高频脉冲电镀纳米晶镍镀层腐蚀行为研究
摘要
纳米晶体材料由于其非常小的尺寸和高的界面体积分数,与普通微晶材料相比,表现出很多优异的物理、化学和力学性能。在众多的纳米材料制备方法中,电沉积法被认为是一种极具优势的制备方法。目前人们对高频脉冲电镀的研究还较少,在本文的实验中实现了脉冲频率达到140 kHz的工艺条件,重点研究了镀层的耐腐蚀性能。
利用高频脉冲电源制备出镍镀层,对镀态镍镀层进行扫描电镜(SEM)、X射线衍射(XRD)测试。观察镀层表面形貌可以看出,相比较直流镀层,高频脉冲镀层的表面形貌粒晶更清晰,表面更加平整,高频条件下镀层表面粒径明显细化。用谢乐公式估算出了镀层表面粒径的大小,其中140 kHz条件下所得的镀层表面最平整粒径也最小,为45nm。
对高频脉冲条件下制备的镍镀层的耐腐蚀性能进行深入的研究。分别以3.5%NaCl溶液、10%NaOH溶液、15%H_2SO_4溶液为腐蚀介质,测试手段包括浸泡腐蚀实验和阳极极化测试。根据各个镀层的浸泡腐蚀失重图以及自腐蚀电流密度与自腐蚀电位数值,判断镀层耐腐蚀性能优劣。在脉冲电镀镀层中,随着脉冲频率的升高,镀层的失重量逐渐变小,表明高频条件使得镀层的耐腐蚀性能更加优异。采用外推法处理阳极极化曲线得到各个镀层的自腐蚀电流密度与自腐蚀电位值,可以看出相比直流镀层,脉冲镀层的自腐蚀电流与自腐蚀电位均正移,而且随着脉冲频率的升高,正移量越大,这与浸泡腐蚀失重曲线的测试结果数据显示相符。
研究了制备镀层的各个工艺参数对镍镀层的耐腐蚀性能的影响。通过采用四因素五水平的正交实验,得到25组不同镀层。分别对这25组镀层进行浸泡腐蚀实验和阳极极化测试,利用镀层的自腐蚀电流密度值与自腐蚀电位值作为正交实验的判断依据,得到各个工艺参数对镀层腐蚀性能影响的趋势图。随着脉冲频率的升高,镀层的耐腐蚀性能更显优异;在脉冲平均电流密度的变化范围(J_m=2.5～11 A·cm~(-2))中,镀层耐腐蚀性能有先增大后减小的变化趋势,其值为3.5 A·cm~(-2)左右时,镍镀层在NaOH溶液中和H_2SO_4溶液中耐腐蚀性能达到最好,值为6 A·cm~(-2)时,镍镀层在NaCl溶液中的耐腐蚀性能达到最好。占空比对于镀层的耐腐蚀性能的影响明显,镀层耐腐蚀性能随着占空比的增大有逐渐减小的变化趋势,在占空比最小时表现出优异的耐腐蚀性能。溶液pH值的影响也存在,当pH为3.3时,镀层的耐腐蚀性能达到最好。
In recent years, nanocrystalline materials with grain size of less than 100nm have received considerable attentions, and become a popular research field in material science. Specially, application and industrialization of nanocrystalline materials have been given more and more attentions. Among numerous synthesis methods for nanocrystalline materials, electrodeposition is considered to be one of the most dominant methods, not only for obtaining pure metals, binary alloys, ternary alloys and composites of nano-structures, but also easily transferring this technology from the research laboratory into industrialization.
At present, there is a little research on high-frequency pulse-electrodeposition, in this thesis, the level of pulse-electrodeposition could reach to 140 kHz. The point of this thesis is on deposits' corrosion behavior.
Prepared Ni deposits using high-frequency pulse power-supply. The surface morphology and configuration were investigated by X-ray diffraction technique(XRD), scanning electronic microscope(SEM). The results show that, compared to DCdeposits, high-frequency pulse deposits have much more clear and level surface. Calculated the average grain size of Ni deposits, using Scherrer formula. Ther result shows that, the deposits which is prepared under the condition of pulse-frequency 140 kHz, has the smallest grain size, about 45nm. Also it's the most level deposit.
The corrosion behavior of high-frequency pulse electrodeposits were deeply researched. Corrosion media included: 3.5% NaCl, 10% NaOH, 15% H_2SO_4. Testing methords were immersing corrosion test and Anodic polarization curse test. The corrosion behavior of Ni deposits could be judged according to the lost weight in these solutions, and the E_(corr)、i_(corr) of different Ni deposits.The result shows that, among all these pulse-deposits, the lost weight value is becoming smaller as the pulse-frequency raises, which means the corrosion resistance is getting much better as the pulse-frequency raises.The Anidic polarization was dealed with by extrapolation, each deposit's E_(corr) and i_(corr) value could be obtained. The value becomes bigger as the pulse-frequency raises, the biggest value means the best corrosion resistance propersity, the high-frequency pulse deposits have good anti-corrosion propersity.
The influence of pulse-electrodeposition parameters on deposit's corrosion behavior was studied.
The parameters include: J_m、r、f、pH. Using orthogonal experiment of 4 factors and 5 levels, 25 deposits could be prepared. The corrosion behavior was investigated by immersing corrosion test and Anodic polarization curse test. According to the E_(corr) and i_(corr) values, the trend curse of parameters on corrosion property could be gained.
The result shows that, as J_m raises, the corrosion propersity raises first and then falls down. The optimum corrosion propersity of deposits in NaOH and H_2SO_4 solutions could be gained when J_m is about 3.5 A·cm~2, and the optimum corrosion propersity in NaCl solution could be gained when Jm is about 6 A·cm~2.
