CN105177578B - Copper electrolyte solution for stripping palladium-nickel alloy plated layer and a method of stripping - Google Patents

Copper electrolyte solution for stripping palladium-nickel alloy plated layer and a method of stripping Download PDF

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CN105177578B
CN105177578B CN 201510674763 CN201510674763A CN105177578B CN 105177578 B CN105177578 B CN 105177578B CN 201510674763 CN201510674763 CN 201510674763 CN 201510674763 A CN201510674763 A CN 201510674763A CN 105177578 B CN105177578 B CN 105177578B
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stripping
palladium
copper
plating
nickel alloy
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CN 201510674763
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CN105177578A (en )
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王琪
黄红缨
杨雨佳
范义春
周全法
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江苏理工学院
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Abstract

本发明公开了种用于铜基钯镍合金镀层退镀的退镀液及退镀方法,退镀液由溴化物45~55份、氧化剂6~10份、缓蚀剂苯并三氮唑0.3~0.6份以及水40~60份混合均匀后得到,退镀液的pH值<4;所述溴化物为氢溴酸、溴化钠中的种或两种的组合物;所述氧化剂为过氧化氢水溶液、二氧化锰、溴酸钠、高溴酸钠中的两种或两种以上的组合物。 The present invention discloses a kind of electrolyte solution for copper plating layer of palladium-nickel alloy plating and stripping back method, bath retreat from the bromide 45 to 55 parts, 6 parts to 10 oxidizer, a corrosion inhibitor benzotriazole 0.3 - 0.6 to 60 parts and 40 parts of water are mixed uniformly to give, pH of the bath back <4; the hydrobromic acid bromide, sodium bromide in the composition of one or two; the oxidizing agent is aqueous hydrogen peroxide, manganese dioxide, sodium bromate, sodium bromine or two of two or more compositions. 本发明采用溴化法退除铜基体上的钯镍合金镀层,镀层退除完全、高效,工艺简单,对铜基体的腐蚀轻微;本发明实现了镀件中铜基体与钯镍合金镀层的分离,即实现了铜基钯镍合金镀层的退镀;退镀液饱和后可从中回收钯、镍。 The present invention employs bromination stripping of palladium nickel alloy plating layer on the copper substrate, the coating stripping complete, efficient and simple process, a slight corrosion of copper matrix; the present invention realizes the separation of the plated copper substrate with a palladium-nickel alloy plating , i.e. to achieve a copper stripping palladium-nickel alloy plated layer; after saturated solution system may be recovered from palladium, nickel.

Description

用于铜基钯镍合金镀层退镀的退镀液及退镀方法 Copper electrolyte solution for palladium-nickel alloy plated layer and stripping the stripping method

技术领域 FIELD

[0001] 本发明涉及一种化学退镀方法,具体涉及一种用于铜基钯镍合金镀层退镀的退镀液及退镀方法。 [0001] The present invention relates to a chemical stripping method specifically relates to retreat copper plating solution for plating a palladium-nickel alloy plating and stripping-off method.

背景技术 Background technique

[0002] 钯是一种优良的电接触材料(电阻系数为0.099 Qmm/m)。 [0002] palladium is an excellent electric contact material (resistivity of 0.099 Qmm / m). 在电子工业,由于良好的耐蚀性、耐磨性、钎焊性和低接触电阻等特性使钯镍镀层代替金镀层在许多方面得到了应用,如金属封装、集成电路引线框架和接插件等电镀。 In the electronics industry, due to good corrosion resistance, abrasion resistance, brazeability and low contact resistance and other properties of palladium gold plating instead of nickel plating has been applied, such as a metal package, IC lead frame connector and the like in many ways plating.

