新型铜锡合金电镀添加剂的制备
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摘要
目的制备一种电镀铜锡合金添加剂,利用此种添加剂制得白亮并且综合性能良好的铜锡合金镀层。方法基础镀液组成为:焦磷酸钾250 g/L,焦磷酸铜16 g/L,焦磷酸亚锡12 g/L。工艺条件为:pH 8.5,室温,电流密度0.3 A/dm~2,电镀时间5 min。以此为基础,设计正交试验,以镀层60°光泽度作为判定标准,优选出电镀添加剂的最佳配方。利用百格刀、维氏硬度计、材料表面性能综合测试仪、盐雾试验箱对最佳配方制备的镀层的附着力、表面硬度、摩擦系数、耐蚀性能等进行分析,利用SEM、XRD对其表面形貌及物相进行分析。结果经过正交试验优选出的最佳添加剂配方为:8×10~(-3) g/L聚二硫二丙烷硫磺酸钠(SPS),8×10~(-3) g/L聚乙烯亚胺烷基盐(PN),8×10~(-4) g/L 2-巯基苯并咪唑(M)。采用该添加剂配方,在上述基础镀液及工艺条件下,可获得全范围白亮Hull槽试片。该镀层60°光泽度达到269.7,表面平整,附着力的ISO等级为2,维氏硬度为154.47HV0.2,摩擦系数为0.2,盐雾试验中超过72 h无腐蚀。结论复配添加剂可以制备出光泽度较高的银白色镀层,且镀层结合力好,硬度、耐磨性以及耐腐蚀性都较高,可以满足工业要求。镀层表面平整,物相为Cu_6Sn_5以及Cu_(13.7)Sn。
The work aims to prepare a new electroplating additive to obtain a white bright copper-tin alloy electroplated coating with comprehensive properties. The electrolyte was composed of K_4P_2O_7·3H_2O of 250 g/L, Cu_2P_2O_7·3 H_2O of 16 g/L and Sn_2P_2O_7 of 12 g/L. The electroplating was conducted in the above electrolyte(pH = 8.5) at ambient temperature and current density of 0.3 A/dm~2 for 5 min. An orthogonal experiment was designed to determine the optimal formula of the electroplating additive, and the 60° gloss of coating was used as a criterion. The adhesion, surface hardness, friction coefficient and corrosion resistance of the coating prepared by the optimal formula were analyzed by cross-cut tester, vickers hardness tester, surface performance tester and salt spray device. The surface morphology and phase were analyzed by SEM and XRD. An optimal formula of additive selected by the orthogonal experiment was composed of SPS of 0.008 g/L, PN of 0.008 g/L and M of 0.0008 g/L. The white bright Hull cell test samples were prepared by the additive formula under the above electrolyte and process conditions. The gloss of the coating at 60° reached 269.7. The electroplated coating showed a smooth surface with adhesion level of ISO grade 2. Vickers hardness of the electroplated coating was 154.47 HV0.2, and the friction coefficient was 0.2. The electroplated coating was free from corrosion after the salt spray test for 72 hours. The obtained additive can be used to prepare a bright silvery electroplated coating with high glossiness. The coating has good bonding force, high hardness, and good abrasion resistance and corrosion resistance. The properties of the prepared coating can meet the requirements of industry. The coating surface is smooth and the phase is Cu_6Sn_5 and Cu_(13.7)Sn.
