Estudo espectroeletroquímico e eletroanalítico de banhos de eletrodeposição de ligas prata-cobre e prata-zinco e caracterização morfológica, química e estrutural dos filmes

Abstract

The purpose of this thesis was to establish the conditions for silver-copper and silver-zinc electrodeposition from ammonium hydroxide and thiourea solutions, respectively, and to investigate the effect of added EDTA and HEDTA on the electrodeposition process. In this way, the influence of solution composition and electrodeposition parameter (deposition potential, deposition charge density, and deposition current density) on the electrodeposition process of silver-copper and silver-zinc was investigated. Relation between chemical species in solution and the reactions at the cathode/solution interface was established. It was verified that the formation of silver(I) complexes with ammonia or thiourea shifted the silver deposition potential to more negative value. As a result, the codeposition of silver and copper or silver and zinc was facilitated. On the other hand, EDTA and HEDTA acted as inhibitor of dendritic growth. This inhibition was attributed to EDTA and HEDTA adsorption on the platinum surface and growth sites of the electrodeposit, which decreased the current density of the charge transfer process. The silver-copper electrodeposit composition was a function of solution composition and electrodeposition parameter. On the other hand, the silver-zinc electrodeposit composition was almost constant, irrespective of the electrodeposition condition. Besides, the silver-copper electrodeposit was amorphous and composed by a mixture of silver, copper and silver-copper supersaturated solid solution. Sulphur was incorporated into the silver-zinc electrodeposit due to alkaline hydrolysis of thiourea in the cathode/solution interface. The silver-zinc electrodeposit was amorphous due to sulphur incorporation.