[0003] 钯的标准电位EPd2+ZPd0为+0.82V,其化学性质稳定,不溶于冷硫酸和盐酸,溶于硝酸、王水和熔融的碱中,不受硫化物腐蚀,可长期保持色泽光亮不变。 [0003] palladium EPd2 + ZPd0 standard potential of + 0.82V, which is chemically stable, insoluble in cold sulfuric acid and hydrochloric acid, dissolved in nitric acid, aqua regia, and the molten alkali, sulfide corrosion is not kept for a long bright color constant. 钯与铜均属面心等轴结构,原子半径也相近(钯1.37A,铜1.28A ),铜和钯的性质非常相似,因此至目前为止,许多国家分离铜钯都采用硫酸浸出分离铜然后富集回收钯残渣的工艺。 Palladium and copper axle structure and the like belong to the heart surface, and the atomic radius similar (palladium 1.37A, copper 1.28A), the nature of the copper and palladium are very similar, so far, many countries have adopted separate copper leaching of palladium and copper separation enrichment process of recovering palladium residues.

[0004] 目前退除铜基钯镍镀层中钯镍的一种工艺是采用电化学方法,但是电化学方法在退除镀镍层过程中低电流密度区难以退除干净且退镀速度慢。 [0004] A process for copper stripping current palladium nickel plating layer of palladium nickel is the use of electrochemical methods, but the method of electrochemical stripping nickel-plated layer during the low current density area is difficult to clean and stripping stripping slow.

[0005] 又一种工艺是以浓硫酸和浓硝酸配制成退镀液,将铜基镀钯镍的物料浸入以退除钯镍镀层,而铜和浓硫酸反应表面生成的硫酸铜不溶于浓硫酸,阻止了硫酸和铜继续反应。 [0005] A further process is the formulation of concentrated sulfuric acid and concentrated nitric acid back into the bath, the nickel-copper-based material is immersed palladium palladium nickel plating addition to retreat, and concentrated sulfuric acid and the copper surface of copper sulfate is not generated in concentrated sulfuric acid, copper sulfate, and prevents the reaction was continued. 此工艺的缺点是用到大量浓硫酸和浓硝酸,对设备的要求很高,且生产过程危险性很大;退镀后的铜基体取出后需要快速用水清洗,此时由于放热进一步促进了铜的溶解并释放出大量的棕色氮氧化物气体,同时清洗水的用量较大;另外硫硝混酸退镀液稀释时放热产生气体,整个工艺过程将产生大量的难处理的酸性含铜废水。 The disadvantage of this process is used concentrated sulfuric acid and concentrated nitric large, high equipment requirements, and the production process great danger; copper matrix after the stripping requires fast water extraction cleaning, this time due to the exothermic further promote copper dissolution and release large amounts of brown nitrogen oxide gas, while a large amount of washing water; additional exotherm upon dilution gas mixed nitric acid sulfuric electrolyte solution, the whole process will produce a lot of acidic wastewater containing copper intractable .

发明内容 SUMMARY

[0006] 本发明所要解决的技术问题是提供一种镀层退镀彻底、高效、对铜基体腐蚀轻微的用于铜基钯镍合金镀层退镀的退镀液及退镀方法。 [0006] The present invention solves the technical problem is to provide a complete coating stripping, efficient, slight corrosion of copper of a copper plating layer of palladium-nickel alloy plating bath retreat back and stripping methods.

[0007] 实现本发明第一目的的技术方案是一种用于铜基钯镍合金镀层退镀的退镀液,由溴化物45〜55份、氧化剂6〜10份、缓蚀剂苯并三氮唑0.3〜0.6份以及水40〜60份混合均匀后得到,退镀液的pH值<4;所述溴化物为氢溴酸、溴化钠中的一种或两种的组合物;所述氧化剂为过氧化氢水溶液、二氧化锰、溴酸钠、高溴酸钠中的两种或两种以上的组合物。 Solution system [0007] achieve the first object of the present invention of a copper plating layer of palladium-nickel alloy plating for the back, by the parts of 45~55 bromide, 6~10 parts oxidant, corrosion inhibitor benzotriazole triazole 0.3~0.6 40~60 parts and rear parts of water were mixed to obtain a uniform, pH, electrolyte solution of <4; the hydrobromic acid bromide, sodium bromide in the composition of one or two; the said oxidizing agent is aqueous hydrogen peroxide, manganese dioxide, sodium bromate, sodium bromine two kinds or two or more compositions.

[0008] 其中作为溴化物使用的氢溴酸的浓度大于等于40%;作为氧化剂使用的过氧化氢水溶液的浓度为20%〜30%。 [0008] wherein a concentration of hydrobromic acid bromide used is 40%; concentration in aqueous solution as oxidizing agent hydrogen peroxide at 20% ~ 30%.

