化学铸镍磷合金工艺及技术研究
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摘要
目前国内红外自调节节流制冷器和鱼雷引信装置中所使用的微型波纹管弹簧,主要是通过电铸纯镍成型或以靠进口为主。选择电铸成型的微型波纹管弹簧由于受电力线分布的影响,存在着波纹部分的峰谷壁厚相差较大和弹簧刚度达不到使用要求的问题；而且铸层含硫还会引起焊接脆性而影响使用。化学沉积的方式可以解决壁厚均匀度和焊接脆性的问题,但由于镍磷合金因其组织结构特性而存在铸层脆性较大的问题。本论文目的在于研制出零件塑性好、应力低、表面光泽性好、厚度均匀且具有较好刚度的镍磷合金微型波纹管弹簧,以满足目前红外节流制冷以及引信装置中的使用需求。
化学铸和化学镀都是利用根据化学沉积原理的加工工艺,而化学镀是指在需要防护的工件上形成具有防护功能的保护层,而化学铸的目的是形成具有一定的机械性能的独立实体零件。
通过大量的平行与正交试验最终得到了完全满足了最初的设计要求的微型波纹管弹簧：其磷含量控制在3-8%；刚度>1700g/cm2；零件均匀性达到90%以上,尺寸为50+5μm；另外零件可焊性以及后续机加工性能优良,表面呈半光亮。
在试验中发现络合剂、主盐和还原剂的改变都能引起镀层中的磷含量的变化,调整铸液的pH值以及温度、搅拌等工艺,也会对铸层中的磷含量有一定的影响,以乳酸+丁二酸钠为复合络合剂时可获得低磷的铸层,且铸液的稳定性好；TN1的加入可以提高铸层硬度和刚度、降低铸层的内应力,增加的铸层表面的光亮度等作用；搅拌可以提高铸层的均匀性,表面活性剂的加入可以保证铸层铸层表面无针孔缺陷；添加剂TN2的加入可以提高铸层的刚度,但使用过量时会造成铸层脆性较大,所以其用量应控制在1g/L以下。温度和搅拌参数对磷含量的影响相对较小；通过Design Expert (Version7.1.6)数值模拟得出合理的还原剂用量、pH值和温度等参数对铸层磷含量和沉积速度都有较大的影响,通过调整这些参数可以较好的控制铸层的沉积速度和磷含量,来提高生产效率、铸层的塑性以及刚度等。
试验中得到的化学铸液具有成分简单,易于维护,稳定性较好,通过磷含量的准确控制可以满足不同批量生产的要求,按装载量1dm2/L的计算,目前的波纹管弹簧的生产效率可达到100个/L左右。
At present, the miniature bellows spring used in infrared self-adjusting throttle cooler and torpedoes fusing, mainly made through pure nickel electroforming or relying on imports. Due to the distribution of power lines, electroformed miniature bellows spring is troubled by the problem of thickness difference between bellow's peak and valley, meanwhile the spring rigidity also could not meet the requirements; In electroforming, the sulfur in pure nickel can also cause welding brittleness. Electroless deposition can solve issues such as welding brittle and thickness difference, but the texture of Ni-P alloy could also cause more brittleness. The purpose of this paper is to develop a Ni-P alloy miniature bellows spring with good ductility, low stress, nice surface glossiness, Good thickness uniformity and also has a good rigidity, to meet domestic need in infrared self-adjusting throttle cooler and torpedoes fusing.
Electroless casting and electroless plating are according to the principle of electroless deposition process, The aim of electroless plating is make a protective coating with a piece of work which needed to form a protective layer of protection, And electroless casting the purpose of forming a certain independent entity parts with the mechanical properties.
Through a large number of parallel and orthogonal experiments, eventually, the electroless forming miniature bellows spring fully meet the designed requirements: phosphorus content3-8%; rigidity>1700g/cm2; part's uniformity reached 90%, sickness 50+5μm; also with good weld ability and suitability for subsequent machining process, and the surface was semi-bright.
The experiment shown out that complexant, main salt and reducing agent can cause changes in phosphorus content of the casting layer, stirring, adjusting pH value and temperature of the casting solution will also affect cast layer's phosphorus content, lactic acid+sodium succinate complexant could obtain a low phosphorus layer, and also could improve the solution's stability; Additive TN1 could improve the solidity and rigidity of the layer, reduce its internal stress, and increase the surface brightness; Stirring could improve the layer's uniformity; Active agent could guarantee the quality of layer surface; additives TN2 can improve the layer's rigidity, but an overdose will increases the brittleness, the amount should be controlled under 1g/L. temperature and stirring have a relative small effect on layer's phosphorus content; The Design Expert (Version7.1.6) numerical simulation found out that a reasonable amount of reducing agent, pH value and temperature selection could control the deposition rate to improve efficiency, also could control the layer's phosphorus content, to improve its plasticity and rigidity.
