Kinetics of passivation and pitting corrosion of polycrystalline copper in borate buffer solutions containing sodium chloride

Chialvo, María R. Gennero de; Salvarezza, Roberto Carlos; Moll, D. Vasquez; Arvía, Alejandro Jorge

doi:10.1016/0013-4686(85)80012-8

Cited by 125 publications

(88 citation statements)

References 25 publications

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“…12, merely loose contour with time after the immersion of the electrode. Similar developments of cyclic voltammograms are described in the literature (see [20,22]). Surface reconstruction caused by adsorbates is well known from ultra-high vacuum studies [24].…”

Section: Discussionmentioning

confidence: 79%

Impedance Studies of Copper in Alkaline Solutions, Especially During Electroless Plating

Wanner

Wiese

Weil

1988

Ber Bunsenges Phys Chem

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An impedance study of the electrochemical double layer of copper in an electro less copper plating bath was performed. Of the bath components (formaldehyde, ethylenediamine-tetraacetic acid (EDTA), CuEDTA 2 -, NaOH, Na ZS04, and NaHCOO) only the influence of hydroxide on the double layer is visible from capacitance data. The estimated surface coverage of hydroxide at the mixed potential of the electroless plating process is about 10%. On copper single crystal surfaces the OH --adsorption shows specific characteristics. Due to a surface reconstruction these characteristics, however, disappear with time after the immersion of the electrode. During the deposition process high electrode capacitances are measured (200-500 J-lF/cm 2 ). They are mainly caused by a surface roughness on the microscopic scale. When the deposition process is terminated, the surface relaxes within about 10 minutes. The addition of cyanide or Gafac (a mixture of organic esters of phosphoric acid) to the electroless plating bath markedly influences the capacitance data. However, always a correlation between the deposition rate and the electrode capacitance is observed. If, on the other hand, at potentiostatic cupric ion reduction formaldehyde in the plating bath is substituted by ethylenediamine, which also catalyzes the CuEDTA2--reduction, the capacitance values decrease with increasing deposition current. Presumably, in the first case the nucleation rate dominates the deposit growth, while in the second case the opposite is true. is of electrochemical nature [3 -5]. A mixed potential is established during the chemical deposition process. Electroless copper plating consists of the electrochemical reactions:[CuEDTA]2-+2H 2CO+40H-------+

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Section: Discussionmentioning

confidence: 79%

Impedance Studies of Copper in Alkaline Solutions, Especially During Electroless Plating

Wanner

Wiese

Weil

1988

Ber Bunsenges Phys Chem

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“…The corrosion potentials observed for a-brasses in neutral chloride solutions are very far from the theoretical values for CulCuCl couple, in contrast to neutral bromide and iodide solutions, so the presence of CuCl is doubtful. According to De Chialvo et al [34], the formation of CuCl occurs at more noble potentials than the corrosion potential.Thus the shift of the corrosion potential to more negative values may be connected with the adsorption of C1-ions onto the metal surface [35]. Such process is assumed to be the first step in the pitting corrosion [36].…”

Section: Methodsmentioning

confidence: 98%

Pitting Corrosion of Some α‐Brasses in Neutral and Alkaline Solutions Containing Halide Ions

El-Rahman

1990

Materialwissenschaft Werkst

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The pitting corrosion behaviour of some a-brasses (Cu%: 85, 70, 67,63 and 60) in neutral and alkaline solutions containing various halide ions was studied. The pitting corrosion resulted in dezincification in all cases and the pitting potential was found with few exceptions to increase in the order: Cu 60 < Cu 67, Cu 70 < Cu 63 < Cu 85 < Cu 100. Increase of pH was found to shift the pitting potential to more positive values and at highly enough pH values the pitting corrosion was inhibited in some cases. The instantaneous current, at constant potential and in absence of pitting, was found to varies linearly with (lltime)lR. at time 3 2 0 seconds. During the initial stages of pitting, the current was found to fit Engell-Stolica equation.The steady corrosion potentials in presence of Br-and I-ions were found to be nearly coincident with those of Cu/Cu halide couples while they were far from the theoretical values in presence of C1-ions and they changed negligibly in presence of F-ions.

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“…17 The interactions of copper oxides with complexing ions such as Cl − are rather complicated. 7,[23][24][25][26] Consequences of such interaction may be a localized attack, with loss of the oxide film. [27][28][29] Previous experimental studies repetitively showed that the presence of Cl − in the electrolyte leads to pitting corrosion, and thus instability of the oxide film, resulting in CuCl formation.…”

Section: -11mentioning

confidence: 99%

State of the Surface of Antibacterial Copper in Phosphate Buffered Saline

Toparlı

Hieke

Altin

et al. 2017

J. Electrochem. Soc.

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The state was investigated of the copper surface in phosphate buffered saline (PBS; 140 mM Cl − , 10 mM phosphate; pH 7) by a combination of cyclic voltammetry (CV) and chronoamperometry (CA) with in situ spectroscopic ellipsometry and Raman spectroscopy. After polarization, samples were analyzed ex situ. In agreement with expectations on the basis of the Pourbaix diagram, Cu 2 O and Cu 4 O 3 were observed when polarizing the system above ≈−0.05 V vs. Ag|AgCl|3M KCl. The formation of Cu 2 O did not lead to a passivation of the system. Rather, the system dissolved under formation of soluble square planar CuCl 2− 4 , identified by its strong Raman peak ≈300 cm −1 . During dissolution, spectroscopic ellipsometry showed a film with a stable steady state thickness. Energy electron loss spectroscopy (EELS) analysis of a cross section of the oxide after removal from the electrolyte showed that the oxide was Cu 2 O. It is suggested that Cl − replaces oxygen vacancies in the oxide layer. As soon as oxidation to Cu II becomes dominant, the dissolution proceeds to soluble Cu II species. The outer surface of copper under these conditions is hence a Cu 2 O-like surface, with Cu II complexes present in solution.

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Kinetics of passivation and pitting corrosion of polycrystalline copper in borate buffer solutions containing sodium chloride

Cited by 125 publications

References 25 publications

Impedance Studies of Copper in Alkaline Solutions, Especially During Electroless Plating

Impedance Studies of Copper in Alkaline Solutions, Especially During Electroless Plating

Pitting Corrosion of Some α‐Brasses in Neutral and Alkaline Solutions Containing Halide Ions

State of the Surface of Antibacterial Copper in Phosphate Buffered Saline

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