[0009] 实现本发明第二目的的技术方案是一种铜基钯镍合金镀层的退镀方法,包括以下步骤: [0009] achieve the second object of the present invention of a palladium-nickel alloy plating copper stripping method, comprising the steps of:

[0010] 笾配置退镀液,将溴化物45〜55份、氧化剂6〜10份、缓蚀剂苯并三氮唑0.3〜0.6 份以及水40〜60份混合均匀,得到退镀液待用,退镀液的pH值<4;所述溴化物为氢溴酸、溴化钠中的一种或两种的组合物;所述氧化剂为过氧化氢水溶液、二氧化锰、溴酸钠、高溴酸钠中的两种或两种以上的组合物。 [0010] ji solution system configuration, bromide parts of 45~55, 6~10 parts oxidant, corrosion inhibitor benzotriazole 0.3~0.6 parts of 40~60 parts of water and uniformly mixed to give bath retreat stand , pH of the bath back <4; the hydrobromic acid bromide, sodium bromide in the composition of one or both; the oxidant is aqueous hydrogen peroxide, manganese dioxide, sodium bromate, two or more of the two compositions in the sodium bromine.

[0011] ②将待退镀的镀件放置于滚动筐中,该镀件的基体为铜,镀层为钯镍合金;将滚动筐浸入退镀液中,待退镀的铜基钯镍合金镀层的镀件浸没在退镀液中;缓慢转动滚动筐使待退镀的镀件翻滚并充分接触退镀液,3〜5分钟后铜基体表面出现灰白色钝化层,此时钯镍镀层完全退除,完成铜基钯镍合金镀层的退镀,将滚动筐中的退镀后的镀件取出,水洗、 干燥得到铜基体。 Plating [0011] ② to be scrolled is placed in the stripping basket, the base member is made of copper plating, nickel alloy plating is palladium; the scroll casing is immersed in the electrolyte solution to be a copper-based stripping of palladium nickel alloy plated layer the plating is immersed in the electrolyte solution; slowly rotated so that the scroll housing member to be plated stripping roll and full contact solution system, an off-white copper surface passivation layer occurs 3 to 5 minutes, then palladium nickel plating layer entirely back in addition, the completion of copper plating of palladium-nickel stripping, rolling back the basket after plating plating removed, washed with water, and dried to give the copper matrix.

[0012] 步骤②中新鲜配置的退镀液20°C〜35°C下对钯镍镀层的退镀速度为0.5〜Ιμπι/ min〇 The [0012] Step ② arranged fresh electrolyte solution 20 ° C~35 ° C for palladium nickel plating stripping speed 0.5~Ιμπι / min〇

[0013] 上述步骤②完成第一批镀件的退镀后,退镀液还能继续用于退镀,在退镀液饱和前依次处理第二批至第N批待退镀镀件时,每一次将待退镀的镀件放置于滚动筐中,将滚动筐浸入退镀液中;缓慢转动滚动筐使待退镀的镀件翻滚并充分接触退镀液,铜基体表面出现灰白色钝化层时钯镍镀层完全退除,完成铜基钯镍合金镀层的退镀;退镀过程中保持退镀液的pH值小于4。 After [0013] completion of the above steps ② first stripping the plating, electrolyte solution for stripping can continue, in retreat bath before treated sequentially with saturated when the second batch to N stripping batch to be plated, each stripping to be plated is placed in a rolling basket, the basket is immersed in the electrolyte solution in the scroll; scroll slowly rotated so that the housing member to be plated stripping roll and full contact solution system, passivated copper surface appears gray when the nickel plating layer is completely stripping palladium, palladium-copper-nickel alloy plated layer to complete the stripping; electrolyte solution to maintain the pH during the stripping of less than 4.

