathode, and electrolyzing for 6 minutes at a current density of 5 A/dm 2 . The chromium carbide film layer is completely removed. After electrolytic deplating, the stainless steel substrate is washed and dried. Example 2 [0022] 1. Preparation of deplating solution [0023] 6〇g sodium hydroxide was slowly dissolved in 5〇〇ml of deionized water, then added 30g sodium citrate, 4〇g sodium gluconate, 6 g of sodium pentapolyphosphate, completely dissolved, and then deionized water to make the volume of the solution a few, to obtain a deplating solution. [0024] 2. Retract the film layer _] (4) ship heating (four) ~ 7 (rc, the steel substrate table (4) into a thickness of about 2ym of chromium carbide film sample dipped in the deplating solution and with 099113801 Form No. A0101 Page 6 / Total π page 0992024314-0 201137190 The deplating solution is used as an electrolyte, the stainless steel substrate forming the chromium carbide film layer is used as the anode, the carbon plate is used as the cathode, and the current density is 5 A/dm 2 . The chromium carbide film layer was completely removed by electrolysis for 6 minutes. After electrolytic deplating, the stainless steel substrate was washed and dried. [0026] Example 3 [0027] 1. Preparation of deplating solution [0028] Sodium hydroxide Slowly dissolve in 5 〇〇ml of deionized water, then add 2 〇g of ethyl edetamine (EDTA), 40 g of sodium gluconate, 4 g of sodium pentapolyphosphate, completely dissolved and then deionized water to make the volume of the solution 1 L, get back [0029] 2. Retreat the film layer.. ;;,:! - ' V;:;' ·: 阙 will retreat the ship to heat, C, will not be table (four) into a thickness of about chrome The sample of the film layer is immersed in the deplating solution and the retort is used as the electrolyte, and the (4) non-recorded steel substrate having the chromium carbide film layer is used as The carbon plate is used as a cathode, and the current is densified by a current density of 6 A/dm 2 for 5 minutes to remove the carbonized chrome layer. After the electrolytic deplating, the stainless steel substrate is washed and dried. [0031] 4-6 Just A Lin according to the method described in _1-3 towel g & de-plating solution, the difference H, the non-recording steel substrate in the example 1-3 is replaced by carbon steel, respectively Electrolytic detachment was carried out under the same conditions as in Example 3. The samples obtained by removing the film layers in the above Examples 1 to 6 were subjected to X-ray diffraction (X-RD) analysis, and none of the elements were found to prove the film. The layer completely retreats 099113801 Form No. A0101 Page 7/Total 11 Page 0992024314-0 201137190 Except; the sample after the film layer is removed is subjected to scanning electron microscopy (SEM) test, and it is found that the substrate is not subjected to rot #. 】 [Main component symbol description] 099113801 Form No. A0101 Page 8 / Total 11 Page 0992024314-0