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Kuznetsov, V. V.; Skibina, L. M.; Loskutnikova, I. N.

doi:10.1023/a:1013800817191

Cited by 6 publications

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“…The diffusion potential drop was eliminated by the Pleskov method. The chronovoltammetric procedures, as well as estimation and calculation of transient time, are already described in [6], the electrode impedance measurements, in [7], and those of tribotechnical characteristics, in [8]. The adhesion to the substrate was estimated by a bend and scratching tests.…”

Section: Methodsmentioning

confidence: 99%

?Anionic effect? in copper plating from sulfate aqueous-ethanolic electrolyte containing cyclic polyester

et al. 2005

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A peculiarity of sulfate copper-plating electrolytes is a possibility of forming of Cu 2+ -S ionic pairs or polynuclear complexes of copper with sulfate ions [2]. The anions were supposed [3] to act as a bridge ligand promoting the electron transfer to the discharging metal ion, thus, in particular, causing a lower electrode polarization in sulfate electrolytes as compared with perchlorate electrolytes. However, replacing the water molecules in the coordination sphere of Cu 2+ cations, organic ligand molecules may be capable of the formation of associates involving sulfate ions, thus causing an "anionic effect" [4]. Electroneutral species, thereby forming in the adsorption layer, can blockade the cathode and significantly inhibit the electrode reaction, which improves the coatings [5]. In this work, we will study copper plating from sulfate baths containing 15-crown-5 cyclic polyester under conditions, when the molecules of both additives and organic component of mixed aqueous-ethanolic solvent adsorb at the cathode. EXPERIMENTAL PROCEDUREAqueous and aqueous-ethanolic electrolytes (alcohol mole fraction x 2 = 0.04) containing 0.01 M CuSO 4 + 0.5 M H 2 SO 4 + y M MgSO 4 ( y = 0, 0.25, 0.5, and 1.0) were studied. 15-Crown-5 in a concentration of 0.01 mol/l was studied as the additive. Chemically pure recrystallized or distilled reagents and twice-distilled water were used. All electrochemical measurements were performed in an atmosphere of electrolytic hydrogen at 298 K in a three-electrode cell with separated cathodic and anodic compartments. Supporting electro-O 4 2-lytes were subjected to preelectrolysis with the aim of removing electrochemically active impurities. A silverchloride electrode was used as the reference one. The diffusion potential drop was eliminated by the Pleskov method. The chronovoltammetric procedures, as well as estimation and calculation of transient time, are already described in [6], the electrode impedance measurements, in [7], and those of tribotechnical characteristics, in [8]. The adhesion to the substrate was estimated by a bend and scratching tests. Figure 1 gives the initial cathodic polarization plots ∆ E in = E i -E 0 (where E i and E 0 are the Cu potentials under the current and open-circuit conditions, respectively, vs. the polarizing current density i ) determined from potential vs. time oscillograms for various bulk concentrations of sulfate ions . At all of i and studied, a single wave of copper(II) ion reduction was observed. The presence of linear (Tafel) segments in the ∆ E in vs. log i curves indicates that, at the initial instants, the electrode process rate is determined by the electrochemical discharge-desolvation stage. The exchange current i 0 of this stage determined from the above plots in aqueous electrolytes free of additive, monotonically increases with an increase in (Fig. 2a, curve 1 ). RESULTS AND DISCUSSIONTo reveal the reaction scheme of the processes, we applied diagnostic criteria commonly used in chronovoltammetry and chronopotentiometry [9]. An analysi...

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Section: Methodsmentioning

confidence: 99%

?Anionic effect? in copper plating from sulfate aqueous-ethanolic electrolyte containing cyclic polyester

et al. 2005

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“…The procedure of chronopotentiometric, chronovoltammetric, and impedance measurements is described in [6]. As additives, we studied benzhydrazides with the general formula where R = H, p -OCH 3 , or o -Cl.…”

Section: Methodsmentioning

confidence: 99%

10.1007/s11124-008-1010-1

2000

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It is shown that, depending on the nature of a substituent R in the molecule of addition agent, the electroactive species in the electron transfer may be either 2:1 metal-ligand complexes or more stable 1:1 ones. In the former case, the complexes formed in the surface layer blockade the electrode surface, increase Ψ ' -potential and thus impede the metal ion discharge; their inhibitive action increases with an increase in the ligand concentration. In the latter case, the complex formation makes the adsorption film be more permeable and thus accelerates the electroreduction reaction. An increase in the addition agent concentration is accompanied with a decrease in its inhibiting effectiveness.

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“…Так, ускорение электродного процесса при избытке иодидионов при электроосаждении кадмия связывается с электровосстановлением адсорбированных комплексов CdI 3 и обусловлено облегчением переноса электрона через анионы I -, которые являются мостиковыми лигандами вследствие наличия у них вакантных 5d-орбиталей [8]. Подобного рода механизм ускоряющего действия Iпри электровосстановлении ионов кадмия в присутствии тетрабутиламмония, N,N-диметилформамида (ДМФА), диметилсульфоксида и других ПАВ наблюдали также авторы работ [9][10][11], что указывает на общность механизма ускоряющего действия анионов Iкак в чистых электролитах, так и содержащих органические добавки.…”

Section: Introductionunclassified

“…Следует заметить, что качество Cd-покрытий (мелкокристалличность, адгезия, внешний вид) улучшается в ряду анионов F -, СН 3 СО 2 -, СlO 4 -, I -. Представленный обзор показывает, что на сегодняшний день достаточно подробно изучены пер-хлоратные [1,10] и йодидные [1,[8][9][10][11] водные и водно-органические системы. Тогда как поведение циклических органических соединений в сульфатных электролитах требует дополнительного изучения, чтобы судить об общих закономерностях их влияния на катодный процесс и морфологию поверхности.…”

Section: Introductionunclassified

КИНЕТИКА ЭЛЕКТРООСАЖДЕНИЯ И МОРФОЛОГИЯ ПОВЕРХНОСТИ КАДМИЕВЫХ И КАДМИЙОРГАНИЧЕСКИХ ПОКРЫТИЙ, СОДЕРЖАЩИХ Ε-Капролактам

Skibina¹,

Duran²,

Sokolenko³

2017

kcmf

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Установлено, что в сульфатных электролитах кадмирования кинетика катодного процесса, микроструктура и свойства покрытий являются функцией природы и концентрации органических добавок, в качестве которых изучены ε-капролактам (КЛ), тетрагидрофуран (ТГФ) и пропиленкарбонат (ПК). Изменение состава жидкой фазы и введение в раствор циклического лактама, меняя условия сольватации, заметно сказываются на адсорбционных и координирующих свойствах компонентов электролита и, как следствие, на характере катодных процессов. Сравнением 3d-сканов поверхностей сформированных покрытий подтверждено образование металлполимерного покрытия на основе кадмия в присутствии КЛ. Расчет параметров решетки кадмия и кадмийорганического покрытия, содержащего КЛ, показал уменьшение среднего размера и объема зерен осадка.

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Cited by 6 publications

References 4 publications

?Anionic effect? in copper plating from sulfate aqueous-ethanolic electrolyte containing cyclic polyester

?Anionic effect? in copper plating from sulfate aqueous-ethanolic electrolyte containing cyclic polyester

10.1007/s11124-008-1010-1

КИНЕТИКА ЭЛЕКТРООСАЖДЕНИЯ И МОРФОЛОГИЯ ПОВЕРХНОСТИ КАДМИЕВЫХ И КАДМИЙОРГАНИЧЕСКИХ ПОКРЫТИЙ, СОДЕРЖАЩИХ Ε-Капролактам

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