纳米复合电铸制造技术研究
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摘要
电铸制造技术是利用电沉积原理制造零件的一种精密加工方法,由于具有加工时不受机械力、无工具损耗、成形精度高等特点,因而受到了越来越多的关注。采用电铸制造技术已经加工出航空、航天、微机电系统、兵器等领域许多关键零部件。
纳米复合电铸是将纳米粒子放入电铸液中,使纳米粒子与金属共沉积获得纳米复合沉积层的一种制造方法。由于纳米粒子-金属复合电铸层具有许多优点,因而成为近年来电铸制造技术的研究热点,纳米复合电铸技术已在微机电系统、放电加工用工具电极及高性能模具等方面获得成功应用。
本文在分析和总结电结晶理论和复合电沉积机理的基础上,探讨了电铸工艺参数对纳米颗粒复合量的影响,并获得了纳米颗粒复合量高,且分布较为均匀的纳米复合电铸层,研究了电铸工艺参数对纳米复合电铸层的显微硬度和耐磨性等性能的影响规律。本文具体研究内容包括以下几个方面:
1.提出了在纳米复合电铸过程中施加超声振动辅助纳米复合电铸制造技术,抑制了纳米复合电铸沉积层中出现大的纳米粒子团聚体问题,进行了相关的试验研究。试验结果表明,电铸过程中施加超声振动可以有效抑制沉积层中出现纳米粒子大团聚体问题。
2.系统研究了复合电铸工艺参数对Ni-CeO_2纳米复合沉积层中嵌入的CeO_2纳米粒子质量百分比、表面形貌、择优取向的影响。通过大量工艺试验,发现电流密度和溶液中纳米粒子加入量对复合沉积层的影响最大。选择合适的电流密度和溶液中纳米粒子添加量,可以获得纳米粒子高嵌入量的Ni-CeO_2复合沉积层。
3.研究了复合电铸工艺参数对Ni-CeO_2纳米复合沉积层显微硬度、耐磨损性能、耐腐蚀性能及高温氧化性能的影响,发现沉积层中嵌入的纳米粒子越多,其显微硬度越高。同时发现如果纳米粒子在沉积层中的嵌入量太多,会导致复合沉积层内应力过大,沉积层表面出现裂纹,这会导致其耐磨损性能、耐腐蚀性能及高温氧化性能的急剧下降。
4.研究了电流密度和溶液中纳米粒子加入量对CoNi-BaFe_(12)O_(19)复合沉积层纳米粒子嵌入量、Co及Ni含量的影响,发现BaFe_(12)O_(19)纳米粒子的嵌入可以抑制Co、Ni的异常共沉积现象。
5.提出了施加外部磁场辅助CoNi-BaFe_(12)O_(19)复合电铸制造技术,建立了此过程的动力学模型,理论上证明了施加外部磁场对提高强磁性纳米粒子-金属复合沉积层强磁性纳米粒子嵌入量的可行性。研究了该条件下电流密度和溶液中纳米粒子加入量对复合电沉积的影响,试验验证了此技术方案的有效性。
6.研究有无辅助外加磁场条件下CoNi-BaFe_(12)O_(19)复合沉积层的最大磁能级、剩磁及矫顽力的情况,研究表明,通过优化复合电铸工艺参数,可以获得最大磁能级为3.09 KJ/m~3的CoNi-BaFe_(12)O_(19)复合沉积层。如果施加外部辅助磁场,可以使CoNi-BaFe_(12)O_(19)复合沉积层的最大磁能级数值有较大幅度的攀升,达到4.14 KJ/m~3。
Electroforming is a nontraditional machining technology, in which a metallic part is produced by the electrodeposition of metal onto a cathode mandrel in the electrolytic bath. Many attention has been paid to it because of its’high fidelity of shape reproduction, cutting force-free, and no tool wear. Electroforming is now employed in many areas, such as aviation, aerospace, weapon, microelectromechanical system and so on.
The nano composite electroforming is a kind of technique in which nano particles are suspended in the electrolyte and embedded in the growing metal layer. The well dispersed nano particles in a metal matrix do not only enhance the mechanical properties including wear and corrosion resistance, but also open up potential applications of the composite materials in microdevices. Recently, a considerable amount of research effort has been spent on electroforming of nanostructured composite, and many parts, such as micro-, mold, and electrode used in electrodischarge machining, have been prepared by using nano composite electroforming.
Both the metal electrocrystallization theory and the codeposition mechanisms were reviewed in this dissertation. The influence of current density, nano particles concentration in the suspension, stir rate, and temperature of the bath on the nano particles inclusion into the deposit was studied, and the nano particles-metal composite layers were obtained with high weight percent of nano particles and uniform dispersion of nano particles. The morphology, component, and microstructure of nano composite electroforming layers were examined. In addition, the micro hardness, wear resistance, corrosion resistance, oxidation resistance, and magnetic properties of the nano composite layers were also evaluated.
