Abstract
Different Zn-Mn coatings were successfully electrodeposited on copper substrates from deep eutectic solvent-based electrolytes containing boric acid as an additive. The main objective of this work was to optimize the Zn/Mn ratios and morphologies of the as-electrodeposited Zn-Mn films in order to obtain better corrosion protection performance coatings. The electrodeposition behaviors of Zn-Mn alloys as studied by cyclic voltammetry showed that with increase in electrolyte Mn(II) concentration, Zn(II) ion reduction occurs at higher overpotentials while Mn reduction occurs at lower overpotentials, and this in turn enhances Mn incorporation into the deposit. Characterization results showed that the electrodeposition potential and electrolyte Mn(II) concentration significantly affects the Mn content, crystal structure, surface morphology, and corrosion performance of the deposits. With increase in electrodeposition potential and electrolyte Mn(II) concentration, the alloy Mn increased and the grain morphology was refined. The crystal structure of Zn-Mn deposits consists of Zn and hexagonal close packed ε-phase Zn-Mn at low electrodeposition potentials and low electrolyte Mn(II) content. However, at high electrodeposition potentials and electrolyte Mn(II) contents, the crystal structure was only composed of hexagonal close packed ε-phase Zn-Mn. Corrosion measurements show that all the Zn-Mn samples have a passivating behavior and exhibits higher corrosion resistances when compared to those from aqueous solutions. Thus, optimum electrodeposition potential and electrolyte Mn(II) concentration were determined producing compact Zn-Mn films with the best corrosion resistance.
Similar content being viewed by others
References
G.D. Wilcox and D.R. Gabe, Electrodeposited Zinc Alloy Coatings, Corros. Sci., 1993, 35, p 1251–1258
D.R. Gabe, G.D. Wilcox, A. Jamani, B.R. Pearson, Zinc-Manganese Alloy Electrodeposition, Met. Finish., 1993, 91, p 34–36
G.D. Wilcox and B. Petersen, Zinc-Manganese Alloy Electrodeposition, Trans. Inst. Met. Finish., 1996, 74, p 115–118
K.N. Srinivasan, M. Selvan, and K.I.S. Venkata, Hydrogen Permeation During Zinc-Manganese Alloy Plating, J. Appl. Electrochem., 1993, 23, p 358–363
M. Sagiyama, T. Urakawa, T. Adaniya, T. Hara, and Y. Fukuda, Zinc-Manganese Alloy Electroplating on Steel Strip, Plat. Surf. Finish., 1987, 74, p 40
N. Boshkov, K. Petrov, S. Vitkova, and G. Raichevsky, Galvanic Alloys Zn-Mn—Composition of the Corrosion Products and their Protective Ability in Sulfate Containing Medium, Surf. Coat. Technol., 2005, 194, p 276–282
N. Boshkov, K. Petrov, D. Kovacheva, S. Vitkova, and S. Nemska, Influence of the Alloying Component on the Protective Ability of Some Zinc Galvanic Coatings, Electrochim Acta, 2005, 51, p 77–84
N. Boshkov, Galvanic Zn-Mn Alloys-Electrodeposition, Phase Composition, Corrosion Behavior and Protective Ability, Surf. Coat. Technol., 2003, 172, p 217–226
N. Boshkov, K. Petrov, and G. Raichevsky, Corrosion Behavior and Protective Ability of Multilayer Galvanic Coatings of Zn and Zn-Mn Alloys in Sulfate Containing Medium, Surf. Coat. Technol., 2005, 200, p 5995–6001
G. Govindarajan, V. Ramakrishnan, S. Ramamurthi, V. Subramanian, and N.V. Parthasaradhy, Electrodeposition of Zinc-Manganese Alloy Coating for Corrosion Resistant Applications, Bull. Electrochem., 1989, 5, p 422–426
T. Urakawa, M. Sagiyama, T. Adaniya, T. Hara, Corrosion-Resistance and Paintability of Zn-Mn Alloy Plated Steel Sheets, SAE Tech 860268, 1986
M. Eyraud, A. Garnier, F. Mazeron, and Crousier, Morphology and Composition of Electrodeposited Zinc-Manganese Alloys, J. Plat. Surf. Finish., 1995, 82, p 63–70
M.V. Ananth and N.V. Parthasaradhy, Magnetization Behaviour of Electrodeposited Zn-Mn Alloys, Mater. Sci. Eng., 1996, 40, p 19–23
