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多孔氧化铝薄膜因其优异的介电、机械和光学性能，广泛应用于电子器件、催化载体等领域。阳极氧化是制备高质量多孔氧化铝薄膜的主要方法，常用的碳棒对电极的导电行为和机制是影响薄膜微结构及其物性的一个重要因素。本文选取6 wt%磷酸为电解液，圆形铝箔为阳极，碳棒作为对电极，电极间距为15 cm，氧化时间为40 s，实验研究了氧化电压在100-140 V下碳棒的导电行为。实验结果显示，氧化铝薄膜的孔洞深度和孔径由薄膜中心向外呈对称性递减分布。当氧化电压低于110 V时，制备的氧化铝薄膜孔深和孔径由薄膜中心向外渐变梯度较小，宏观上呈现均一的结构色；当氧化电压达到110 V时，氧化铝薄膜孔深和孔径渐变梯度较大，薄膜呈现虹彩环形的结构色，随着氧化电压的增大，薄膜孔深和孔径渐变梯度增加，结构色环的数量增多，可见光内色域宽度显著增大。利用电磁学和电化学理论计算了碳棒在不同氧化电压下的导电行为并分析了其导电机制，得到了碳棒具有“准点电极”导电特性的结论，揭示了碳棒上点电极位置的选择遵循两极间的电阻最小原则。这一发现不仅丰富了阳极氧化的电化学理论，并为制备多功能的氧化铝薄膜提供了理论和实验支撑。Porous anodic aluminum oxide (AAO) films, owing to their excellent dielectric, mechanical, and optical properties, have been widely applied in electronic devices, catalytic supports, and optical materials. Anodization is the primary method for fabricating high-quality porous AAO films, The conductive behavior and mechanism of commonly used carbon rod counter electrodes represent significant factors influencing the microstructure and properties of the films. In this study, a 6 wt% phosphoric acid solution was employed as the electrolyte, circular aluminum foil served as the anode, and carbon rods were used as the counter electrode with an inter-electrode distance of 15 cm, The oxidation time was fixed at 40 s. The conductive behavior of the carbon rod under oxidation voltages ranging from 100 V to 140 V was experimentally investigated. Results showed that the pore depth and diameter of the AAO film symmetrically decreased from the film center toward the edges. When the oxidation voltage was below 110 V, the gradients of pore depth and diameter from the center outward were relatively small, resulting in a macroscopically uniform structural color. At an oxidation voltage of 110 V, the gradients of pore depth and diameter increased significantly, producing iridescent concentric ring structural colors. With further increase in voltage, the gradients became more pronounced, the number of structural color rings increased, and the visible color gamut was significantly broadened. Electromagnetic and electrochemical theories were utilized to calculate the conductive behavior of the carbon rod under different oxidation voltages and to analyze its conduction mechanism. The carbon rod was found to exhibit “quasi-point electrode” conductive characteristics, with the selection of point electrode positions on the carbon rod following the principle of minimizing the resistance between the two electrodes. This finding not only enriches the electrochemical theory of anodization but also provides theoretical and experimental support for the fabrication of multifunctional AAO films.
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Keywords:
- Porous anodic aluminum oxide /
- quasi-point electrode /
- current density gradient /
- structural color modulation
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