化学镀Ni - W - P合金工艺的研究 - 赵晴-

1、化学镀N-i W -P 合金工艺的研究南昌航空工业学院(330034 赵 晴 杜 楠 熊友泉 黎 华 郭勇华摘 要 为了研究化学镀N-i W -P 镀液中硫酸镍、钨酸钠、次亚磷酸钠、柠檬酸三钠、稀土添加剂含量对镀层中磷、钨含量和镀速的影响以及镀层中钨含量对其耐蚀性和耐磨性的影响,采用721B 分光光度计、EDTA 络合滴定法和磨损试验法对化学镀N-i W -P 合金工艺进行了研究。结果表明:加入适量稀土添加剂可提高镀速1/4左右,但镀层中钨含量下降,磷含量增加;在硫酸和盐酸中镀层的耐蚀性随钨含量的增加而提高。本工艺性能稳定,操作方便。关键词 化学镀; 非晶态合金; 耐蚀性; 耐磨性; 稀土添加

2、剂中图分类号 TQ153.2 文献标识码 A 文章编号 1001-1560(200105-0028-02收稿日期 2000-12-20基金项目 江西省自然科学基金资助化学镀N-i W -P 三元合金与N-i P 合金相比,具有结合力好、硬度高,耐蚀、耐磨性能好等优点,近年来已得到广泛研究和应用14。由于合金中W,P 的含量对镀层的诸多性能有较大的影响,因此研究镀液的组成及各组分含量对镀层中合金含量的影响具有十分重要的价值。为此,重点讨论了化学镀N-i W -P 溶液中的主要成分和稀土添加剂含量变化对镀层中钨、磷含量及镀速的影响,同时也探讨了钨含量对镀层的耐蚀、耐磨性的影响。1 镀液、工艺条件及

3、性能测试方法将45.024.00.5的A3钢板经打磨y 除油y 热水洗y 酸洗y 流动水洗y 活化y 水洗y 施镀y 清洗y 吹干后在下列工艺条件下进行电镀:1540g/L 硫酸镍,4080g/L 钨酸钠,1530g/L 次亚磷酸钠,70130g/L 柠檬酸三钠,2535g /L 硫酸铵,28mg/L 稀土添加剂,乳酸、硝酸铅适量,p H=9.0,90e ,23h 。镀层组成测定:用721B 分光光度计测定钨含量,用EDTA 络合滴定镍含量。镀层性能测试:镀层耐蚀性用失重法和盐雾实验法评定;镀层的耐磨性的评定方法为用试片在PMJ -2型平面磨耗试验机(沈阳仪器仪表研究所产上磨400次,称量磨耗

4、前后的重量;镀层与基体的结合力用划痕法或弯曲法测定。2 各影响因素2.1 镀液成分含量对镀层中钨磷含量及镀速的影响(1钨酸钠浓度 钨酸钠是化学镀N-i W -P 合金镀液的主盐之一,镀层中的W 是由WO 2-4还原产生的,图1为镀液中硫酸镍26g/L,次亚磷酸钠20g/L,柠檬酸三钠100g/L,硫酸铵30g/L,乳酸5mg/L,硝酸铅20mg/L,pH=9.0,t =90e 时钨酸钠含量与镀层中W,P 含量及沉积速度的关系曲线。随着镀液中钨酸钠浓度的提高,镀层中钨含量逐渐增加,磷含量的变化甚微,而镀速在钨酸钠浓度为50g/L 最大。为了保证镀层中较大的含钨量及较大的镀速,镀液中钨酸钠的浓度以

5、60g/L 为宜。(2硫酸镍浓度 硫酸镍是化学镀N-i W -P 合金镀液的另一主盐。图2为钨酸钠60g /L,次亚磷酸钠20g/L,柠檬酸三钠100g/L ,硫酸铵30g/L,乳酸5mg/L,硝酸铅20mg/L,p H 值为9.0,t 为90e 时硫酸镍浓度与镀层中W,P 含量及沉积速度的关系曲线。从图2可看出,随着镀液中硫酸镍含量的增加,镀层中的钨、磷含量都呈下降的趋势,考虑到镀速的关系,硫酸镍的浓度以2530g/L 为宜,此时不仅镀速较高,且钨、磷含量也较高, 镀层光滑细致。(3次亚磷酸钠浓度 次亚磷酸钠是化学镀N-i W -P 合金镀液的还原剂,同时它还是镀层中磷的来源。从图3可看出,

