Influence of additives on the electrodeposition of zinc from a deep eutectic solvent

The effects of nicotinic acid (NA), boric acid (BA) and benzoquinone (BQ) on the electrodeposition of Zn have been studied in a choline chloride (ChCl) ethylene glycol (EG) based deep eutectic solvent (DES), (1ChCl:2 EG), and for the first time a bright zinc coating has been achieved when NA was used. In metal electroplating processes, small-molecule additives are often included in the plating bath to improve properties of coating such as brightness, roughness, thickness, hardness and resistance to corrosion. The effects of additives on the electrodeposition of Zn from aqueous solution have been extensively investigated. However, very few studies have considered the effects of additives on the electrodeposition of Zn from ionic liquids or deep eutectic solvents. The electrochemical properties of the plating liquid have been studied here using cyclic voltammetry, chronocoulometry, chronoamperometry and microgravimetry (EQCM). Redox peak currents decrease when additives were included in the Zn solution and total charge was also reduced in experiments where additives were present. The Zn deposition in the absence of additive is in good agreement with an instantaneous growth mechanism at short experimental time scales (being indeterminate over longer periods), however, this changes to one of a progressive growth mechanism when additives were included in the coating bath. The current efficiency of zinc deposition in the DES without additives was 95%, which was reduced when additives were included. The resultant surface morphologies, thickness, topography, roughness and crystal structure of the Zn coating were revealed by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD), demonstrating that those additives serve as effective brighteners that can produce highly uniform and smooth zinc deposits

Detailed investigation of zinc coating behaviours in various deep eutectic solvents

Determining the optimum conditions of a metal coating is significant for its possible applications in many fields. The present work described the electrodynamic process of zinc coating from six different deep eutectic solvents (DESs), especially type-III DES systems prepared with a quaternary ammonium salt and hydrogen bond type. Non-reversible processes without oxidation were found in DES systems prepared with choline chloride and zinc nitrate salts, and also, propylene glycol and zinc nitrate salts, termed as type-II and type-IV, respectively. The most attracted type-III DES prepared by a mixture of 1 molar choline chloride and 2 molar ethylene glycols, commercially known as Ethaline (E200), were examined for its electronucleation and possible reactions for zinc electrodeposition. For the first time, the Pt working electrode was investigated under high-resolution optical microscopy to visualize the in-situ morphology change during oxidation and reduction in E200. Furthermore, the morphological change during the anodic dissolution of zinc was also investigated in situ under a high-resolution microscope. It was found that insoluble species forming during anodic dissolution blocks the surface. Bulk electrolysis was performed in these solvents to investigate the formed zinc nucleates' morphological differences. XRD analysis was performed to differentiate the crystal planes of each deposition obtained from six DESs. It was found that the type-II and type-IV DESs consisting of zinc nitrates revealed zinc hydroxy nitrate dominated zinc deposition, which can be helpful in various applications