Abstract
This study is focused on the fabrication, characterization, and application of corrosion protective coatings to magnesium alloy ZK30. Hybrid organic–inorganic coatings were synthesized using organic-modified silicates together with resins based on bisphenol A diglycidyl ether. Cerium molybdate nanocontainers (ncs) with diameter 100 ± 20 nm were loaded with corrosion inhibitor 2-mercaptobenzothiazole and incorporated into the coatings in order to improve their anticorrosion properties. The coatings were investigated for their anticorrosion and nanomechanical properties. The morphology of the coatings was examined by scanning electron microscopy. The composition was estimated by energy-dispersive X-ray analysis. The mechanical integrity of the coatings was studied through nanoindentation and nanoscratch techniques. Scanning probe microscope imaging of the coatings revealed that the addition of ncs creates surface incongruity; however, the hardness to modulus ratio revealed significant strengthening of the coating with increase of ncs. Studies on their corrosion behavior in 0.5 M sodium chloride solutions at room temperature were made using electrochemical impedance spectroscopy. Artificial defects were formatted on the surface of the films in order for possible self-healing effects to be evaluated. The results showed that the coated magnesium alloys exhibited only capacitive response after exposure to corrosive environment for 16 months. This behavior denotes that the coatings have enhanced barrier properties and act as an insulator. Finally, the scratched coatings revealed a partial recovery due to the increase of charge–transfer resistance as the immersion time elapsed.
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References
Barsoukov E, Macdonald JR (2005) Impedance spectroscopy theory, experiment, and applications. Wiley, Hoboken, pp 13–20
Bei H, George EP, Hay JL, Pharr GM (2005) Influence of indenter tip geometry on elastic deformation during nanoindentation. Phys Rev Lett 95:045501–045504
Bhushan B (1999) Principles and applications of tribology. Wiley, New York
Bhushan B (2002) Introduction to tribology. Wiley, New York
Bull SJ (1999) Can scratch testing be used as a model for the abrasive wear of hard coatings? Wear 233–235:412–423
Charitidis CA, Logothetidis S (2005) Effects of normal load on nanotribological properties of sputtered carbon nitride films. Diam Relat Mater 14:98–108
Cheng YT, Cheng CM (2000) What is indentation hardness? Surf Coat Technol 133–134:417–424
Choi J, Nakao S, Kim J, Ikeyama M, Kato T (2007) Corrosion protection of DLC coatings on magnesium alloy. Diam Relat Mater 16:1361–1364
Cole KS, Cole RH (1942) Dispersion and absorption in dielectrics. II. Direct current characteristics. J Chem Phys 10:98–105
Dasari A, Yu Z-Z, Mai Y-W (2007) Nanoscratching of nylon 66-based ternary nanocomposites. Acta Mater 55:635–646
Dasari A, Yu Z-Z, Mai Y-W (2009) Fundamental aspects and recent progress on wear/scratch damage in polymer nanocomposites. Mater Sci Eng R 63:31–80
Froes FH, Elieser D, Aghion E (1998) The science, technology and application of magnesium. J Miner Met Mater Soc 5:30–34
Han YC, Schmitt S, Friedrich K (1999) Nanoscale indentation and scratch of short carbon fiber reinforced PEEK/PTFE composite blend by atomic force microscope lithography. Appl Compos Mater 6:1–18
Hoche H, Scheerer H, Probst D, Broszeit E, Berger C (2003) Plasma anodisation as an environmental harmless method for the corrosion protection of magnesium alloys. Surf Coat Technol 174:1002–1007
Hodzic A, Stachurski ZH, Kim JK (2000) Nano-indentation of polymer–glass interfaces. Part I. Experimental and mechanical analysis. Polymer 41:6895–6905
Hsu CH, Mansfeld F (2001) Technical Note: concerning the conversion of the constant phase element parameter Y0 into a capacitance. Corrosion 57:747–748
Kartsonakis IA, Ioannis Daniilidis I, Kordas G (2008) Encapsulation of the corrosion inhibitor 8-hydroxyquinoline into Ceria Nanocontainers. J Sol-Gel Sci Technol 48:24–31
Kartsonakis IA, Balaskas AC, Koumoulos EP, Charitidis CA, Kordas G (2012) Evaluation of corrosion resistance of magnesium alloy ZK10 coated with hybrid organic–inorganic film including containers. Corros Sci 65:481–493
Kim JK, Hodzic A (2003) Nanoscale characterisation of thickness and properties of interphase in polymer matrix composites. J Adhesion 79:383–414
Kim JK, Sham ML, Wu JS (2001) Nanoscale characterisation of interphase in silane treated glass fibre composites. Composites A 32:607–618
King RB (1987) Elastic analysis of some punch problems for a layered medium. Int J Solids Struct 23:1657–1664
Koumoulos EP, Charitidis CA, Daniolos NM, Pantelis DI (2011) Nanomechanical properties of friction stir welded AA6082-T6 aluminum alloy. Mater Sci Eng B 176:1585–1589