M. Selvam and S. Guruviah, Corrosion of Electrodeposited Zinc-Manganese Alloys, Bull. Electrochem., 1990, 6, p 485–486
B. Bozzini, F. Pavan, G. Bollini, and P.L. Cavallotti, Zn-Mn Alloy Electrodeposition on Steel, Trans. Inst. Met. Finish., 1997, 75, p 175–180
B. Bozzini, F. Pavan, and P.L. Cavallotti, Experience with a Pilot Plant for the Electrodeposition of Zn-Mn on Wire, Trans. Inst. Met. Finish., 1998, 76, p 171–178
F. Soto, Electrodeposition of Zn-Mn Alloys on Steel for Corrosion Resistance, Ph.D. Thesis, Universite de Provence, Aix Marseille 1, 1998
N. Boshkov, S. Vitkova, and K. Petrov, Corrosion Products of Zn-Mn Coatings: Part I. Investigations Using Microprobe Analysis and X-Ray Diffraction, Met. Finish., 2001, 99, p 56–60
N. Boshkov, K. Petrov, and S. Vitkova, Corrosion Products of Zn-Mn Coatings: Part III. Double-protective Action of Manganese, Met. Finish., 2002, 100, p 98–102
C. Muller, M. Sarret, and T. Andreu, Electrodeposition of Zn-Mn Alloys at Low Current Densities, J. Electrochem. Soc., 2002, 149, p C600–C606
C. Muller, M. Sarret, and T. Andreu, Zn-Mn Alloys Obtained Using Pulse, Reverse and Superimposed Current Modulations, Electrochim. Acta, 2003, 48, p 2397–2404
L.D. Ballote, R. Ramanauskas, and P.B. Perez, Mn Oxide Film as Corrosion Inhibitor of Zn-Mn Coatings, Corros. Rev., 2000, 18, p 41–51
M.S. Chandrasekara and M. Shanmugasigamani, Synergetic Effects of Pulse Constraints and Additives in Electrodeposition of Nanocrystalline Zinc: Corrosion, Structural and Textural Characterization, Mater. Chem. Phys., 2010, 124, p 516–528
M. Bucko, J. Rogan, S.I. Stevanovic, S. Stankovic, and J.B. Bajat, The Influence of Anion Type in Electrolyte on the Properties of Electrodeposited Zn\Mn Alloy Coatings, Surf. Coat. Technol., 2013, 228, p 221–228
F. Endres, Ionic Liquids: Solvents for the Electrodeposition of Metals and Semi-Conductors, ChemPhysChem, 2002, 3, p 144–154
S.Z. EI Abedin, F. Endres, Electrodeposition of Metals and Semiconductors in Air- and Water-stable Ionic Liquids, ChemPhysChem, 2006, 7, p 58–61
J.F. Huang and I.W. Sun, Nonanomalous Electrodeposition of Zinc-Iron Alloys in an Acidic Zinc Chloride-1-Ethyl-3-Methylimidazolium Chloride Ionic Liquid, J. Electrochem. Soc., 2004, 151, p C8–C14
J.F. Huang and I.W. Sun, Electrochemical Studies Tin in Zinc Chloride-1-Ethyl-3-Methylimidazolium Chloride Ionic Liquids, J. Electrochem. Soc., 2003, 150, p E299–E306
M.C. Lin, P.Y. Chen, and I.W. Sun, Electrodeposition of Zinc Telluride from a Zinc Chloride-1-Ethyl-3-Methylimidazolium Chloride Molten Salt, J. Electrochem. Soc., 2001, 148, p C653–C658
P.Y. Chen and I.W. Sun, Electrodeposition of Cobalt and Zinc-Cobalt from a Lewis Acidic Zinc Chloride-1-Ethyl-3-Methylimidazolium Chloride Molten Salt, Electrochim. Acta, 2001, 46, p 1169–1177
J.F. Huang and I.W. Sun, Electrodeposition of Pt-Zn in a Lewis Acidic ZnCl2-1-Ethyl-3-Methylimidazolium Chloride Ionic Liquid, Electrochim. Acta, 2004, 49, p 3251–3258
A.P. Abbott, G. Capper, D. Davies, and R.K. Rasheed, Ionic Liquid Analogues Formed from Hydrated Metal Salts, Chem. Eur. J., 2004, 10, p 3769–3774
A.P. Abbott, K. El Ttaib, G. Grish, K.J. McKenzie, and K.S. Ryder, Electrodeposition of Copper Composites from Deep Eutectic Solvents Based on Choline Chloride, Phys. Chem. Chem. Phys., 2009, 11, p 4269–4277
R. Bock and S.E. Wulf, Electrodeposition of Iron Films from an Ionic Liquid (ChCl/urea/FeCl3 Deep Eutectic Mixtures, Trans. Inst. Met. Finish., 2009, 87, p 28–32
A. Bakkar and V. Neubert, Electrodeposition onto Magnesium in Air and Water Stable Ionic Liquids: From Corrosion to Successful Plating, Electrochem. Commun., 2007, 9, p 2428–2435