The casting solution used in the experiment is simple in formulation, easy to maintain, also has a good stability, so it could meet the requirements of different mass production. According to the loading capacity as 1dm2/L, the current bellows spring production efficiency can about reach 100/L
化学铸和化学镀都是利用根据化学沉积原理的加工工艺,而化学镀是指在需要防护的工件上形成具有防护功能的保护层,而化学铸的目的是形成具有一定的机械性能的独立实体零件。
通过大量的平行与正交试验最终得到了完全满足了最初的设计要求的微型波纹管弹簧：其磷含量控制在3-8%；刚度>1700g/cm2；零件均匀性达到90%以上,尺寸为50+5μm；另外零件可焊性以及后续机加工性能优良,表面呈半光亮。
在试验中发现络合剂、主盐和还原剂的改变都能引起镀层中的磷含量的变化,调整铸液的pH值以及温度、搅拌等工艺,也会对铸层中的磷含量有一定的影响,以乳酸+丁二酸钠为复合络合剂时可获得低磷的铸层,且铸液的稳定性好；TN1的加入可以提高铸层硬度和刚度、降低铸层的内应力,增加的铸层表面的光亮度等作用；搅拌可以提高铸层的均匀性,表面活性剂的加入可以保证铸层铸层表面无针孔缺陷；添加剂TN2的加入可以提高铸层的刚度,但使用过量时会造成铸层脆性较大,所以其用量应控制在1g/L以下。温度和搅拌参数对磷含量的影响相对较小；通过Design Expert (Version7.1.6)数值模拟得出合理的还原剂用量、pH值和温度等参数对铸层磷含量和沉积速度都有较大的影响,通过调整这些参数可以较好的控制铸层的沉积速度和磷含量,来提高生产效率、铸层的塑性以及刚度等。
试验中得到的化学铸液具有成分简单,易于维护,稳定性较好,通过磷含量的准确控制可以满足不同批量生产的要求,按装载量1dm2/L的计算,目前的波纹管弹簧的生产效率可达到100个/L左右。
At present, the miniature bellows spring used in infrared self-adjusting throttle cooler and torpedoes fusing, mainly made through pure nickel electroforming or relying on imports. Due to the distribution of power lines, electroformed miniature bellows spring is troubled by the problem of thickness difference between bellow's peak and valley, meanwhile the spring rigidity also could not meet the requirements; In electroforming, the sulfur in pure nickel can also cause welding brittleness. Electroless deposition can solve issues such as welding brittle and thickness difference, but the texture of Ni-P alloy could also cause more brittleness. The purpose of this paper is to develop a Ni-P alloy miniature bellows spring with good ductility, low stress, nice surface glossiness, Good thickness uniformity and also has a good rigidity, to meet domestic need in infrared self-adjusting throttle cooler and torpedoes fusing.
Electroless casting and electroless plating are according to the principle of electroless deposition process, The aim of electroless plating is make a protective coating with a piece of work which needed to form a protective layer of protection, And electroless casting the purpose of forming a certain independent entity parts with the mechanical properties.
Through a large number of parallel and orthogonal experiments, eventually, the electroless forming miniature bellows spring fully meet the designed requirements: phosphorus content3-8%; rigidity>1700g/cm2; part's uniformity reached 90%, sickness 50+5μm; also with good weld ability and suitability for subsequent machining process, and the surface was semi-bright.
The experiment shown out that complexant, main salt and reducing agent can cause changes in phosphorus content of the casting layer, stirring, adjusting pH value and temperature of the casting solution will also affect cast layer's phosphorus content, lactic acid+sodium succinate complexant could obtain a low phosphorus layer, and also could improve the solution's stability; Additive TN1 could improve the solidity and rigidity of the layer, reduce its internal stress, and increase the surface brightness; Stirring could improve the layer's uniformity; Active agent could guarantee the quality of layer surface; additives TN2 can improve the layer's rigidity, but an overdose will increases the brittleness, the amount should be controlled under 1g/L. temperature and stirring have a relative small effect on layer's phosphorus content; The Design Expert (Version7.1.6) numerical simulation found out that a reasonable amount of reducing agent, pH value and temperature selection could control the deposition rate to improve efficiency, also could control the layer's phosphorus content, to improve its plasticity and rigidity.
The casting solution used in the experiment is simple in formulation, easy to maintain, also has a good stability, so it could meet the requirements of different mass production. According to the loading capacity as 1dm2/L, the current bellows spring production efficiency can about reach 100/L
引文
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[5]李日昌.无硫镍电沉积波纹管[J].仪表技术与传感器,1987(4)：29～31
[6]李宁.化学镀镍实用技术[M].化学工业出版社,2003：1-4；43-52；529～533
[7]胡信国.化学镀镍新技术及其在工业中的应用[J].电镀与精饰,1998,20(2)：30～32
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[10]姜晓霞,沈伟.化学镀理论及实践[M].国防工业出版社,2000：2-60；100～112；150～200
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[13]张俊.镍钻合金冷屏件电铸技术研究[D].昆明理工大学硕士毕业论文,2008：15～60
[14]A.Malecki,A.Micek-llnicka.Electroless nickel plating from acid bath[J].Surface and Coatings Technology,2000,123(1):72～77
[15]Juan Hajdu,Stanley Zabrocky.The Future of Electroless Nickel[J].Metal Finishing, 2000,98(5):42
[16]黄高山,陶莉,周桂香等.酸性化学镀镍.磷工艺研究[J].电镀与涂饰,2001,20(2)：15～18
[17]邓联文,江建军,何华辉.酸性化学镀机理讨论及高磷含量磷镍合金镀层制各[J].腐蚀与防护,2002,23(11)：479～481
[18]蔡晓兰,黄鑫,刘志坚.化学镀镍溶液中络合剂对镀速影响的研究[J].吉林化工学院学报,2000,17(4)：21～23
[19]M.Reda Gad,A.E1-Magd.Additives for dcctroless nickel alloy coating processes[J], Metal Finishing,2001,99(2):77～83
[20]崔国锋,李宁,黎德育等.化学镀镍液的缓冲容量与沉积速度的关系[J].电镀与环保,2003,23(6)：19～22
[21]尹国光,张自广,吴文锟.稳定剂对化学镀镍液及镀层性能的影响[J].电镀与环保,2006,26(2)：20～23
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