The following work has been finished in this dissertation:
1. The nano composite electroforming technology with the aid of ultrasonic vibration was present to inhibit the agglomeration of nano particles in the nano composite layers. The experiments about the technology have been carried out, and its’feasibility was confirmed.
2. The effect of electroforming parameters on the weight percent of CeO_2 nano particles, morphology, and the preferred orientation of the Ni-CeO_2 composite layers was investigated, and the experiments’results indicated that both the current density and the CeO_2 particles concentration in the suspension play a major role in the Ni-CeO_2 composite electroforming. The Ni-CeO_2 composite layer with high weight percent of CeO_2 inclusion into the layer might be acquired by using the optimized parameters.
3. The influence of electroforming parameters on the micro hardness, wear resistance, corrosion resistance, and oxidation resistance of the Ni-CeO_2 nano composite layers were also examined. The experiments’results showed that the micro hardness of layer increased with the increment of weight percent of CeO_2 inclusion into the layer, and the wear resistance, corrosion resistance, and oxidation resistance of the composite layer were also enlarged while the weight percent of CeO_2 inclusion into the layer rose from 0 to 4.02%. However, the micro cracks occurred at the 4.98% weight percent of CeO_2 inclusion into the layer, which led to poor wear resistance, corrosion resistance, and oxidation resistance.
4. The influence of both BaFe_(12)O_(19) nano particles concentration and current density on the CoNi-BaFe_(12)O_(19) composite deposit compositions have been investigated, respectively. The introduction of BaFe_(12)O_(19) nano particles into the composite layers could prohibit the anomalous codeposition of Co-Ni alloy.
5. The magnetic field was introduced to electroform the magnetic particles- ferromagnetic matrix composites. The effect of both BaFe_(12)O_(19) nano particles concentration and current density on the CoNi-BaFe_(12)O_(19) composite deposit compositions has been evaluated, and the experiments’result demonstrated that the high BaFe_(12)O_(19) nano particles percent could be acquired by using a magnetic field.
6. The maximum magnetic energy density, coercivity, and remanence of the CoNi-BaFe_(12)O_(19) composite layers were investigated produced by nano composite electroforming with and without a magnetic field. With proper choice of electroforming parameters, the CoNi-BaFe_(12)O_(19) composite layer with the maximum magnetic energy density 3.09 KJ/m3 could be fabricated without a magnetic field, and one with the maximum magnetic energy density 4.14 KJ/m3 might be prepared in the presence of a magnetic field.
纳米复合电铸是将纳米粒子放入电铸液中,使纳米粒子与金属共沉积获得纳米复合沉积层的一种制造方法。由于纳米粒子-金属复合电铸层具有许多优点,因而成为近年来电铸制造技术的研究热点,纳米复合电铸技术已在微机电系统、放电加工用工具电极及高性能模具等方面获得成功应用。
本文在分析和总结电结晶理论和复合电沉积机理的基础上,探讨了电铸工艺参数对纳米颗粒复合量的影响,并获得了纳米颗粒复合量高,且分布较为均匀的纳米复合电铸层,研究了电铸工艺参数对纳米复合电铸层的显微硬度和耐磨性等性能的影响规律。本文具体研究内容包括以下几个方面:
1.提出了在纳米复合电铸过程中施加超声振动辅助纳米复合电铸制造技术,抑制了纳米复合电铸沉积层中出现大的纳米粒子团聚体问题,进行了相关的试验研究。试验结果表明,电铸过程中施加超声振动可以有效抑制沉积层中出现纳米粒子大团聚体问题。
2.系统研究了复合电铸工艺参数对Ni-CeO_2纳米复合沉积层中嵌入的CeO_2纳米粒子质量百分比、表面形貌、择优取向的影响。通过大量工艺试验,发现电流密度和溶液中纳米粒子加入量对复合沉积层的影响最大。选择合适的电流密度和溶液中纳米粒子添加量,可以获得纳米粒子高嵌入量的Ni-CeO_2复合沉积层。
3.研究了复合电铸工艺参数对Ni-CeO_2纳米复合沉积层显微硬度、耐磨损性能、耐腐蚀性能及高温氧化性能的影响,发现沉积层中嵌入的纳米粒子越多,其显微硬度越高。同时发现如果纳米粒子在沉积层中的嵌入量太多,会导致复合沉积层内应力过大,沉积层表面出现裂纹,这会导致其耐磨损性能、耐腐蚀性能及高温氧化性能的急剧下降。
4.研究了电流密度和溶液中纳米粒子加入量对CoNi-BaFe_(12)O_(19)复合沉积层纳米粒子嵌入量、Co及Ni含量的影响,发现BaFe_(12)O_(19)纳米粒子的嵌入可以抑制Co、Ni的异常共沉积现象。
5.提出了施加外部磁场辅助CoNi-BaFe_(12)O_(19)复合电铸制造技术,建立了此过程的动力学模型,理论上证明了施加外部磁场对提高强磁性纳米粒子-金属复合沉积层强磁性纳米粒子嵌入量的可行性。研究了该条件下电流密度和溶液中纳米粒子加入量对复合电沉积的影响,试验验证了此技术方案的有效性。
6.研究有无辅助外加磁场条件下CoNi-BaFe_(12)O_(19)复合沉积层的最大磁能级、剩磁及矫顽力的情况,研究表明,通过优化复合电铸工艺参数,可以获得最大磁能级为3.09 KJ/m~3的CoNi-BaFe_(12)O_(19)复合沉积层。如果施加外部辅助磁场,可以使CoNi-BaFe_(12)O_(19)复合沉积层的最大磁能级数值有较大幅度的攀升,达到4.14 KJ/m~3。
Electroforming is a nontraditional machining technology, in which a metallic part is produced by the electrodeposition of metal onto a cathode mandrel in the electrolytic bath. Many attention has been paid to it because of its’high fidelity of shape reproduction, cutting force-free, and no tool wear. Electroforming is now employed in many areas, such as aviation, aerospace, weapon, microelectromechanical system and so on.
