<p class="PaperAbstract"><span lang="EN-US">The voltammetry induced growth of tin oxides on tin in the buffer solution of 0.18 mol L<sup>-1</sup> Na<sub>2</sub>H<sub>2</sub>PO<sub>4</sub> and 0.18 mol L<sup>-1</sup> KH<sub>2</sub>PO<sub>4</sub> (pH 8.7) has been studied. Ex-situ ellipsometric measurements were made in an order to determine thicknesses of the grown oxides. From these results the film volume per charge unit, </span><span lang="EN-US">V</span><sub><span lang="EN-US">f</span></sub><span lang="EN-US">, was calculated for different charge densities of the film. This parameter was used to calculate the variable ionic resistivity of the film, </span><span lang="EN-US">ρ</span><sub><span lang="EN-US">f</span></sub><span lang="EN-US">, considered by the Ohmic model for the case of voltammetric growth of oxides on metals having a previously existing continuous film. Tin oxide films grown at 2 mV s<sup>-1</sup> showed to be less dense for values of charge density below 50 C m<sup>-2</sup>, having </span><span lang="EN-US">V</span><sub><span lang="EN-US">f</span></sub><span lang="EN-US"> near <br /> 5.7x10<sup>-10</sup> m<sup>3</sup> C<sup>-1</sup>. For higher values of charge density, tin oxide films become denser, having </span><span lang="EN-US">V</span><sub><span lang="EN-US">f</span></sub><span lang="EN-US"> near 0.5x10<sup>-10</sup> m<sup>3</sup> C<sup>-1</sup>. The calculated values of the variable ionic resistivity of the film during voltammetric growth showed that </span><span lang="EN-US">ρ</span><sub><span lang="EN-US">f</span></sub><span lang="EN-US"> passes through a minimum (justifying the maximum in current densities). This behavior was also found by other authors in the cases of Zn, Nb, Ni and galvanized steel sheets.</span></p>
No presente trabalho foi desenvolvida uma metodologia para obter-se reprodutibilidade da área superficial de um eletrodo de estanho durante o estudo do crescimento de óxidos de estanho em soluções tampão borato e fosfato, pH 8,7. Para isto, o tratamento superficial anterior a cada crescimento voltamétrico anódico do óxido de estanho foi realizado a potencial catódico na mesma solução a – 1,2 V durante 10 minutos. A reprodutibilidade da área superficial pode ser comprovada pela reprodutibilidade das densidades de carga anódicas dos voltamogramas anódicos a 50 mVs-1 posteriores a cada tratamento.
The aim of this study was to verify the applicability of the Ohmic Model with variable ionic resistivity to the voltammetric zinc oxide growth on galvanized steel sheets, without chromate passivating film. Two kind of galvanized steel sheets were studied: one produced from a bath of molten zinc containing antimony and the other containing lead. The galvanized steel sheets produced from a bath containing Sb presented better performance against corrosion in comparison on with those produced from a bath containing Pb. The electrochemical experiments were performed in a buffer solution of pH 8.7 with of 0.3 mol L-1 H3BO3 plus 0.15 mol L-1 Na2B4O7. It was found that the passivating zinc oxide grown on the galvanized steel sheet containing Sb showed higher ionic resistivity than that of the galvanized sheet containing Pb. This can explain the corrosion results.
O crescimento voltamétrico de óxido de estanho em solução tampão fosfato, pH 8,7 foi estudado. Medidas elipsométricas ex-situ foram realizadas para determinar a espessura dos óxidos crescidos. A partir desses resultados, o volume do filme por unidade de carga, Vf , foi calculado para diferentes densidades de carga. As medidas elipsométricas mostram que filmes de óxido de estanho crescidos a 2 mVs-1 são menos densos para valores de espessura 3,37 nm, tendo Vf próximo a 1,70 x 10-4 cm3 C-1. Para valores mais altos de espessura (11,0 – 12,4 nm) os filmes se tornam mais densos tendo Vf próximo a 0,5 x 10-4 cm3 C-1. No caso de 100 mVs1 os filmes apresentam o mesmo comportamento, tendo Vf próximo de 3,74 x 10-4 cm3 .C-1 para espessura de 4,56 nm e Vf próximo de 1,32 x 10-4 cm3 .C-1 para espessura de 7,42 nm. Imagens de Microscopia de Força Atômica mostraram que a morfologia muda e a rugosidade dos filmes aumenta com o aumento da espessura e do potencial final da voltametria.
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