论文标题
电沉积中的重核和树突生长之间的跨界未经电解质的跨界生长
Crossover between re-nucleation and dendritic growth in electrodeposition without supporting electrolyte
论文作者
论文摘要
这项工作的重点是由Hele-shaw细胞内的电静脉电沉积形成的金属沉积物的微观结构,而无需支撑电解质和流动。对于低应用电流密度J,沉积物在分支分支的形式下生长。如Fleury所示(自然,390,1997年),这些分支由小的金属晶体组成。该微观结构是由在生长方面之前的空间电荷区域(非电气中性溶液)的动力学引起的重新核过程构建的。当增加J时,晶体尺寸会减小,而成核频率会增加。如实验观察到的,形成树突而不是分支分支时,对于高J时,这些后一种趋势被逆转。成核/生长状态(分支分支)与纯生长状态(树突)之间必须有过渡。通过通过SEM仔细观察分支微观结构来对此过渡进行实验检查。对于铜和银分支,当J低于临界电流密度J_C(浓度依赖性)时,分支仅由非树枝状晶体组成。鉴于,当j> j_c时,观察了树突状晶体,它们成为构成较高J的分支的主要晶体。这些观察结果表明,模式尺度上的形态学转变(在分支分支和树突之间)源自构成分支的晶体的形态学转变。通过分析生长晶体的形状稳定性,从理论上讲后者。 Mullins&Sekerka模型(通过扩散生长的球形粒子的形状稳定性)通过预测晶体始终不稳定而不同意这些观察结果。有人提出,围绕生长晶体的空间电荷层诱导稳定效果。
This work focuses on the microstructure of metallic deposits formed by galvanostatic electrodeposition inside a Hele-Shaw cell without both supporting electrolyte and flow. For a low applied current density j, the deposit grows under the form of ramified branches. As shown by Fleury (Nature, 390,, 1997), these branches are composed of small metallic crystals. This microstructure is built up by a re-nucleation process induced by the dynamics of a space charge region (non-electrically neutral solution) ahead of the growth front. When increasing j the crystal size decreases whereas the nucleation frequency increases. These latter tendencies are reversed for high j when, as experimentally observed, dendrites are formed instead of ramified branches. There must be a transition between the nucleation/growth regime (ramified branches) and the pure growth regime (dendrites). This transition is examined experimentally by carefully observing the branch microstructure by SEM. For copper and silver branches, when j is lower than a critical current density j_c (concentration-dependent), the branches are composed only of non-dendritic crystals. Whereas, when j>j_c, dendritic crystals are observed and they become the main kind of crystals constituting the branches for higher j. These observations show that the morphological transition on the pattern scale, between ramified branches and dendrites, originates from a morphological transition on the scale of the crystals constituting the branches. This latter is considered theoretically by analyzing the shape stability of the growing crystals. The Mullins & Sekerka model (shape stability of a spherical particle growing by diffusion) disagrees with these observations by predicting that the crystals are always unstable. It is proposed that the space charge layer, surrounding the growing crystals, induces a stabilizing effect.