C.D. Gu, Y.H. You, Y.L. Yu, S.X. Qu, J.P. Tu Microstructure, Nanoindentation, and Electrochemical Properties of the Nanocrystalline Nickel Film Electrodeposited from Choline Chloride-Ethylene Glycol, Surf Coat. Technol., 2011, 205, p 4928–4933
C.D. Gu and J.P. Tu, Fabrication and Wettability of Nanoporous Silver Film on Copper from Choline Chloride-Based Deep Eutectic Solvents, J. Phys. Chem., 2010, 114, p 13614–13619
S. Fashu, C.D. Gu, X.L. Wang, and J.P. Tu, Influence of Electrodeposition Conditions on the Microstructure and Corrosion Resistance of Zn-Ni Alloy Coatings from a Deep Eutectic Solvent, Surf. Coat. Technol., 2014, 242, p 34–41
A.P. Abbott, G. Capper, K. Mckenzie, and K. Ryder, Electrodeposition of Zinc-Tin Alloys from Deep Eutectic Solvents Based on Choline Chloride, J. Electroanal. Chem., 2007, 599, p 288–294
P. Dale, A. Samantilleke, D. Shivagan, and L. Peter, Synthesis of Cadmium and Zinc Semiconductor Compounds from an Ionic Liquid Containing Choline Chloride and Urea, Thin Solid Films, 2007, 515, p 5751–5754
H.Y. Yang, X.W. Guo, X.B. Chen, S.H. Wang, G.H. Wu, W.J. Dingb, and N. Birbilis, On the Electrodeposition of Nickel-Zinc Alloys from a Eutectic-Based Ionic Liquid, Electrochim. Acta, 2012, 63, p 131–138
Y.H. You, C.D. Gu, X.L. Wang, and J.P. Tu, Electrodeposition of Ni-Co Alloys from a Deep Eutectic Solvent, Surf. Coat. Technol., 2012, 206, p 3632–3638
C. Savall, C. Rebere, D. Sylla, M. Gadouleau, Ph Refait, and J. Creus, Morphological and Structural Characterisation of Electrodeposited Zn-Mn Alloys from Acidic Chloride Bath, Mater. Sci. Eng. A, 2006, 430, p 165–171
S. Ganesan, G. Prabhu, and B.N. Popov, Electrodeposition and Characterization of Zn-Mn Coatings for Corrosion Protection, Surf. Coat. Technol., 2014, 238, p 143–151
D. Sylla, C. Rebere, M. Gadouleau, C. Savall, J. Creus, and Ph Refait, Electrodeposition of Zn-Mn Alloys in Acidic and Alkaline Baths, Influence of Additives on the Morphological and Structural Properties, J. Appl. Electrochem., 2005, 35, p 1133–1139
D. Sylla, J. Creus, C. Savall, O. Roggy, M. Gadouleau, and Ph Refait, Electrodeposition of Zn-Mn Alloys on Steel from Acidic Zn-Mn Chloride Solutions, Thin Solid Films, 2003, 424, p 171–178
M. Farzaneh, K. Raeissi, and M. Golozar, Effect of Current Density on Deposition Process and Properties of Nanocrystalline Ni-Co-W Alloy Coatings, J. Alloys Compd., 2010, 489, p 488–492
R. Ramanauskas, Structural Factor in Zn Alloy Electrodeposit Corrosion, Appl. Surf. Sci., 1999, 153, p 53–64
S. Tezuka, S. Sakai, and Y. Nakagawa, Ferromagnetism of Mn-Zn Alloy, J. Phys. Soc. Jpn., 1960, 15, p 931
Y. Nakagawa and T. Hori, Neutron Diffraction Studies of Mn-Zn Alloys, J. Phys. Soc. Jpn., 1964, 19, p 2082–2087
M.V. Tomic, M.M. Bucko, M.G. Pavlovic, and J.B. Bajat, Corrosion Stability of Electrochemically Deposited Zn-Mn Alloy Coatings, Contemp. Mater., 2010, 1, p 1
R. Ramanauskas, L. Gudaviciute, R. Juskenas, and O. Scit, Structural and Corrosion Characterization of Pulse Plated Nanocrystalline Zinc Coatings, Electrochim. Acta, 2007, 53, p 1801–1810
A.C. Hegde, K. Venkatakrishna, and N. Eliaz, Electrodeposition of Zn-Ni, Zn-Fe and Zn-Ni-Fe Alloys, Surf. Coat. Technol., 2010, 205, p 2031–2041
Acknowledgments
This work was supported by the National Natural Science Foundation of China (51271169, 51001089) and the Key Science and Technology Innovation Team of Zhejiang Province under Grant Number 2010R50013.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Fashu, S., Gu, C.D., Zhang, J.L. et al. Electrodeposition, Morphology, Composition, and Corrosion Performance of Zn-Mn Coatings from a Deep Eutectic Solvent. J. of Materi Eng and Perform 24, 434–444 (2015). https://doi.org/10.1007/s11665-014-1248-5
Received:
Revised:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11665-014-1248-5