Abstract
A characteristic of obtaining metal powders by direct current electrolysis is changes in the morphology of particles over the loose deposit layer thickness up to the formation of large spherulites. Deposits should be periodically removed from the cathode in order to obtain a powder with homogeneous composition. This paper justifies the choice of the parameter describing the change in loose deposit properties and proposes a method for determining the periodicity of its removal from the cathode. Loose zinc deposits were obtained at 25°C from zincate electrolyte containing 0.3 mol L–1 of ZnO and 4 mol L–1 of NaOH at a current setpoint exceeding six times the limiting diffusion current calculated using the smooth electrode. Electrode potential, deposit thickness and evolved hydrogen volume were measured directly in the process of electrolysis. Current redistribution between the metal reduction and hydrogen evolution leads to a change in the structure of loose deposit particles. It is shown that the differential current efficiency of zinc is the parameter describing the change in the loose zinc deposit density. Its value should not exceed 0.96, in order to ensure deposition of loose deposit with homogeneous properties. A further increase in current efficiency will lead to the formation of aggregates at the deposit growth front. It is proposed to determine the periodicity of loose deposit removal from the cathode using the empirical equation for the time dependency of differential current efficiency of zinc. The mathematical and statistical analysis of the data obtained in six replicates was carried out. The interval approach made it possible to significantly narrow the range of permissible differential current efficiency values and, as a consequence, to determine empirical equation coefficients with acceptable accuracy and calculate the growth time period of a deposit with homogeneous structure. The obtained approach can be used to estimate the time period of loose metal deposition accompanied by hydrogen evolution.
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REFERENCES
Neikov, O.D., Naboychenko, S.S., and Yefimov, N.A., Handbook of Non-Ferrous Metal Powders: Technologies and Applications, Elsevier, 2019. https://doi.org/10.1016/C2014-0-03938-X
Petrii, O.A., Electrosynthesis of nanostructures and nanomaterials, Russ. Chem. Rev., 2015, vol. 84, no. 2, pp. 159–193. https://doi.org/10.1070/RCR4438
Antsiferov, V.N., Bobrov, G.V., and Druzhinin, L.K., Poroshkovaya metallurgiya i napylennye pokrytiya (Powder Metallurgy and Sputtered Coatings), Moscow: Metallurgiya, 1987.
Mattarozzi, L., Cattarin, S., Comisso, N., Gambirasi, A., Guerriero, P., Musiani, M., Vázquez-Gómez, L., and Verlato, E., Hydrogen evolution assisted electrodeposition of porous Cu–Ni alloy electrodes and their use for nitrate reduction in alkali, Electrochim. Acta, 2014, vol. 140, pp. 337–344. https://doi.org/10.1016/j.electacta.2014.04.048
Shin, H.-C. and Liu, M., Three-dimensional porous copper-tin alloy electrodes for rechargeable lithium batteries, Adv. Funct. Mater., 2005, vol. 15, pp. 582–586. https://doi.org/10.1002/adfm.200305165
Blake, J.P., Lathe, A.J., and Suresh, K.B., Building with bubbles: the formation of high surface area honeycomb-like films via hydrogen bubble templated electrodeposition, Chem. Commun., 2015, vol. 51, pp. 4331–4346. https://doi.org/10.1039/C4CC06638C
Ullah, S., Badshah, A., Ahmed, F., Raza, R., Altaf, A.A., and Hussain, R., Electrodeposited zinc electrodes for high current Zn/AgO bipolar batteries, Int. J. Electrochem. Sci., 2011, no. 6, pp. 3801–3811.
