H.G. de Melo

EIS and microstructural characterization of artificial nitrate patina layers produced at room temperature on copper and bronze

Artificial patina layers are often used to give final appearance and also to restore damaged old copper and bronze surfaces. The main inconvenient of this process is that it frequently requires surface heating or total immersion of the metallic object in the patina solution, which is sometimes impossible to accomplish, mainly with big outdoor exposed objects or ancient artefacts. In the present investigation the corrosion behaviour in NaCl solution of bare copper and bronze was compared with the response exhibited by samples of these metals covered with two different artificial nitrate-based patinas obtained at room temperature by dabbing a soaked cotton swab above their surfaces. The electrochemical techniques used to assess the response of the samples were electrochemical impedance spectroscopy (EIS) and anodic polarization curves. The anodic polarization responses have shown that, for short immersion times, the presence of the patina layer does not change the corrosion mechanism of the samples, which seems, as proposed in the literature, to be dominated by the diffusion of a soluble Cu complex to the bulk of the solution. However, EIS diagrams have evidenced differences between the responses of the bare and patina-treated samples. While in the formers the diagrams exhibited a low frequency diffusion controlled phenomenon, in the latter the response is dependent of the structure of the patina layers. Moreover, EIS response have indicated differences between the corrosion behaviour of the samples treated with the different patina solutions, which were not evidenced by the anodic polarization curves, but which are in accordance with the microstructural features revealed by SEM images.

Local electrochemical investigation of copper patina

The patination of copper is known for its complexity and heterogeneous formation. For a deeper investigation, a locally resolved surface analysis was considered. An exact determination of the accessed area and a potentiostatic control in a three-electrode configuration was reached with the use of the electrochemical microcell technique, which enables local electrochemical measurement such as local electrochemical impedance spectroscopy and cyclic voltammetry. Such a technique provides a unique way for performing the investigation of heterogeneities on electrode surfaces. The local electrochemical measurements on the artificially patinated surface have allowed distinguishing areas of different reactivity even when the analysis of the surface revealed a homogenous chemical composition of patina. Local measurements with the electrochemical microcell showed the presence of small defects on the patina layer that can be modelled by considering a hemispherical diffusion process at small active areas surrounded by larger less reactive domains.

Corrosion of Pure Aluminium in Organic Acid Media in the Presence and in the Absence of Chloride Ions: Mass Transport Effects

The influence of mass transport on the corrosion behaviour of pure aluminium in 0.75% citric acid solution in the presence and in the absence of 104 ppm of chloride ions under anodic and cathodic polarisation was investigated with a rotating disk electrode and using electrochemical impedance spectroscopy. For anodically polarised electrodes, the impedance diagrams are composed of a high frequency (HF) capacitive loop followed by a low frequency (LF) inductive loop, whose shape and size are modified neither with immersion time nor with rotation speed. Addition of chloride ions causes a diminution of the diameter of the HF capacitive loop while the influence on the inductive loop cannot be clearly detected due to data scattering. Under conditions of cathodic polarisation, the diagrams present the shape described above, however, the diameter of both loops decreases with immersion time and electrode rotation speed.

Assessment of the Corrosion Behavior of Nd-Fe-B Magnets used in Dentistry

Permanent magnets based on intermetallic compounds are employed in dentistry to fix dental prosthesis. However, these materials are very sensitive to corrosion. In this study the corrosion behavior of a sintered commercial Nd-Fe-B magnet has been investigated at neutral pH in a phosphate buffered solution (PBS). With this aim demagnetized specimens were immersed in the test solution and their corrosion behavior were monitored at increasing test times by means of electrochemical impedance spectroscopy ( EIS ), potentiodynamic polarization curves and surface observation by scanning electron microscopy ( SEM ). Experimental results indicated that the corrosion resistance is seriously affected in this solution. Moreover, no decrease in the intensity of the corrosive attack was verified during test periods of up 4 hours. Impedance results have indicated the occurrence of diffusion controlled phenomenon, likely linked to the presence of pores in the magnet microstructure.

An Investigation on the Corrosion Behaviour of Nd-Fe-B Magnets in a Chloride Solution

In this study, the corrosion behaviour of a sintered commercial Nd-Fe-B magnet has been investigated in naturally aerated and deaerated 3.5 (m/v)% sodium chloride solutions. Magnetized specimens were used in this investigation. The corrosion behaviour of the specimens was monitored at increasing test times by means of electrochemical impedance spectroscopy (EIS). Potentiodynamic polarization curves and surface observation by scanning electron microscopy (SEM), were also carried out after 30 days of immersion in the test solutions. Experimental results indicated that the corrosion resistance was affected by aeration of the solution. The corrosive attack penetrates deeply into the specimens and, consequently, the magnetic properties decreased with immersion time. The magnetic properties most influenced by corrosion were the remanence (Br) and the maximum energy product (BHmax), both presenting a reduction corresponding to 6%, after 30 days of immersion.