The work aims to prepare a new electroplating additive to obtain a white bright copper-tin alloy electroplated coating with comprehensive properties. The electrolyte was composed of K_4P_2O_7·3H_2O of 250 g/L, Cu_2P_2O_7·3 H_2O of 16 g/L and Sn_2P_2O_7 of 12 g/L. The electroplating was conducted in the above electrolyte(pH = 8.5) at ambient temperature and current density of 0.3 A/dm~2 for 5 min. An orthogonal experiment was designed to determine the optimal formula of the electroplating additive, and the 60° gloss of coating was used as a criterion. The adhesion, surface hardness, friction coefficient and corrosion resistance of the coating prepared by the optimal formula were analyzed by cross-cut tester, vickers hardness tester, surface performance tester and salt spray device. The surface morphology and phase were analyzed by SEM and XRD. An optimal formula of additive selected by the orthogonal experiment was composed of SPS of 0.008 g/L, PN of 0.008 g/L and M of 0.0008 g/L. The white bright Hull cell test samples were prepared by the additive formula under the above electrolyte and process conditions. The gloss of the coating at 60° reached 269.7. The electroplated coating showed a smooth surface with adhesion level of ISO grade 2. Vickers hardness of the electroplated coating was 154.47 HV0.2, and the friction coefficient was 0.2. The electroplated coating was free from corrosion after the salt spray test for 72 hours. The obtained additive can be used to prepare a bright silvery electroplated coating with high glossiness. The coating has good bonding force, high hardness, and good abrasion resistance and corrosion resistance. The properties of the prepared coating can meet the requirements of industry. The coating surface is smooth and the phase is Cu_6Sn_5 and Cu_(13.7)Sn.
引文
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[16]黄新,余祖孝.焦磷酸盐电镀Cu-Sn合金添加剂研究[J].腐蚀与防护,2011,32(12):1009-1012.HUANG Xin,YU Zu-xiao.Additives of pyrophosphate bath for electoroplating of Cu-Sn alloy coating[J].Corrosion&protection,2011,32(12):1009-1012.
[17]赵仲勋,曾鹏,谢光荣,等.电刷镀铜锡合金镀层成分控制与性能的研究[J].电镀与涂饰,2015(11):595-601.ZHAO Zhong-xun,ZENG Peng,XIE Guang-rong,et al.Study on composition control and performance of brush plated copper-tin alloy deposits[J].Electroplating&finishing,2015(11):595-601.
[18]鲜广,范洪远,郭智兴.化学镀工艺及镀层性能检测在实验教学中的应用[J].实验科学与技术,2017,15(5):171-174.XIAN Guang,FAN Hong-yuan,GUO Zhi-xing.Application of electroless plating process and performance testing on experimental teaching[J].Experiment science and technology,2017,15(5):171-174.
[19]黄秉升.盐雾试验标准及其实施[J].涂料工业,2002,32(12):39-41.HUANG Bing-shen.Salt spray test standard and its implement[J].Paint&coatings industry,2002,32(12):39-41.
[2]袁诗璞.代镍节镍工艺评述[J].电镀与精饰,2008,27(3):15-18.YUAN Shi-pu.Review on alternatives to nickel plating and nickel saving technicses[J].Electroplating&finishing,2008,27(3):15-18.
[3]YOSHIDA K,KITAGAWA S,MITOSE K,et al.Development of Cu-Sn alloy plating with superior excellent sliding characteristics and corrosion resistance[J].Furukawa review,2011,40:8-11.
[4]SUBRAMANIAN B,MOHAN S,JAYAKRISHNAN S.Structural,microstructural and corrosion properties of brush plated copper-tin alloy coatings[J].Surface&coatings technology,2006,201(3-4):1145-1151.
[5]AL-GANAINY G S,MOSTAFA M M.Transient creep and creep recovery behaviour of Cu-2wt%Sn alloy near the transformation temperature[J].Egyptian journal of solids,2004,27(1):121-133.
[6]赵洋.焦磷酸盐溶液体系电镀白铜锡新工艺及电沉积动力学[D].广州:华南理工大学,2013.ZHAO Yang.New process and electrochemical kinetics of bright copper-tin alloy electroplating from pyrophosphatebased electrolytes[D].Guangzhou:South China University of Technology,2013.
[7]阳洪英.四会市龙甫镇电镀厂危险有害因素分析及其安全对策措施[J].广东化工,2017,44(9):166-168.YANG Hong-ying.Harmful dangerous factors analysis and safety measures of electroplating factory in Sihui city Longfu zhen[J].Guangdong chemical industry,2017,44(9):166-168.