As r raises, the corrosion propersity falls, so the smallest r value is needed. The pH level of solution is important too, pH=3.3 is preferred for a better corrosion propersity.
利用高频脉冲电源制备出镍镀层,对镀态镍镀层进行扫描电镜(SEM)、X射线衍射(XRD)测试。观察镀层表面形貌可以看出,相比较直流镀层,高频脉冲镀层的表面形貌粒晶更清晰,表面更加平整,高频条件下镀层表面粒径明显细化。用谢乐公式估算出了镀层表面粒径的大小,其中140 kHz条件下所得的镀层表面最平整粒径也最小,为45nm。
对高频脉冲条件下制备的镍镀层的耐腐蚀性能进行深入的研究。分别以3.5%NaCl溶液、10%NaOH溶液、15%H_2SO_4溶液为腐蚀介质,测试手段包括浸泡腐蚀实验和阳极极化测试。根据各个镀层的浸泡腐蚀失重图以及自腐蚀电流密度与自腐蚀电位数值,判断镀层耐腐蚀性能优劣。在脉冲电镀镀层中,随着脉冲频率的升高,镀层的失重量逐渐变小,表明高频条件使得镀层的耐腐蚀性能更加优异。采用外推法处理阳极极化曲线得到各个镀层的自腐蚀电流密度与自腐蚀电位值,可以看出相比直流镀层,脉冲镀层的自腐蚀电流与自腐蚀电位均正移,而且随着脉冲频率的升高,正移量越大,这与浸泡腐蚀失重曲线的测试结果数据显示相符。
研究了制备镀层的各个工艺参数对镍镀层的耐腐蚀性能的影响。通过采用四因素五水平的正交实验,得到25组不同镀层。分别对这25组镀层进行浸泡腐蚀实验和阳极极化测试,利用镀层的自腐蚀电流密度值与自腐蚀电位值作为正交实验的判断依据,得到各个工艺参数对镀层腐蚀性能影响的趋势图。随着脉冲频率的升高,镀层的耐腐蚀性能更显优异;在脉冲平均电流密度的变化范围(J_m=2.5～11 A·cm~(-2))中,镀层耐腐蚀性能有先增大后减小的变化趋势,其值为3.5 A·cm~(-2)左右时,镍镀层在NaOH溶液中和H_2SO_4溶液中耐腐蚀性能达到最好,值为6 A·cm~(-2)时,镍镀层在NaCl溶液中的耐腐蚀性能达到最好。占空比对于镀层的耐腐蚀性能的影响明显,镀层耐腐蚀性能随着占空比的增大有逐渐减小的变化趋势,在占空比最小时表现出优异的耐腐蚀性能。溶液pH值的影响也存在,当pH为3.3时,镀层的耐腐蚀性能达到最好。
In recent years, nanocrystalline materials with grain size of less than 100nm have received considerable attentions, and become a popular research field in material science. Specially, application and industrialization of nanocrystalline materials have been given more and more attentions. Among numerous synthesis methods for nanocrystalline materials, electrodeposition is considered to be one of the most dominant methods, not only for obtaining pure metals, binary alloys, ternary alloys and composites of nano-structures, but also easily transferring this technology from the research laboratory into industrialization.
At present, there is a little research on high-frequency pulse-electrodeposition, in this thesis, the level of pulse-electrodeposition could reach to 140 kHz. The point of this thesis is on deposits' corrosion behavior.
Prepared Ni deposits using high-frequency pulse power-supply. The surface morphology and configuration were investigated by X-ray diffraction technique(XRD), scanning electronic microscope(SEM). The results show that, compared to DCdeposits, high-frequency pulse deposits have much more clear and level surface. Calculated the average grain size of Ni deposits, using Scherrer formula. Ther result shows that, the deposits which is prepared under the condition of pulse-frequency 140 kHz, has the smallest grain size, about 45nm. Also it's the most level deposit.
The corrosion behavior of high-frequency pulse electrodeposits were deeply researched. Corrosion media included: 3.5% NaCl, 10% NaOH, 15% H_2SO_4. Testing methords were immersing corrosion test and Anodic polarization curse test. The corrosion behavior of Ni deposits could be judged according to the lost weight in these solutions, and the E_(corr)、i_(corr) of different Ni deposits.The result shows that, among all these pulse-deposits, the lost weight value is becoming smaller as the pulse-frequency raises, which means the corrosion resistance is getting much better as the pulse-frequency raises.The Anidic polarization was dealed with by extrapolation, each deposit's E_(corr) and i_(corr) value could be obtained. The value becomes bigger as the pulse-frequency raises, the biggest value means the best corrosion resistance propersity, the high-frequency pulse deposits have good anti-corrosion propersity.
The influence of pulse-electrodeposition parameters on deposit's corrosion behavior was studied.
The parameters include: J_m、r、f、pH. Using orthogonal experiment of 4 factors and 5 levels, 25 deposits could be prepared. The corrosion behavior was investigated by immersing corrosion test and Anodic polarization curse test. According to the E_(corr) and i_(corr) values, the trend curse of parameters on corrosion property could be gained.
The result shows that, as J_m raises, the corrosion propersity raises first and then falls down. The optimum corrosion propersity of deposits in NaOH and H_2SO_4 solutions could be gained when J_m is about 3.5 A·cm~2, and the optimum corrosion propersity in NaCl solution could be gained when Jm is about 6 A·cm~2.
As r raises, the corrosion propersity falls, so the smallest r value is needed. The pH level of solution is important too, pH=3.3 is preferred for a better corrosion propersity.
引文
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