Mojtahedi, M., Goodarzi, M., Sharifi, B., and Khaki, J.V., Effect of electrolysis condition of zinc powder production on zinc-silver oxide battery operation, Energy Convers. Manage., 2011, vol. 52, no. 4, pp. 1876–1880. https://doi.org/10.1016/j.enconman.2010.11.001
Nekouei, R.K., Rashchi, F., and Amadeh, A.A., Using design of experiments in synthesis of ultra-fine copper particles by electrolysis, Powder Technol., 2013, vol. 237, pp. 165–171. https://doi.org/10.1016/j.powtec.2013.01.032
Nekouei, R.K., Rashchi, F., and Ravanbakhsh, A., Copper nano-powder synthesis by electrolysis method in nitrate and sulfate solutions, Powder Technol., 2013, vol. 250, pp. 91–96. https://doi.org/10.1016/j.powtec.2013.10.012
Nikolić, N.D., Vaštag, D.D., Živković, P.M., Jokić, B., and Branković, G., Influence of the complex formation on the morphology of lead powder particles produced by the electrodeposition processes, Adv. Powder Technol., 2013, vol. 24, no. 3, pp. 674–682. https://doi.org/10.1016/j.apt.2012.12.008
Sharifi, B., Mojtahedi, M., Goodarzi, M., and Vahdati, K.J., Effect of alkaline electrolysis conditions on current efficiency and morphology of zinc powder, Hydrometallurgy, 2009, vol. 99, no. 1, pp. 72–76. https://doi.org/10.1016/j.hydromet.2009.07.003
Ostanina, T.N., Rudoi, V.M., Patrushev, A.V., Darintseva, A.B., and Farlenkov, A.S., Modelling the dynamic growth of copper and zinc dendritic deposits under the galvanostatic electrolysis conditions, J. Electroanal. Chem., 2015, vol. 750, pp. 9–18. https://doi.org/10.1016/j.jelechem.2015.04.031
Orhan, G. and Gezgin, J.G.G., Effect of electrolysis parameters on the morphologies of copper powders obtained at high current densities, J. Serb. Chem. Soc., 2012, vol. 77, no. 5, pp. 651–665. https://doi.org/10.1016/j.powtec.2010.03.003
Nikolić, N.D., Branković, G., and Popov, K.I., Optimization of electrolytic process of formation of open and porous copper electrodes by the pulsating current (PC) regime, Mater. Chem. Phys., 2011, vol. 125, no. 3, pp. 587–594. https://doi.org/10.1016/j.matchemphys.2010.10.013
Nikolić, N.D., Branković, G., and Pavlović, M.G., Correlate between morphology of powder particles obtained by the different regimes of electrolysis and the quantity of evolved hydrogen, Powder Technol., 2012, vol. 221, pp. 271–277. https://doi.org/10.1016/j.powtec.2012.01.014
Nikolić, N.D., Branković, G., and Maksimović, V.M., Influence of potential pulse conditions on the formation of honeycomblike copper electrodes, J. Electroanal. Chem., 2009, vol. 635, pp. 111–119. https://doi.org/10.1016/j.jelechem.2009.08.005
Pavlović, M.G., Pavlović, L.J., Maksimović, V.M., Nikolić, N.D., and Popov, K.I., Characterization and morphology of copper powder particles as a function of different electrolytic regimes, Int. J. Electrochem. Sci., 2010, vol. 5, no. 12, pp. 1862–1878.
