D318
Journal of The Electrochemical Society, 159 (5) D310-D318 (2012)
deposited with the current densities lower than the diffusion limiting
References
−
2
one (j
d
≈ 12.0 mA cm , Fig. 8) onto Ni electrode. At the highest
−2
1. S. C. Britton and R. M. Angels, J. Electrodep. Tech. Soc., 27, 293 (1951).
. S. A. M. Rafaey, F. Taha, and T. H. A. Hasanin, Electrochim. Acta, 51, 2942 (2006).
3. G. C. Wilson, Trans. Inst. Met. Finish., 50, 109 (1972).
4. S. K. Jalota, Metal Finish., 99, 320 (2001).
. H. Jimenez, L. Gil, M. H. Staia, and E. S. Puchi-Cabrera, Surf. Coat. Technol., 202,
072 (2008).
current density of −20 mA cm (which is not much higher than the
diffusion limiting one) the deposit is rough, as shown in Fig. 11b.
Accordingly, the current efficiencies for samples (1), (2) and (3) are
higher than that for sample (4) (Table III). As shown in Table III the
composition of samples (1)–(3) is uniform all over the cross–section
2
5
2
6
. H. P. Zhao, C. Y. Jiang, X. M. He, J. G. Ren, and C. R. Wan, Electrochim. Acta, 52,
(
very similar composition is detected at all spectra positions), while
7820 (2007).
for sample (4) the composition changes with the deposit thickness.
The amount of Ni close to the substrate surface is higher than that at
the surface of the deposit and consequently the amount of Sn increases
over the cross–section (Fig. 11b) of sample (4). Taking into account
that simultaneous hydrogen evolution occurs during the deposition
of sample (4) it is possible that either intensive convection or local
increase of the pH in the vicinity of the electrode surface produce the
change of the Ni–Sn alloy composition over the cross–section of the
deposit.
7. J. Hassoun, S. Penero, and B. Scrosati, J. Power Sources, 160, 1336 (2006).
. F. S. Ke, L. Huang, H. H. Jiang, H. B. Wei, F. Z. Yang, and S. G. Sun, Electrochem.
8
Comm., 9, 228 (2007).
9
. J. Hassoun, S. Penero, P. Simon, P. L. Taberna, and B. Scrosati, Adv. Mater., 19, 1632
(2007).
10. D. Zhang, C. Yang, J. Dai, J. Wen, L. Wang, and C. Chen, Trans. Nonferrous Met.
Soc. China, 19, 1489 (2009).
1
1
1. J. A. Augis and J. E. Bennet, J. Electrochem. Soc., 125, 330 (1978).
2. E. W. Brooman, Metal Finish., 99, 100 (2001).
13. M. B. F. Santos, E. Peres Da Silva, R. Andrade Jr., and J. A. F. Dias, Electrochim.
Acta, 37, 29 (1992).
1
4. H. Yamashita, T. Yamamura, and K. Yoshimoto, J. Electrochem. Soc., 140, 2238
Since the Ni–Sn alloy coatings could be good catalyst for hydro-
13,14
(1993).
gen evolution,
our further research will be focused on the influ-
1
5. A. G. Gray, Modern Electroplating, p. 387, John Willy & Sons, Inc., New York
ence of chemical composition, phase composition and morphology
of electrodeposited Ni–Sn alloy coatings on the hydrogen evolution
reaction.
(1953).
16. J. W. Cuthberton, in Tin and Its Alloys, E. S. Hedges, Editor, p. 99, Edward Arnold
Ltd., London (1960).
1
1
1
7. F. A. Lowenheim, Electroplating, p. 307, McGraw-Hill Book Company, New York
(1978).
8. J. I. Duffy, Electroplating Technology-Recent Developments, p. 92, Noyes Data Cor-
poration, Park Ridge, New Jersey (1981).
9. J. W. Price, Tin and Tin Alloy Plating, p. 5, Electrochemical Publications Ltd., Ayr,
Scotland (1983).