6、随着次亚磷酸钠浓度的提高,镀层中磷含量增加,镀速也随之加快,当次亚磷酸钠浓度较低时,镀层中的钨含量随次亚磷酸钠浓度增加而增加,当其浓度增至20g/L 后,镀层中的钨含量呈缓慢下降的趋势。因次亚磷酸钠浓度高于25g/L 镀液出现黑色沉淀物,低于10g/L 沉积速度太慢,故其浓度取20g/L 较合适(实验条件:钨酸钠60g/L,硫酸镍26g/L,次亚磷酸钠1530g/L,柠檬酸三钠为100g/L,硫酸铵30g/L,乳酸5m g/L,硝酸铅20mg/L,pH=9.0,t =90e 。28M ateri alsProtectionElectroless N-i W -P PlatingMay 2001

7、Vol.34No.5 (4柠檬酸三钠浓度 柠檬酸三钠是化学镀N-i W -P 合金镀液中的络合剂,当钨酸钠为60g/L,硫酸镍26g/L,次亚磷酸钠26g/L,硫酸铵30g /L,乳酸5mg/L,硝酸铅20mg/L,p H 值为9.0,t 是90e 时,其在镀液中的浓度与镀层组成及镀速的关系见图4。镀层中的磷含量随柠檬酸三钠浓度的增加而提高,这主要是Ni 2+与其络合后镀液中的Ni 2+浓度降低之故。在柠檬酸三钠浓度为100g/L 时钨含量最高, 故取此浓度较为合适。(5稀土添加剂 许多化学镀镍液中添加稀土添加剂都会产生一定作用5,6。在化学镀N-i W -P 合金镀液中加入少量稀土添加剂对镀

8、层合金组成及镀速的影响见图5(实验条件:钨酸钠60g/L,硫酸镍26g/L,次亚磷酸钠26g/L ,柠檬酸三钠100g/L,硫酸铵30g/L,乳酸5mg/L,硝酸铅20mg/L,p H 值为9.0,t =90e 。从图5可以看出,稀土添加剂的适量加入可较大提高镀速,但在一定范围使钨含量下降。综合考虑镀速、钨磷含量几方面因素,稀土添加剂的量以2mg/L 为宜。盐雾实验结果显示,溶液中加入稀土添加剂所得镀层的耐蚀性优于未添加稀土 添加剂的镀层。2.2 N -i W -P 镀层中钨含量对耐蚀性及耐磨性的影响(1耐蚀性 不同钨含量的N-i W -P 镀层在硫酸和盐酸中浸泡24h 后的腐蚀数据见表1和表

9、2。表中数据说明,钨含量高于2.93%的N-i W -P 镀层在硫酸中未腐蚀,在盐酸中的腐蚀速度随合金中钨含量的降低而增大,当钨含量降至2.04%时,镀层在10%(体积盐酸中严重溶解。试样镀覆2.5h,镀层厚度在35L m 以上,几乎不存在贯穿到基体的孔隙,除发生溶解的试样外,可以认为A3钢基体对镀层的腐蚀速度没有影响。表1 不同含钨量的N-i W -P 镀层在硫酸中的耐蚀性(浸泡24h,夏季室温试 样腐蚀速度(mg/d #cm 210%H 2SO 4(体积20%H 2SO 4(体积5.41%W -11.85%P03.58%W -12.26%P 002.93%W -10.28%P 001.39