[0014] 随着退镀作业的不断进行、退镀量的增加,待退镀件浸没在退镀液中10分钟后铜基体表面仍未出现灰白色钝化层时向退镀液中投加氧化剂,氧化剂的加入量为最初退镀液中水的质量的10%〜20%,所述氧化剂为20%〜30%过氧化氢水溶液、溴酸钠或高溴酸钠中的一种或一种以上的组合物。 [0014] With the continuous stripping operation, increasing the back coating amount of the oxidizing agent to be added back to the electrolyte solution was administered when the member is immersed in the plating bath for 10 minutes after the back surface of an off-white copper passivation layers she has not yet seen , the oxidizing agent is added in an amount of 10 percent by mass% ~ 20 water bath initially of withdrawal, one of the oxidants% ~ 30 20 percent aqueous hydroperoxide, sodium bromide or sodium or one of bromo combinations of the above composition.

[0015] 所述退镀液饱和时,待退镀的镀件浸没在其中后镀层不再被退除,即便添加氧化剂,10分钟内铜基体表面未出现灰白色钝化层,而是呈现出灰黑色。 [0015] When the extractor saturated bath, stripping the plating member to be immersed in the plating layer which no longer stripping, even if an oxidizing agent is added, over 10 minutes copper surface passivation layer is not an off-white appears, presenting a Gray black.

[0016] 本发明具有积极的效果:(1)本发明采用溴化法退除铜基体上的钯镍合金镀层,镀层退除完全、高效,工艺简单,对铜基体的腐蚀轻微;本发明实现了镀件中铜基体与钯镍合金镀层的分离,即实现了铜基钯镍合金镀层的退镀;退镀液饱和后可从中回收钯、镍。 [0016] The present invention has positive effects: (1) the present invention uses bromination stripping palladium-nickel plated layer on the copper substrate, the coating stripping complete, efficient and simple process, a slight corrosion of copper matrix; implement the present invention separation of the copper matrix palladium plating nickel alloy plated layer, i.e., to achieve a copper stripping palladium-nickel alloy plated layer; after saturated solution system may be recovered from palladium, nickel.

[0017] (2)本发明所使用的含溴退镀液在其pH<4时退镀速度较快,退镀液的pH值的范围较广;退镀过程可在常温下(20°C〜35°C下)进行,避免了退镀液中溴的挥发。 [0017] (2) used in the present invention the bromine-containing electrolyte solution in which pH <4 faster stripping, the pH of the bath retreat wide range; stripping procedure (20 ° C at room temperature at ~35 ° C), to avoid volatilization of the electrolyte solution of bromine.

[0018] (3)本发明的退镀液中不包含硝酸,因此退镀过程不会有氮氧化物生成而污染环境,也避免了硝酸对铜基体的腐蚀作用;退镀液中各组分的浓度低,对设备的要求也相应降低。 [0018] (3) The electrolyte solution of the present invention does not contain nitric acid, thus stripping process does not generate nitrogen oxide pollute the environment, but also to avoid the corrosive effects of copper nitrate body; electrolyte solution of each component low concentration, the equipment required is correspondingly reduced.

[0019] (4)将本发明的退镀方法可应用在资源化回收报废的表面镀钯镍的铜基电接触元件等废料上,报废镀件的镀层厚度约为2〜5μπι,镀层中钯含量约80%,镍含量约为20%;本发明可以将钯镍合金镀层与铜基体完全分离,钯镍溶解在退镀液中,铜以金属形式存在,退镀后的滚动筐中的固体物料清洗后首先得到金属铜,而退镀液中的钯镍经过进一步处理,可以获得单质钯、镍,也可以制成其他有价值的钯化合物或镍化合物,报废镀件的铜基体和镀层金属均能得到回收,因此完成资源化回收后可以获得较大的经济价值。 [0019] (4) The stripping method of the present invention may be applied to the resource recovery surface palladium-nickel scrap copper plating electrical contact elements and other waste, scrap plating coating thickness of about 2~5μπι, palladium plating content of approximately 80%, a nickel content of about 20%; the present invention may be palladium-nickel alloy plated layer and the copper matrix completely separated, dissolved in degenerative palladium nickel plating solution, copper is present in metallic form, after stripping basket rolling solids after the material was first cleaned copper, palladium nickel plating bath is deflected further treatment, can be obtained elemental palladium, nickel, may also be made in other valuable nickel compound or palladium compound, scrap copper metal plating and the plating body member It can be recycled, so after the completion of resource recovery can achieve greater economic value.