[8]程沪生.取代氰化物的热扩散法镀黄铜线[J].电镀与涂饰,2013,32(1):14-17.CHENG Hu-sheng.Brass plating on steel wire by thermal diffusion method as an alternative to cyanide platin[J].Electroplating&finishing,2013,31(1):14-17.
[9]欧阳飞,徐元,徐小平,等.焦磷酸盐镀铜溶液中柠檬酸铵含量的测定[J].电镀与精饰,2016,38(12):42-43.OUYANG Fei,XU Yuan,XU Xiao-ping,et al.Determination of ammonium citrate content in pyrophosphate electroplating copper solution[J].Plating&finishing,2016,38(12):42-43.
[10]黄灵飞.无氰Cu-Sn合金仿金电镀新工艺及其镀层性能研究[D].广州:华南理工大学,2015.HUANG Ling-fei.Study on the new process of non-cyanide Cu-Sn alloy imitation gold plating and coating performance[D].Guangzhou:South China University of Technology,2015.
[11]郭艳,曾振欧,谢金平,等.焦磷酸盐溶液体系电镀白铜锡的添加剂研究[J].电镀与涂饰,2013,34(4):171-175.GUO Yan,ZENG Zhen-ou,XIE Jin-ping,et al.Study on additive for white copper-tin alloy electroplating from pyrophosphate electrolyte[J].Electroplating&finishing,2013,34(4):171-175.
[12]ABBOTT A P,BALLANTYNE A,HARRIS R C,et al.Bright metal coatings from sustainable electrolytes:the effect of molecular additives on electrodeposition of nickel from a deep eutectic solvent[J].Physical chemistry chemical physics,2017,19(4):3219-3231.
[13]KELLY J,NOGAMI T,STRATEN O,et al.Electorte additive chemistry and feature size-dependent impurity incorporation for Cu interconnects[J].Journal of the electrochemical society,2012,159(10):D563-D569.
[14]曹强,汤智慧,程宗辉.300M钢刷镀镉性能及在某型飞机起落架修理中的应用[J].装备环境工程,2016(1):39-44.CAO Qiang,TANG Zhi-hui,CHENG Zong-hui.Performance of electric-brush plating cadmium on 300M steel and application in landing gear repair for a certain type of aircraft[J].Equipment environmental engineering,2016(1):39-44.
[15]赵洋,曾振欧,谢金平,等.添加剂对无氰电镀白铜锡工艺的影响[J].电镀与涂饰,2013,32(2):1-5.ZHAO Yang,ZENG Zhen-ou,XIE Jin-ping,et al.Effects of additives on cyanide-free white copper-tin alloy electroplating[J].Electroplating&finishing,2013,32(2):1-5.
[16]黄新,余祖孝.焦磷酸盐电镀Cu-Sn合金添加剂研究[J].腐蚀与防护,2011,32(12):1009-1012.HUANG Xin,YU Zu-xiao.Additives of pyrophosphate bath for electoroplating of Cu-Sn alloy coating[J].Corrosion&protection,2011,32(12):1009-1012.
[17]赵仲勋,曾鹏,谢光荣,等.电刷镀铜锡合金镀层成分控制与性能的研究[J].电镀与涂饰,2015(11):595-601.ZHAO Zhong-xun,ZENG Peng,XIE Guang-rong,et al.Study on composition control and performance of brush plated copper-tin alloy deposits[J].Electroplating&finishing,2015(11):595-601.
[18]鲜广,范洪远,郭智兴.化学镀工艺及镀层性能检测在实验教学中的应用[J].实验科学与技术,2017,15(5):171-174.XIAN Guang,FAN Hong-yuan,GUO Zhi-xing.Application of electroless plating process and performance testing on experimental teaching[J].Experiment science and technology,2017,15(5):171-174.
[19]黄秉升.盐雾试验标准及其实施[J].涂料工业,2002,32(12):39-41.HUANG Bing-shen.Salt spray test standard and its implement[J].Paint&coatings industry,2002,32(12):39-41.