10、%W -6.23%P1.242.92表2 不同含钨量的N-i W -P 镀层在盐酸中的耐蚀性(浸泡24h,夏季室温试 样腐蚀速度(mg/d #cm 25%HCl(体积10%HCl(体积5.43%W -11.84%P2.474.314.25%W -12.76%P 3.155.512.93%W -10.28%P 4.577.782.04%W -13.02%P6.23溶解(2耐磨性 表3列出了不同钨含量的N-i W -P 镀层以及N-i P 镀层的耐磨性。从表3可以看出,N-i W -P 镀层的耐磨性都优于N-i P 镀层;在N-i W -P 镀层中,当磷含量变化不大时,耐磨性随钨含量的提高而增加。

11、因此,镀层中钨的含量对耐磨性有很大的影响。表3 不同含钨量的N-i W -P 镀层的耐磨性试 样耐磨性(次/mg5.18%W -12.05%P 1954.25%W -12.76%P 1553.58%W -12.26%P 1333.08%W -13.00%P 1242.04%W -13.00%P 1199.8%P(N-i P 镀层1033 结 语(1镀液中的主盐、还原剂、络合剂含量以及稀土添加剂对镀层的钨含量和镀速都有较大的影响。(2化学镀N-i W -P 镀层的耐蚀性和耐磨性均随镀层中的钨含量增加而提高。(3适量稀土添加剂的加入可以加快沉积速度。参考文献1 阎 洪.现代化学镀镍和复合镀新技术M

12、 .北京:国防工业出版社,1999.2 李 青.非晶态镀层发展趋势J.化工腐蚀与防腐,1996,18(2:983 宋锦福.镍-钨-磷合金化学镀的研究J.福州大学学报,1997,25(6:60644 朱一民.化学镀非晶态镍磷和镍钨磷双层组合镀工艺研究J.化学研究与应用,1998,109(50:5545575 汤皎宁.稀土对化学镀镍的影响J.材料保护,1997,30(3:8126 李卫清.稀土元素化学镀镍工艺研究J.材料保护,1998,31(1:1214(责任编辑 徐 军材料保护化学镀N -i W -P 合金工艺的研究2001年5月第34卷第5期29Rhodium Electroplating o

13、f Printed Circuit BoardWU Zu-chang,Li Jing-bo,Z HU Geng-hui(Xiangtan Electric Manu-facturing Croup Corporation Ltd,Xiangtan,P.R.China411101.Cailiao Baohu2001,34(5,2425(Ch.A newly developed rhodium electoplat-ing process for printed circuit board was introduced.The characteristics of the process,affe

14、cting factors and operation were described.Thickness of Micro-Arc Oxided Ceramic Layer on Hot D ip Alu minized Carbon SteelGAO Dian-kui,SHEN De-jiu,WANG Yu-lin(School of Machinery Engineering,Yanshan University,Qinghuangdao,P.R.China066004. Cailiao Baohu2001,34(5,2627(Ch.The factors affecting the th

15、ick-ness of micro-arc oxided ceramic layer on hot dip alu minized low carbon steel were di scussed.The experimental results showed that the predominant affecting factor was ti me for oxidation.Electroless Ni-W-P PlatingZHAO Qing,DU,Nan,XIONG You-quan et al(Nanchang Insti tute of Aeronautical Technol

16、ogy,Nanchang,P.R.Chi na330034.Cailiao Baohu 2001,34(5,2829(Ch.The effects of main in gredients inthe bath on deposi tion rate and on W,P contents in the deposit were investigated.The deposi tion rate could increase1/4by adding26mg/L rare element in the bath.The corrosion resistance and wear resistan

17、ce increased as the tungsten con ten t increasi ng.Room Temperature Sealing of Anodized Aluminum and Its Alloys GUO Xian-luo,D UAN jin-di,XIAO Qin-fang et al(Hunan College of Engineering,Xiangtan,P.R.China411101.Cailiao Baohu2001,34(5, 3031(Ch.The sealing treatment of anodized aluminum and its alloy

18、s is required for improving the anti-fouling and corrosion resistance perfor-mances.The effects of addition of cyclohexarone into the GA-93(Asea-l ing agent and reduction of the quanti ty of buffer solution were then invest-i gated and discussed.It was shown that the room temerature sealed film coul