[0020] 现有的方法用在铜基镀钯镍镀件的铜和钯的分离和资源再生时,因镀层孔隙率极低,甚至用浓热硫酸也无法溶出其中的铜;而若用混酸或其他方法将铜溶出的话需消耗大量的酸,会造成环境污染,同时从高浓度铜溶液中富集和分离钯极为困难,资源再生和废水处理成本很高。 [0020] The conventional method used in the separation of copper and palladium and palladium-nickel-plated copper resources regeneration member, by coating low porosity, even with concentrated hot sulfuric acid can not be eluted wherein copper; and if a mixed acid or other means, then the copper dissolution consumes large amount of acid will cause environmental pollution, enrichment and isolation palladium extremely difficult from a high concentration of copper in solution, recycling and waste water treatment cost is high.

具体实施方式 detailed description

[0021] (实施例1) [0021] (Example 1)

[0022] 本实施例的铜基钯镍合金镀层的退镀方法包括以下步骤: [0022] The copper stripping method of palladium-nickel coating of the present embodiment comprises the steps of:

[0023] ①配置退镀液。 [0023] ① configuration retreat bath. 将氢溴酸45〜55份、二氧化锰3〜5份、过氧化氢水溶液3〜5份、苯并三氮唑0.3〜0.6份以及水40〜60份混合均匀,得到退镀液待用,退镀液的pH值<4。 The parts of 45~55 hydrobromic acid, manganese dioxide ~ 5 parts, 3 ~ 5 parts of aqueous hydrogen peroxide, benzotriazole and 0.3~0.6 parts of 40~60 parts of water were uniformly mixed to obtain a standby bath retreat , pH of the bath back <4. 其中氢溴酸的浓度大于等于40%,过氧化氢水溶液的浓度为20%〜30%。 The concentration of hydrobromic wherein% is 40, the concentration of hydrogen aqueous peroxide 20 percent% ~ 30.

[0024] 本实施例中称取47%氢溴酸50kg、二氧化锰4kg、30%过氧化氢4kg,苯并三氮唑0.5 kg和水50kg,将上述称取的物料混合均匀后得到退镀液,其pH值彡1,不需加其它酸调节pH; 配置好的退镀液转移至退镀槽中待用。 [0024] Example 47% hydrobromic acid was weighed 50kg present embodiment, the manganese dioxide 4kg, 30% hydrogen peroxide 4kg, Benzotriazole 0.5 kg and 50kg of water, the above materials were weighed to give a uniform mixed back plating solution, the pH San 1, without adding other acid to adjust pH; configured electrolyte solution was transferred to a stripping vessel stand.

[0025] ②将待退镀的镀件放置于滚动筐中,该镀件的基体为铜,镀层为钯镍合金,镀层的厚度为2〜5μπι,镀层中钯含量约为80%,余量为镍。 [0025] ② stripping to be plated is placed in a rolling basket, the base member is made of copper plating, a palladium-nickel alloy plating, the plating thickness of 2~5μπι, plating palladium content of about 80%, the balance nickel.

[0026] 将滚动筐浸入退镀液中,待退镀的铜基钯镍合金镀层的镀件浸没在退镀液中;缓慢转动滚动筐使待退镀的镀件翻滚并充分接触退镀液,3〜5分钟后铜基体表面出现灰白色钝化层,此时钯镍镀层完全退除,取出退镀完毕的镀件。 [0026] The scroll casing is immersed in the electrolyte solution to be a copper-based stripping of the palladium-nickel alloy plated layer is immersed in the plating bath back; scrolling slowly rotated so that the housing member to be plated stripping roll in contact with electrolyte solution and sufficiently , the surface of copper occurs 3 to 5 minutes after an off-white passivation layer, then stripping palladium nickel plating layer completely removed complete stripping member plating. 在25°C下新鲜的退镀液对镀层的退镀速度为〇.8ym/min。 At 25 ° C for a fresh back stripping rate of the plating bath is 〇.8ym / min.

