Pattern formation during electrodeposition of copper-antimony alloys

Kostov, Vasil S.; Krastev, I.; Dobrovolska, Tsvetina

doi:10.5599/jese.235

Cited by 6 publications

(3 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Electrodeposition studies (for a comprehensive list of references, see Bozzini et al 2 ) have initially dealt with a range of Ag alloys (Ag−Sb, Ag−Sn, Ag− In, Ag−Bi, Ag−Cd), but it has been recently shown that similar phenomena also occur with Bi, In and Sb alloys not involving Ag: Ni−P−W−Bi, 2 Au−In, 4 Co−In, 5,6 Pd−In, 7 Cu− Sb. 8 Moreover, alloys with Pt-group metals, as Ir−Ru 9 and Pt− Ir, 10 electrodeposited from molten salts, have been found to exhibit the same type of dynamic behavior. Ag−In is the alloy that has been most intensively investigated 11−24 and for this reason we chose this system for the present study.…”

Section: Introductionmentioning

confidence: 99%

“…Notwithstanding the large corpus of systems investigated, recently reviewed in Bozzini et al and Krastev et al, still the mechanisms governing the spatiotemporal organization during electrochemical phase formation are poorly understood. Electrodeposition studies (for a comprehensive list of references, see Bozzini et al) have initially dealt with a range of Ag alloys (Ag–Sb, Ag–Sn, Ag–In, Ag–Bi, Ag–Cd), but it has been recently shown that similar phenomena also occur with Bi, In and Sb alloys not involving Ag: Ni–P–W–Bi, Au–In, Co–In, , Pd–In, Cu–Sb . Moreover, alloys with Pt-group metals, as Ir–Ru and Pt–Ir, electrodeposited from molten salts, have been found to exhibit the same type of dynamic behavior.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Depth-Dependent Scanning Photoelectron Microspectroscopy Unravels the Mechanism of Dynamic Pattern Formation in Alloy Electrodeposition

et al. 2018

View full text Add to dashboard Cite

Fascinating spatiotemporal patterns forming during the electrodeposition of some alloys have attracted the interest of the scientific communities dealing with electrochemical materials science and dynamic processes. Notwithstanding extensive experimental work and recently achieved theoretical insights, several aspects of the physical chemistry of these dynamic structures are still elusive. In particular, the analytical methods employed so far to characterize these structures invariably failed to pinpoint any chemical or structural patterns correlated to those perceived by the naked eye or with a light microscope. In this work, we have made systematic use of the extreme surface sensitivity provided by synchrotron-based scanning photoelectron microspectroscopy, combined with progressive erosion by precisely controlled Ar + sputtering, to achieve quantitative 3D understanding of the compositional and chemical-state distribution of an Ag−In electrodeposited layer, following the key elements Ag, In, and O. The results revealed that the pattern is present only in the topmost region (ca. 100 nm) of the layer and exhibits a regular distribution of the alloying elements in certain chemical states. Specifically, pattern formation in Ag−In electrodeposits is crucially controlled by the space distribution of surface In 3+ oxi-/ hydroxides, deriving from reaction-diffusion processes taking place during alloy growth, and this pattern disappears in depth because of the delayed reduction of In 3+ present in this film to elemental In, followed by intermetallic formation.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Depth-Dependent Scanning Photoelectron Microspectroscopy Unravels the Mechanism of Dynamic Pattern Formation in Alloy Electrodeposition

et al. 2018

View full text Add to dashboard Cite

show abstract

“…The fabrication of alloys by self-organized nonlinear reactions has been extensively studied by Krastev and co-workers. − The authors have reported the electrodeposition of several alloys, such as Ag–Sb, Ag–Bi, Ag–In, Ag–Sn, Ag–Cd, Cu–Sb, and In–Co, resulting in spatiotemporal structures on the surface . In addition, Perini et al. , explored the properties of the Pt 3 Sn intermetallic ordered structures toward the oscillatory formic acid electrochemical reaction.…”

Section: Introductionmentioning

confidence: 99%

Investigation of the Oscillatory Electrodissolution of the Nickel–Iron Alloy

et al. 2019

View full text Add to dashboard Cite

Among many chemical systems displaying oscillatory behavior, the anodic dissolution of transition metals is considered one of the first, with the reports dating from as early as 1828. Since then, electrochemical oscillators have been studied as single or in a multielectrode configuration coupled under different network topologies. The coupling is basically made up of electrical connections between the electrodes, keeping them far apart from each other in such a way that only electric coupling is present. Here, we report experimental studies of the coupling between two electrochemical oscillators, namely, the oscillatory corrosion of Ni and Fe, not as two separated electrodes but as in the form of an alloy. The phenomenon is described in terms of stationary and dynamic electrochemical techniques as well as a bifurcation diagram, depicting the region of a R ext versus E plane in which the oscillations are found. Also, a plot with the rate of the electrode potential change was calculated, which revealed the separation of the activation and passivation processes during an oscillatory cycle. These results suggest that there is a change in the mechanism by which the oscillations are observed when comparing Ni, Ni–Fe, and Fe. It is shown that, for the alloy, at potentials lower than the Flade potential, there is a mixed contribution from both Ni and Fe dissolution on the oscillations. This is a different potential region in comparison to Ni (∼1.2 to 1.5 V vs SCE), which is at the transpassive domain and compared to Fe (∼0.4 to 0.6 V vs SCE), with a mass transport-limited process at the current plateau just before the complete passivation. It is proposed that the oscillations found for the dissolution of the Ni–Fe alloy are produced by a mixed contribution from Fe and Ni in terms of their oxides and salts present in the passivation step, which impacts on the nonlinear dynamics of the system. In conclusion, a small amount of Fe (only 20%) is enough to induce a change in the mechanism by which the oscillations emerge, suggesting that a new process is taking place.

show abstract