Abstract
A comparison between the experimental process parameters employed for the pulse plating of nanocrystalline nickel and the solution-side mass transfer and electrokinetic characteristics has been carried out. It was found that the experimental process parameters (on-time, off time and cathodic pulse current density) for cathodic rectangular pulses are consistent and within the physical constraints (limiting pulse current density, transition time, capacitance effects and integrity of the waveform) predicted from theory with the adopted postulates. This theoretical analysis also provides a means of predicting the behaviour of the process subject to a change in the system, kinetic and process parameters. The product constraints (current distribution, nucleation rate and grain size), defined as the experimental conditions under which nanocrystalline grains are produced, were inferred from electrocrystallization theory. High negative overpotential, high adion population and low adion surface mobility are prerequisites for massive nucleation rates and reduced grain growth; conditions ideal for nanograin production. Pulse plating can satisfy the former two requirements but published calculations show that surface mobility is not rate-limiting under high negative overpotentials for nickel. Inhibitors are required to reduce surface mobility and this is consistent with experimental findings. Sensitivity analysis on the conditions which reduce the total overpotential (thereby providing more energy for the formation of new nucleation sites) are also carried out. The following lists the effect on the overpotential in decreasing order: cathodic duty cycle, charge transfer coefficient, Nernst diffusion thickness, diffusion coefficient, kinetic parameter (γ) and exchange current density.
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Abbreviations
- A :
-
constant employed in Fig. 8, (αnFi0)/(RT e C a)(s−1)
- B :
-
constant in Equation 38 (V2)
- C :
-
cation concentration (molcm−3)
- C a :
-
capacitance of double layer (µFcm−2)
- C s :
-
cation surface concentration (molcm−3)
- C *s :
-
dimensionless cation surface concentration, C s/C ∞(−)
- C ∞ :
-
cation bulk concentration (molcm−3)
- D :
-
diffusion coefficient of cation (cm2s−1)
- ΔE :
-
total applied potential (V)
- ΔE 0 :
-
standard cell potential (V)
- F :
-
Faraday constant (Cmol−1)
- ℱ:
-
function defined in Appendix C(−)
- Fr :
-
frequency of waveform (Hz)
- f i,p :
-
function defined in Appendix C for pth period (−)
- f i,∞ :
-
function defined in Appendix C for p → ∞ period (−)
- G j :
-
function defined in Appendix B (−)
- gi :
-
function defined in Appendix B (−)
- i :
-
current density (Acm¨)
- i ac :
-
unsteady fluctuating a.c. current density (Acm−2)
- i c :
-
capacitance current density (Acm−2)
- i dc :
-
steady time-averaged d.c. current density (Acm−2)
- i F :
-
Faradaic current density (Acm−2)
- i lim :
-
limiting d.c. current density (Acm−2)
- i 0 :
-
exchange current density (Acm−2)
- i PL :
-
limiting pulse current density, i 1{Cs = 0 at t = (p − 1) T + t 1(Acm−2)
- i 1 :
-
cathodic pulse current density (Acm−2)
- i 2 :
-
relaxed or low current pulse current density (Acm−2)
- iin:
-
anodic pulse current density (Acm−2)
- i * :
-
dimensionless current density, i/|i lim| (−)
- i *0 :
-
dimensionless exchange current density, i dc/|i lim| (−)
- i *dc :
-
dimensionless steady time-averaged d.c. current density, i dc/|i lim| (−)
- i *PL :
-
dimensionless limiting cathodic pulse current density, i PL/|i lim| (−)
- i *PL,p :
-
dimensionless limiting pulse current density at pth period, i 1(C s = 0)/|i lim| (−)
- i *PL,∞ :
-
dimensionless limiting pulse current density for p → ∞, i 1(C s = 0)/|i lim| (−)
- i *1 :
-
dimensionless cathodic pulse current density, i 1/|i lim| (−)
References
H. Gleiter, Prog. Mat. Sci. 33 (1989) 223.
G. Herzer, Mat. Sci. Eng. A133 (1991) 1.
S. J. Thorpe, B. Ramaswami and K. T. Aust, J. Electrochem. Soc. 135 (1988) 2162.
K. Boylan, D. Ostrander, U. Erb, G. Palumbo and K. T. Aust, Scripta Metall. Mater. 25 (1991) 2711.
R. W. Siegel and H. Hahn, ‘Nanophase Materials: Current Trends in Physics of Materials’ (edited by M. Youssef), World Scientific Publications, Singapore (1988).
J. Karch, R. Birringer and H. Gleiter, Nature 330 (1987) 556.
G. McMahon and U. Erb, J. Mater. Sci. Lett. 8 (1989) 865.
A. M. EI-Sherik and U. Erb, ‘Production of nanocrystalline metals’, US Patent Allowed 07/983205 (1992).
M. Cherkaoui, E. Chassaing and K. Vu Quang, Surf. Coat. Technol. 34 (1988) 242.
N. Ibl, Surf. Technol. 10 (1980) 81.
K. I. Popov, M. D. Maksimovic, B. M. Ocokoljie and B. J. Lazarevic, ibid. 11 (1980) 99.
K. Hosokawa, J. C. Puippe and N. Ibl, Proceedings of the World Congress on Met. Finish, 10th, Interfinish 80, Met. Soc. of Japan, Tokyo (1980) pp. 59–62.