[0027] 然后向滚动筐中装入另一批待退镀的镀件,装件完毕后重复上述使镀件浸没、翻滚的操作,待3〜5分钟后铜基体表面出现灰白色钝化层时退镀完毕,取出滚动筐中退镀完毕的镀件。 [0027] The basket was then charged to another group of the rolling-off to be completed after repeating the above that the plating plating, immersion plating attachments, rolling operation, the surface of copper passivation layer appears gray when three to five minutes later stripping is completed, remove the stripping basket scroll member plating completed. 在退镀液饱和之前可重复上述装件、退镀、取件操作。 Before a saturated solution system may repeat the attachments, stripping, pick operation.

[0028] 随着退镀作业的不断进行、退镀量的增加,退镀液的粘度不断增大,颜色逐渐加深,退镀速度降低,此时向退镀液中补充氧化剂,所述氧化剂为20%〜30%过氧化氢水溶液、 溴酸钠或高溴酸钠中的一种或一种以上的组合物,并适当添加浓度大于等于40%的氢溴酸保持退镀液的PH值小于4。 [0028] With the continuous operation for the stripping, stripping amount, increasing the viscosity of the electrolyte solution, the color gradually deepened, reduced stripping speed, when added to the electrolyte solution in the oxidant, the oxidant is aqueous hydrogen peroxide, sodium bromate or sodium bromine in a 20% ~ 30% or more through the composition, and adding a suitable concentration of greater than or equal to 40% hydrobromic acid electrolyte solution holding PH value of less than 4.

[0029] 其中氧化剂的加入原则是:待退镀件浸没在退镀液中10分钟后铜基体表面仍未出现灰白色钝化层,此时向退镀液中投加氧化剂,氧化剂的加入量为最初退镀液中水的质量的10%〜20%。 [0029] wherein the oxidizing agent is added to the principle: the stripping member to be immersed in the bath 10 minutes after the back surface of an off-white copper passivation layer not occur, this time adding to the oxidant solution system, the oxidizing agent is added in an amount 10% ~ 20% by mass of water in the first withdrawal bath.

[0030] 退镀液饱和时,待退镀的镀件浸没在其中后镀层不再被退除或退出不完全,即便添加氧化剂,10分钟内铜基体表面呈现灰黑色未出现灰白色钝化层。 [0030] When the saturated solution system, stripping the plating member to be immersed in the plating layer which no longer exits stripping or incomplete, even if an oxidizing agent is added, over 10 minutes copper surface passivation layer exhibits an off-white gray-black does not appear.

[0031] ③将步骤②中各次退镀完毕取出的镀件收集合并,用水清洗、干燥后得到铜基体; 此时铜基体的表面没有钯镍镀层残留,完成退镀作业;铜基体的表面只有轻微腐蚀,一方面铜基体的表面由CuBr沉淀覆盖而钝化,另一方面苯并三氮唑的保护作用阻止了铜被进一步腐蚀。 [0031] ③ ② the step back each time the completion of plating plating were pooled and extracted, washed with water, and dried to give a copper matrix; copper substrate surface at this time no residual palladium nickel plating, complete stripping operation; copper substrate surface only slight corrosion, on the one hand the surface of the passivated copper matrix covered precipitated CuBr, on the other hand the protective effect of benzotriazole prevents further corrosion of copper.

[0032] 饱和的退镀液收集,可资源化处理提取其中的钯、镍。 [0032] collecting saturated solution system, can process the extracted resource wherein palladium, nickel.

[0033] (实施例2) [0033] (Example 2)

[0034] 本实施例的铜基钯镍合金镀层的退镀方法其余与实施例1相同,不同之处在于:步骤①配置退镀液时,将氢溴酸35份、溴化钠15份、二氧化锰3份、溴酸钠5份、苯并三氮唑0.3 份以及水45份混合均匀,得到pH<4的退镀液待用。 Remaining the same [0,034] The present copper nickel alloy plated layer of palladium stripping Example Example 1, except that the steps of: ① When configured bath retreat, 35 parts of hydrobromic acid, sodium bromide 15 parts 3 parts of manganese dioxide, 5 parts of sodium bromate, 0.3 parts of benzotriazole and 45 parts of water were uniformly mixed to give pH <4 stand electrolyte solution.