Conclusions
From the results of Sn electrodeposition in the pyrophosphate so-
lution recorded at different substrates (Ni, GC), it could be concluded
that the process of Sn electrodeposition on both electrodes commences
at −0.90 V. Deposit is characterized by the presence of isolated 3D
rectangular crystals growing perpendicular to the electrode surface
with no overlapping between them onto GC substrate. The deposit
obtained at the Ni electrode is denser on most of the surface, but at
the certain part of the surface isolated 3D rectangular crystals could
be detected. It is shown that 3D nucleation and growth of Sn onto GC
electrode does not fit any theoretically predicted model. In the pres-
ence of Ni ions in the pyrophosphate/glycine solution the Ni–Sn alloy
deposition commences at about −0.96 V onto Ni electrode produc-
ing thick and compact Ni–Sn alloy coating of different composition
depending on the applied current density/potential. The Ni–Sn alloy
deposit obtained onto GC electrode is characterized by the presence
of isolated 3D crystals with no overlapping between them at the cer-
tain part of the electrode surface and denser deposit with overlapping
between 3D crystals on the rest of the surface, with the ball–like shape
of the Ni–Sn alloy crystals.
2
2
0. A. He, Q. Liu, and D. G. Ivey, J. Mater. Sci: Mater. Electron., 19, 553 (2008).
1. B. Neveu, F. Lallemand, G. Poupon, and Z. Mekhalif, Appl. Surf. Sci., 252, 3561
(2006).
22. N. M. Martyak and R. Seefeldt, Electrochim. Acta, 49, 4303 (2004).
23. V. I. Kravtsov and V. V. Kondratiev, Electrochim. Acta, 36, 421 (1991).
24. V. V. Kondratiev and V. I. Kravtsov, EIektrokhimiya, 18, 1502 (1982).
25. V. V. Kondratiev and V. I. Kravtsov, Elektrokhimiya, 23, 1118 (1987).
26. V. I. Kravtsov, V.-V. Kondratiev, and I. Ya. Tur’yan, Elektrokhimiya, 24, 1157 (1988).
27. J. A. Daen, Lange’s Handbook of Chemistry, 15th Edition, McGraw-Hill Inc., New
York (1999).
28. J. R. Duffield, D. R. Williams, and I. Kron, Polyhedron, 10, 377 (1991).
29. I. Ya. Turyan, V. I. Kravtsov, and V. V. Kondratev, Elektrokhimiya, 22, 1388;1618
(
1986).
30. V. V. Orekhova, F. K. Andryuschenko, and N. D. Sakhnenko, Elektrokhimiya, 16,
304 (1980).
1
31. P. Djurdjevic and D. Djokic, J. Inorg. Biochem., 62, 17 (1996).
32. C. Han, Q. Liu, and D. G. Ivey, Electrochim. Acta, 53, 8332 (2008).
33. E. Budevski, G. Staikov, and W. J. Lorenz, Electrochemical Phase Formation and
Growth, in Advances in Electrochemical Science and Engineering, R. C. Alkire, H.
Gerischer, D. M. Kolb, and C. W. Tobias, Editors, VCH, Weinheim, New York, Basel,
Cambridge, Tokyo (1996).
3
4. M. Fleischmann and H. R. Thirsk, in Advances in Electrochemistry and Electrochem-
ical Engineering, p. 123, P. Delahay, Editor, Wiley, New York (1963).
5. J. A. Harrison and H. R. Thirsk, in Electroanalytical Chemistry, p. 67, A. J. Bard,
Editor, Marcel Dekker, New York (1971).
3
3
3
3
3
4
6. G. J. Hills, D. J. Schiffrin, and J. Thompson, Electrochim. Acta, 19, 657 (1974).
7. D. Kashchiev and K. Milchev, Thin Solid Films, 28, 189 (1975).
8. B. Scharifker and G. Hills, Electrochim. Acta, 28, 879 (1983).
9. G. Hills, A. K. Pour, and B. Scharifker, Electrochim. Acta, 28, 891 (1983).
0. C. Han, Q. Liu, and D. G. Ivey, Electrochim. Acta, 54, 3419 (2009). ubaciti
Acknowledgments
The authors are indebted to the Ministry of Education and Science
of the Republic of Serbia (Project No. 172054) for the financial support
of this work.
41. V. D. Jovi c´ and N. To sˇ i c´ , J. Electroanal. Chem., 441, 69 (1998).