N. Ibl, J. Cl. Puippe and H. Angerer, Surf. Technol. 6 (1978) 287.
D. T. Chin, R. Sethi and J. McBreen, J. Electrochem. Soc. 129 (1982) 2677.
J. Cl. Puippe and N. Ibl, Plating Surf. Finish. 67 (1980) 68.
M. G. Pavlovic, M. D. Maksimovic and K. I. Popov, J. Appl. Electrochem. 8 (1978) 61.
O. Chène and D. Landolt, ibid. 19 (1989) 188.
J. O'M. Bockris and A. K. N. Reddy, ‘Modern Electrochemistry’, vol. 2, Plenum Press, New York (1970) pp. 1173–1231.
J. O'M. Bockris and A. Damjanovic, The Mechanism of the Electrodeposition of Metals, in ‘Modern Aspects of Electrochemistry’, vol. 3, (edited by J. O'M. Bockris and B. E. Conway), Butterworth, London (1964) pp. 224–346.
J. O'M. Bockris and G. A. Razumney, ‘Fundamental Aspects of Electrocrystallization’, Plenum Press, New York (1967) pp. 27–38.
D.-T. Chin and S. Venkatesh, J. Electrochem. Soc. 128 (1981) 1439.
G. Holmbom and B. E. Jacobson, ibid. 135 (1988) 2720.
J. O'M. Bockris and B. E. Conway (eds), op. cit. [19], p. 279.
M. Y. Abyaneh and M. Fleischmann, J. Electrochem. Soc. 139 (1991) 2491.
E. B. Budevski, Deposition and Dissolution of Metals and Alloys. Part A: Electrocrystallization, in ‘Comprehensive Treatise of Electrochemistry’, vol. 7, (edited by B. E. Conway, J. O'M. Bockris, E. Yeager, S. U. M. Khan and R. E. White), Plenum Press, New York (1983) pp. 399–450.
W. Kim and R. Weil, Surf. Coat. Technol. 38 (1989) 289.
W. Kossel, Nachr. Ges. Wiss. Göttinger, Math. Physik. Kl. (1929) 135.
I. N. Stranski, Z. Physik. Chem. Leipzig 136 (1928) 259.
D. L. Rehrig, Plating 61 (1974) 43.
N. V. Parthasaradhy, ‘Practical Electroplating Handbook’, Prentice Hall, Englewood Cliffs, NJ (1989).
D. T. Chin, J. Electrochem. Soc. 130 (1983) 1657.
Yu G. Silver, Zh. Fiz. Khim. 34 (1960) 577.
J. M. Hale, J. Electroanal. Chem. 6 (1963) 187.
N. Osero, Pulse plating equipment, in ‘Theory and Practice of Pulse Plating’, (edited by J. Cl. Puippe and F. Leaman), AESF, Orlando, FA (1986) pp. 221–228.
T. R. Rosebrugh and W. L. Miller, J. Physical Chem. 14 (1910) 816.
D. Landolt, Mass transport in pulse plating, in ‘Theory and Practice of Pulse Plating’, (edited by J. Cl. Puippe and F. Leaman), AESF, Orlando, Florida (1986) pp. 55–71.
S. Venkatesh, M. Meyyappan and D.-T. Chin, J. Colloid & Interf. Sci. 85 (1982) 216.
S. Sethi and D.-T. Chin, J. Electroanal. Chem. 160 (1984) 79.
J. Cl. Puippe and N. Ibl, J. Appl. Electrochem. 10 (1980) 775.
J. Cl. Puippe, Influence of charge and discharge of double layer in pulse plating, in ‘Theory and Practice of Pulse Plating’, (edited by J. Cl. Puippe and F. Leaman), AESF, Orlando, FA (1986) pp. 41–54.
C. M. Gilmore and J. A. Sprague, ‘Molecular dynamics simulations of thin film nanostructures’, 1993 TMS AIME Annual General Meeting, Denver, paper in session on nanocrystalline materials.
J. Cl. Puippe, Qualitative approach to pulse plating, in ‘Theory and Practice of Pulse Plating’, (edited by J. Cl. Puippe and F. Leaman), AESF, Orlando, FA (1986) pp. 1–15.
M. Fleischmann and H. R. Thirsk, Metal deposition and electrocrystallization, in ‘Advances in Electrochemistry and Electrochemical Engineering’, (edited by P. Delahay and C. W. Tobias), Interscience, New York (1963) pp. 123–210.
J. O'M. Bockris and G. A. Razumney, op. cit. [20], pp. 51–53.
Idem, op. cit. [20], p. 38.
B. E. Conway and J. O'M. Bockris, Electrochim. Acta 3 (1961) 340.
O. Dossenbach, Current distribution in pulse plating, in ‘Theory and Practice of Pulse Plating’, (edited by J. Cl. Puippe and F. Leaman), AESF, Orlando, FA (1986) pp.73–92.
D.-T. Chin and S. Venkatesh, J. Electrochem. Soc. 128 (1981) 1439.
E. B. Budevski, op. cit. [25], p. 441.
A. J. Arvia and D. Posadas, Nickel, in ‘Encyclopaedia of Electrochemistry of the Elements’, vol. 3, (edited by A. J. Bard), Marcel and Dekker, New York (1975) pp. 211–421.
N. Tanaka and R. Tamamushi, Electrochim. Acta 9 (1964) 963.
J. Y. Wang, D. Balamurugan and D.-T. Chin, J. Appl. Electrochem. 22 (1992) 240.
S.-C. Yen and T. W. Chapman, Chem. Eng. Comm. 38 (1985) 159.
M. Datta and D. Landolt, Electrochim. Acta 26 (1981) 899.
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Choo, R.T.C., Toguri, J.M., El-Sherik, A.M. et al. Mass transfer and electrocrystallization analyses of nanocrystalline nickel production by pulse plating. J Appl Electrochem 25, 384–403 (1995). https://doi.org/10.1007/BF00249659
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DOI: https://doi.org/10.1007/BF00249659