Studies on Nano-Electroplating using Liquid Membrane of Electrolyte Solution in Supercritical CO_2

作者提出了一种新的电镀技术“零排放超临界纳米电镀”，它是超临界流体和电镀技术的结合。在这项技术中，电镀反应是在超临界二氧化碳(CO_2)乳状液和含有表面活性剂的电镀溶液中进行的。用这种方法镀制的薄膜没有任何针孔，这些针孔来自于电解水产生的氢气杂音。与纯溶液电镀相比，该方法制备的镍膜具有更高的均匀性、更小的颗粒尺寸(约10 nm)和更高的维氏硬度。我们用连接到可编程电源的微小终端测量乳状液中的电流值，同时通过…观察乳状液的分散状态，从而阐明了ZSNP反应更多的高压观察室，这是在本项目中设计和制造的。乳状液体系中的电流值是波动的，随着压力的增加，电流值随波动电流的幅度减小。研究了ZSNP中新型含氟表面活性剂F(CF(CF_3)CF_2O)_3CF(CF_3)COO(CH_2CH_2O)_7CH_3.在一系列乳状液中的电镀反应，聚合物表面活性剂对乳状液的稳定起到了重要的作用。为了使电流随分散状态的变化而波动，控制镀膜的质量，还在超临界二氧化碳(sc-CO2)乳化液和含有表面活性剂的化学镀液中进行了化学镀反应。用该方法得到的Ni-P膜为均匀的共形薄膜，没有因电解水产生的氢气泡而形成的针孔，也没有由化学镀反应中的晶核生长形成的结节。较少

The authors have proposed an innovative electroplating technology "Zero-Emission Supercritical Nanoplating", which is a hybrid of supercritical fluid and electroplating technology. In this technology, electroplating reactions are carried out in emulsion of supercritical carbon dioxide (CO_2) and electroplating solution with surfactants. The plated film by this method did not have any pinholes, which come from hydrogen babbles produced by the electrolysis of water. Compared to electroplating from the solution only, higher quality nickel films have been prepared by this method, which have higher uniformity, smaller grain size (about 10 nm), and significantly higher Vickers hardness.We have elucidated the ZSNP reaction by measuring the current values in the emulsion with functions of pressure, surfactant concentration, and the solution/ CO_2 ratio, using minute terminals connected to a programmable power supply, while simultaneously observing the dispersion state of the emulsion through a … More high-pressure view cell, which was designed and produced in this project. The flow of current values in the emulsion system fluctuated, and the current value decreased together with the amplitude of the fluctuant current when the pressure was increased. The fluctuant current flow in the emulsion was concluded to play an important role in the fabrication of the nano grain nickel structure in the plated film.Moreover, we investigated an electroplating reaction in a series of emulsions between an electroplating solution and dense carbon dioxide (CO_2) using a novel fluorinated surfactant F(CF(CF_3)CF_2O)_3CF(CF_3)COO(CH_2CH_2O)_7CH_3. In ZSNP, the polymeric surfactant plays some important roles to stabilize the emulsion, to make the electric current fluctuant by the dispersion state and to control the quality of the plated film.The electroless plating reactions are also carried out in an emulsion of supercritical carbon dioxide (sc-CO_2) and an electroless plating solution with surfactant. The Ni-P film obtained by this proposed technique was a uniform and conformal film without the pinholes that form from the hydrogen bubbles produced by the electrolysis of water, and without the nodules that form from the nuclear growth on the electroless plating reaction. Less