[0035] (实施例3) [0035] (Example 3)

[0036] 本实施例的铜基钯镍合金镀层的退镀方法其余与实施例1相同,不同之处在于:步骤①配置退镀液时,将氢溴酸40份、溴化钠15份、过氧化氢水溶液2份、二氧化锰2份、高溴酸钠5份、苯并三氮唑0.4份以及水60份混合均匀,得到pH< 4的退镀液待用。 Remaining the same [0036] The method of the present embodiment copper stripping palladium-nickel alloy plating embodiment of Example 1, except that: ① the step back when the configuration bath, 40 parts of hydrobromic acid, 15 parts of sodium bromide, 2 parts of aqueous hydrogen peroxide, 2 parts of manganese dioxide, 5 parts of sodium bromo, 0.4 parts of benzotriazole and 60 parts of water were mixed uniformly to obtain pH <4 stand electrolyte solution.

Claims (6)

  1. 1. 一种用于铜基钯镍合金镀层退镀的退镀液,其特征在于:由溴化物45〜55份、氧化剂6〜10份、缓蚀剂苯并三氮唑0.3〜0.6份以及水40〜60份混合均匀后得到,退镀液的?!1值< 4;所述溴化物为氢溴酸或者是氢溴酸和溴化钠的组合物,作为溴化物使用的氢溴酸的浓度大于等于40%;所述氧化剂为过氧化氢水溶液、二氧化锰、溴酸钠、高溴酸钠中的两种或两种以上的组合物,作为氧化剂使用的过氧化氢水溶液的浓度为20%〜30%。 A copper electrolyte solution of palladium nickel alloy plated layer is used for stripping, wherein: the parts of 45~55 bromide, 6~10 parts oxidant, corrosion inhibitor benzotriazole and 0.3~0.6 parts 40~60 parts of water were mixed uniformly to obtain, bath retreat value 1 <4;?! hydrobromide the bromide or sodium bromide and hydrobromic acid composition, used as the bromide hydrobromide concentration greater than or equal to 40%; the oxidant is aqueous hydrogen peroxide, manganese dioxide, sodium bromate, sodium bromine in two kinds or more kinds of compositions, as aqueous hydrogen peroxide in a concentration of oxidizing agent 20% ~ 30%.
  2. 2. —种铜基钯镍合金镀层的退镀方法,其特征在于包括以下步骤: ① 配置退镀液,将溴化物45〜55份、氧化剂6〜10份、缓蚀剂苯并三氮唑0.3〜0.6份以及水40〜60份混合均匀,得到退镀液待用,退镀液的pH值<4;所述溴化物为氢溴酸或者是氢溴酸和溴化钠的组合物,作为溴化物使用的氢溴酸的浓度大于等于40%;所述氧化剂为过氧化氢水溶液、二氧化锰、溴酸钠、高溴酸钠中的两种或两种以上的组合物,作为氧化剂使用的过氧化氢水溶液的浓度为20%〜30%; ② 将待退镀的镀件放置于滚动筐中,该镀件的基体为铜,镀层为钯镍合金;将滚动筐浸入退镀液中,待退镀的铜基钯镍合金镀层的镀件浸没在退镀液中;缓慢转动滚动筐使待退镀的镀件翻滚并充分接触退镀液,3〜5分钟后铜基体表面出现灰白色钝化层,此时钯镍合金镀层完全退除,完成铜基钯镍合金镀层的退镀 2. - The method of stripping copper seed palladium-nickel alloy plating, characterized by comprising the following: ① From bath retreat configuration, bromide parts of 45~55, 6~10 parts oxidant, corrosion inhibitor benzotriazole 0.3~0.6 parts of 40~60 parts of water and uniformly mixed to give back stand bath, pH of the bath back <4; the hydrobromide or hydrobromide bromide and sodium bromide composition, the concentration of the bromide used is greater than or equal to 40% hydrobromic acid; the oxidant is aqueous hydrogen peroxide, manganese dioxide, sodium bromate, sodium bromine in two kinds or more kinds of compositions, as the oxidizing agent using the concentration of the aqueous hydrogen peroxide 20% ~30%; ② stripping to be plated is placed in a rolling basket, the base member is made of copper plating, nickel alloy plating is palladium; the scroll casing is immersed in electrolyte solution , the member to be plated copper stripping palladium-nickel alloy plated layer is immersed in the electrolyte solution; rolling slowly rotated so that the housing member to be plated stripping roll and full contact solution system, the surface of copper occurs 3 to 5 minutes gray passivation layer, this time palladium nickel alloy plated layer is completely stripping, copper completion of palladium nickel alloy plated layer stripping ,将滚动筐中的退镀后的镀件取出,水洗、 干燥得到铜基体。 , After the stripping of the scroll casing plated removed, washed with water, and dried to give the copper matrix.