19、d meet the requi rements of ISO3210.Preparation o f Epoxy Modified Nylon1010Anti-C orrosion PaintLI Zhen-fang(Jinhua College of profession and Technology Science and Engineering Branch,Jinhua,P.R.China321017.Cailiao Baohu2001,34 (5,3233(Ch.The modified Nylon1010was prepared by mixing e-p oxy resin a

20、nd Nylon1010.The effects of auxilary agent and filler were discussed.It was shown that the adhesive strength,chemical stabili ty and acid resistance of the modified Nylon paint were im-proved. Electroless Ni-p-C f C oplex PlatingLIU Bing-yu,MU Bai-chun,YOU x iang-qun(Departmen t of Materials and Che

21、mical Engineering,Liaoni ng Insti tute of Technology,Jinzhou,P.R. China121001.Ca iliao Baohu2001,34(5,3435(Ch.The effects of technological parameters and carbon fibre on the hardness and wear resis-tance of the deposit were investigated and di scussed.The experimen tal re-sults showed that the addit

22、ion of carbon fibre could obvi ously increase the hardness.Afrer ageing at500e the wear resistance of the Ni-P-C f coating could be6ti mes as high as that Ni-P coating.Structure and Corrosion Resistance of Room Tem perature Blackened phosphate FilmLIN Zi-hua(Shougang M inshan Machinery Factory of Ti

23、anshui City of Gansu Province,T ianshui,P.R.China.Cailiao Baohu2001,34(5,36 37(Ch.An Investigation of Coarse Grains Form ed on Zn Hot Dipped Steel Plate and Its Preventive MeasureC HEN Ji n-hong,LU Jin-tang,XU Qiao-yu(Institu te of Material Engi -neering,South China Universi ty of Technology,Cuangzh

24、ou,P.R.China 5105640.Cailiao Baohu2001,34(5,3839(Ch.The coarse grains-formed on steel plate during Zn hot dipping were investigated by OM,SE M and EPMA.It was shown the formati on of coarse grains on the plate surface was related to dross and contents of Al and Fe in the bath.Photometric Determinati

25、on of Sn in Sn-Co Plating SolutionQIU Xing-chu,QIU Shan(Panyu Fulong Hard wave Electronic Industry Co.Ltd.Guangzhou,P.R.China511483.Cailiao Baohu2001,34(5,40 41(Ch.Optimized Design of Cathodic Protecion of Underground Steel Pipe GONG Min,LUO Bin,Z HANG Yuna-sheng et al(Material and Chemical Engineer

26、ing Department Sichuan Insti tute of Industry&Chemical T echno-ogy,Zigong,P.R.Chi na643033.Cailiao Baohu2001,34(5,4245 (Ch.CPAS Corrosion Prevention C onsultant SystemLIU Chen,XIAO Y i-de,ZHANG San-ping et al(Wuhan Research Inst-i tute of Materials Protection Wuhan,P.R.China430030.Cailiao Baohu

27、2001,34(5,4647(Ch.The established corrosion prevention consultant sys tem could provide the consultant information on engineerin g structural design,materials and sys tem selections preven tivetechnology application and economy analysis.The CPAS system also had the advantage of corro-sion forecastin

28、g.The long-term corrosion behaviors could be forecasted by using stored corrosion data in the bank.Preparation of Room Temperature Zn-Mn Phosphating Bath Solu-tionZHANG Lian-hong(Liaoning T ianlong Chemis try Co.Ltd,Dandong Liaoning,P.R.China118000.Ca iliao Baohu2001,34(5,48(Ch. Hard Anodizing of2A12Alum inum A lloy PartsLU Xin-yuan(Nanji ng Chenguang Group Co.Ltd,Nanjing,P.R.China 210006.Cailiao Baohu2001,34(5,4950(Ch.Cleaning and Protecting of Oil PipeXU Jia-you,XIAO Dong,LU Deng-hua(Jianghan Oil Production Tech-nology Research Institution,Qianjiang,P.R.China433123.Cailiao Bao