Jagtap, R.N., Rakesh, N., Zaffar, H.S., and Malshe, V.C., Predictive power for life and residual life of the zinc rich primer coatings with electrical measurement, Prog. Org. Coat., 2007, vol. 58, no. 4, pp. 253–258. https://doi.org/10.1016/j.porgcoat.2006.08.015
Kalendová, A., Effects of particle sizes and shapes of zinc metal on the properties of anticorrosive coatings, Prog. Org. Coat., 2003, vol. 46, no. 4, pp. 324–332. https://doi.org/10.1016/S0300-9440(03)00022-5
Sokolovskaya, E.E., Osipova, M.L., Murashova, I.B., Darintseva, A.B., Savel’ev, A.M., and Mukhamadeev, F.F., Analysis of structural variations of the precipitate based on monitoring the industrial electrolysis of copper powders of various brands, Russ. J. Non-Ferrous Met., 2013, vol. 54, no. 6, pp. 497–503. https://doi.org/10.3103/S1067821213060291
Ostanina, T.N., Rudoy, V.M., Nikitin, V.S., Darintseva, A.B., and Demakov, S.L., Change in the physical characteristics of the dendritic zinc deposits in the stationary and pulsating electrolysis, J. Electroanal. Chem., 2017, vol. 784, pp. 13–24. https://doi.org/10.1016/j.jelechem.2016.11.063
Nikolić, N.D., Branković, G., Pavlović, M.G., and Popov, K.I., The effect of hydrogen co-deposition on the morphology of copper electrodeposits. II. Correlation between the properties of electrolytic solutions and the quantity of evolved hydrogen, J. Electroanal. Chem., 2008, vol. 621, no. 1, pp. 13–21. https://doi.org/10.1016/j.jelechem.2008.04.006
Nicolić, N.D., Popov, K.I., Pavlović, L.J., and Pavlović, M.G., The effect of hydrogen codeposition on the morphology of copper electrodeosits. I. The concept of effective overpotential, J. Electroanal. Chem., 2006, vol. 588, no. 1, pp. 88–98. https://doi.org/10.1016/j.jelechem.2005.12.006
Nikolić, N.D., Pavlović, Lj.J., Pavlović, M.G., and Popov, K.I., Morphologies of electrochemically formed copper powder particles and their dependence on the quantity of evolved hydrogen, Powder Technol., 2008, vol. 185, no. 3, pp. 195–201. https://doi.org/10.1016/j.powtec.2007.10.014
Yakubova, T.V. and Murashova, I.B., Modeling of electro-crystallization of loose deposits from aqueous solution. Localization of hydrogen reduction reaction and ways for its removal, Elektrokhimiya, 1995, vol. 31, pp. 463–486.
Osipova, M.L., Murashova, I.B., Darintseva, A.B., and Onuchina, D.L., Current efficiency of dendritic copper deposit for PMS11 powder as a parameter determining its structure, Gal’vanotekh. Obrab. Poverkhn., 2012, vol. 19, no. 3, pp. 35–41.
Ostanina, T.N., Rudoi, V.M., Nikitin, V.S., Darintseva, A.B., Zalesova, O.L., and Porotnikova, N.M., Determination of the surface of dendritic electrolytic zinc powders and evaluation of its fractal dimension, Russ. J. Non-Ferrous Met., 2016, vol. 57, no. 1, pp. 47–51. https://doi.org/10.3103/S1067821216010120
Diggle, J.W., Despić, A.R., and Bockris, J.O., The mechanism of the dendritic crystallization of zinc, J. Electrochem. Soc., 1969, vol. 116, no. 11, pp. 1503–1514. https://doi.org/10.1149/1.2411588
R (Recommendations) no. 40.2.028-2003: The State System for Providing Uniqueness of Measuring. Recommendations on Generating the Calibration Characteristics. Estimation of Errors (Uncertainties) of Linear Calibration Characteristics by Using the Least Square Means Method, Moscow: Goststandart, 2003.
Jaulin, L., Kieffer, M., Didrit, O., and Walter, E., Applied Interval Analysis, London: Springer, 2001.
Shary, S.P., Finite-Dimensional Interval Analysis. http:// www.nsc.ru/interval/Library/InteBooks. Accessed September 1, 2019.
Kumkov, S.I., An estimation problem of chemical process with confluent parameters: An interval approach, Reliab. Comput., 2016, vol. 22, pp. 15–25.
Kumkov, S.I. and Mikushina, Yu.V., Interval approach to identification of catalytic process parameters, Reliab. Comput., 2014, vol. 19, no. 2, pp. 197–214.
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This study was supported by the Government of the Russian Federation, regulation no. 211, state assignment no. 0836-2020-003.
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Nikitin, V.S., Ostanina, T.N., Kumkov, S.I. et al. Determination of the Growth Time Period of Loose Zinc Deposit Using Interval Analysis Methods. Russ. J. Non-ferrous Metals 61, 540–548 (2020). https://doi.org/10.3103/S1067821220050119
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DOI: https://doi.org/10.3103/S1067821220050119