The nano composite electroforming is a kind of technique in which nano particles are suspended in the electrolyte and embedded in the growing metal layer. The well dispersed nano particles in a metal matrix do not only enhance the mechanical properties including wear and corrosion resistance, but also open up potential applications of the composite materials in microdevices. Recently, a considerable amount of research effort has been spent on electroforming of nanostructured composite, and many parts, such as micro-, mold, and electrode used in electrodischarge machining, have been prepared by using nano composite electroforming.
Both the metal electrocrystallization theory and the codeposition mechanisms were reviewed in this dissertation. The influence of current density, nano particles concentration in the suspension, stir rate, and temperature of the bath on the nano particles inclusion into the deposit was studied, and the nano particles-metal composite layers were obtained with high weight percent of nano particles and uniform dispersion of nano particles. The morphology, component, and microstructure of nano composite electroforming layers were examined. In addition, the micro hardness, wear resistance, corrosion resistance, oxidation resistance, and magnetic properties of the nano composite layers were also evaluated.
The following work has been finished in this dissertation:
1. The nano composite electroforming technology with the aid of ultrasonic vibration was present to inhibit the agglomeration of nano particles in the nano composite layers. The experiments about the technology have been carried out, and its’feasibility was confirmed.
2. The effect of electroforming parameters on the weight percent of CeO_2 nano particles, morphology, and the preferred orientation of the Ni-CeO_2 composite layers was investigated, and the experiments’results indicated that both the current density and the CeO_2 particles concentration in the suspension play a major role in the Ni-CeO_2 composite electroforming. The Ni-CeO_2 composite layer with high weight percent of CeO_2 inclusion into the layer might be acquired by using the optimized parameters.
3. The influence of electroforming parameters on the micro hardness, wear resistance, corrosion resistance, and oxidation resistance of the Ni-CeO_2 nano composite layers were also examined. The experiments’results showed that the micro hardness of layer increased with the increment of weight percent of CeO_2 inclusion into the layer, and the wear resistance, corrosion resistance, and oxidation resistance of the composite layer were also enlarged while the weight percent of CeO_2 inclusion into the layer rose from 0 to 4.02%. However, the micro cracks occurred at the 4.98% weight percent of CeO_2 inclusion into the layer, which led to poor wear resistance, corrosion resistance, and oxidation resistance.
4. The influence of both BaFe_(12)O_(19) nano particles concentration and current density on the CoNi-BaFe_(12)O_(19) composite deposit compositions have been investigated, respectively. The introduction of BaFe_(12)O_(19) nano particles into the composite layers could prohibit the anomalous codeposition of Co-Ni alloy.
5. The magnetic field was introduced to electroform the magnetic particles- ferromagnetic matrix composites. The effect of both BaFe_(12)O_(19) nano particles concentration and current density on the CoNi-BaFe_(12)O_(19) composite deposit compositions has been evaluated, and the experiments’result demonstrated that the high BaFe_(12)O_(19) nano particles percent could be acquired by using a magnetic field.
6. The maximum magnetic energy density, coercivity, and remanence of the CoNi-BaFe_(12)O_(19) composite layers were investigated produced by nano composite electroforming with and without a magnetic field. With proper choice of electroforming parameters, the CoNi-BaFe_(12)O_(19) composite layer with the maximum magnetic energy density 3.09 KJ/m3 could be fabricated without a magnetic field, and one with the maximum magnetic energy density 4.14 KJ/m3 might be prepared in the presence of a magnetic field.
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