  3. 3. 根据权利要求2所述的铜基钯镍合金镀层的退镀方法,其特征在于:步骤②中新鲜配置的退镀液20 °C〜35 °C下对钯镍合金镀层的退镀速度为0.5〜Ιμπι/min。 The copper stripping method of said palladium-nickel alloy plated layer as claimed in claim 2, wherein: the stripping of the palladium-nickel alloy plating speed step ② arranged fresh electrolyte solution 20 ° C~35 ° C It is 0.5~Ιμπι / min.
  4. 4. 根据权利要求2所述的铜基钯镍合金镀层的退镀方法,其特征在于:步骤②完成第一批镀件的退镀后,退镀液还能继续用于退镀,在退镀液饱和前依次处理第二批至第N批待退镀镀件时,每一次将待退镀的镀件放置于滚动筐中,将滚动筐浸入退镀液中;缓慢转动滚动筐使待退镀的镀件翻滚并充分接触退镀液,铜基体表面出现灰白色钝化层时钯镍合金镀层完全退除,完成铜基钯镍合金镀层的退镀;退镀过程中保持退镀液的PH值小于4。 4. The method of stripping copper plated layer of palladium-nickel alloy according to claim 2, wherein: after completion of the first step ② of plating stripping, electrolyte solution for stripping can continue, in retreat successively processing the second batch to be granted back to N when the plating plating, stripping each time to be plated is placed in a rolling basket, the basket is immersed in the electrolyte solution in the rolling bath before saturation; be slowly rotated so that the scroll housing stripping the plating bath retreat fully contact and rolling, the surface of copper alloy plated layer of palladium nickel appears completely gray passivation layer upon stripping, copper complete stripping of the palladium-nickel alloy plated layer; stripping bath is maintained during the retreat PH value of less than 4.
  5. 5. 根据权利要求4所述的铜基钯镍合金镀层的退镀方法,其特征在于:随着退镀作业的不断进行、退镀量的增加,待退镀件浸没在退镀液中10分钟后铜基体表面仍未出现灰白色钝化层时向退镀液中投加氧化剂,氧化剂的加入量为最初退镀液中水的质量的1 〇%〜20%, 所述氧化剂为2 0 %〜3 0 %过氧化氢水溶液、溴酸钠或高溴酸钠中的一种或一种以上的组合物。 5. The method of stripping copper plated layer of palladium-nickel alloy as claimed in claim 4, wherein: as the continuous stripping operation, the amount of back coating increases, to be immersed in a stripping bath retreat member 10 when adding an off-white copper surface passivation layer not to retreat after minutes oxidant bath, the oxidizing agent added in an amount of 1% ~ 20% by mass of the square of water in the bath initially withdrawal, the oxidizing agent is 20% ~ 3 0% aqueous hydrogen peroxide, sodium bromate and sodium bromine or one or more than one composition.
  6. 6. 根据权利要求5所述的铜基钯镍合金镀层的退镀方法,其特征在于:退镀液饱和时, 待退镀的镀件浸没在其中后镀层不再被退除,即便添加氧化剂,10分钟内铜基体表面未出现灰白色钝化层,而是呈现出灰黑色。 The method of stripping copper plating layer of palladium-nickel alloy according to claim 5, wherein: when a saturated solution system, stripping the plating member to be immersed in the plating layer which no longer stripping, even if an oxidizing agent is added , within 10 minutes an off-white copper substrate surface passivation layer does not occur, but showing a gray-black.
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