Koumoulos EP, Charitidis CA, Papageorgiou DP, Papathanasiou AG, Boudouvis AG (2012) Nanomechanical and nanotribological properties of hydrophobic fluorocarbon dielectric coating on tetraethoxysilane for electrowetting applications. Surf Coat Technol 206:3823–3831
Lamaka SV, Knornschild G, Snihirova DV, Taryba MG, Zheludkevich ML, Ferreira MGS (2009) Complex anticorrosion coating for ZK30 magnesium alloy. Electrochim Acta 55:131–141
Leyland A, Matthews A (2004) Design criteria for wear-resistant nanostructured and glassy-metal coatings. Surf Coat Technol 177–178:317–324
Li X, Bhushan B (2002) A review of nanoindentation continuous stiffness measurement technique its applications. J Mater Charact 48:11–36
Liang J, Srinivasan PB, Blawert C, Dietzel W (2009) Comparison of electrochemical corrosion behavior of MgO and ZrO2 coatings on AM50 magnesium alloy formed by plasma electrolytic oxidation. Corros Sci 51:2483–2492
Loose WS (1976) Magnesium and magnesium alloys. In: Uhlig HH (ed) Corrosion handbook, 1st edn. The Electrochemical Society, Wiley, New York, pp 218–251
Ma Y, Hu H, Northwood D, Nie X (2007) Optimization of the electrolytic plasma oxidation processes for corrosion protection of magnesium alloy AM50 using the Taguchi method. J Mater Process Technol 182:58–64
Makar GL, Kruger J (1993) Corrosion of magnesium. Int Mater Rev 38:138–153
Montemor MF, Pinto R, Ferreira MGS (2009) Chemical composition and corrosion protection of silane films modified with CeO2 nanoparticles. Electrochim Acta 54:5179–5189
Ni H, Li XD, Gao HS, Nguyen TP (2005) Nanoscale structural and. mechanical characterization of bamboo-like polymer/silicon nanocomposite films. Nanotechnology 16:1746–1753
Nie HY, Walzak MJ, McIntyre NS (2006) Scratch resistance anisotropy in biaxially oriented polypropylene and poly(ethylene terephthalate) films. Appl Surf Sci 253:2320–2326
Oliver WC, Pharr GM (1992) An improved technique for determining hardness and elastic-modulus using load and displacement sensing indentation experiments. J Mater Res 7:1564–1583
Overney RM (1995) Nanotribological studies on polymers. Trends Polym Sci 3:359–364
Patel MA, Bhanvase BA, Sonawane SH (2013) Production of cerium zinc molybdate nano pigment by innovative ultrasound assisted approach. Ultrason Sonochem 20:906–913
Sanyal B (1981) Organic compounds as corrosion inhibitors in different environments—a review. Prog Org Coat 9:165–236
Scharnagl N, Blawert C, Dietzel W (2009) Corrosion protection of magnesium alloy AZ31 by coating with poly(ether imides) (PEI). Surf Coat Technol 203:1423–1428
Schuh CA (2006) Nanoindentation studies of materials. J Mater Today 9:32–40
Sneddon IN (1948) Boussinesq’s problem for a rigid cone. Math Proc Camb Philos Soc 44:492–507
Sonawane SH, Bhanvase BA, Jamali AA, Dubey SK, Kale SS, Pinjari DV, Kulkarni RD, Gogate PR, Pandit AB (2012) Improved active anticorrosion coatings using layer-by-layer assembled ZnO nanocontainers with benzotriazole. Chem Eng J 189–190:464–472
Stippich F, Vera E, Wolf GK, Berg G, Friedrich Chr (1998) Enhanced corrosion protection of magnesium oxide coatings on magnesium deposited by ion beam-assisted evaporation. Surf Coat Technol 103–104:29–35
Trabelsi W, Triki E, Dhouibi L, Ferreira MGS, Zheludkevich ML, Montemor MF (2006) The use of pre-treatment based on doped silane solutions for improved corrosion resistance of galvanised steel substrates. Surf Coat Technol 200:4240–4250
Troyon M, Huang L (2006) Comparison of different analysis methods in nanoindentation and influence on the correction factor for contact area. Surf Coat Technol 201:1613–1619
Wang H, Akid R, Gobara M (2010) Scratch-resistant anticorrosion sol–gel coating for the protection of AZ31 magnesium alloy via a low temperature sol–gel route. Corros Sci 52:2565–2570
Winston Revie R (2000) Uhlig’s corrosion handbook, 2nd edn. Wiley, New York, pp 799–800
Wong JSS, Sue HJ, Zeng KY, Li RKY, Mai Y-W (2004) Scratch damage of polymers in nanoscale. Acta Mater 52:431–443
Yang X, Chen L, Huang B, Bai F, Yang X (2009) Synthesis of pH-sensitive hollow polymer microspheres and their applications drug carriers. Polymer 50:3556–3563
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The authors want to thank Alubin, Israel for providing the samples of Mg ZK30.
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Special Issue Editors: Juan Manuel Rojo, Vasileios Koutsos
This article is part of the topical collection on Nanostructured Materials 2012
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Kartsonakis, I.A., Koumoulos, E.P., Charitidis, C.A. et al. Hybrid organic–inorganic coatings including nanocontainers for corrosion protection of magnesium alloy ZK30. J Nanopart Res 15, 1871 (2013). https://doi.org/10.1007/s11051-013-1871-3
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DOI: https://doi.org/10.1007/s11051-013-1871-3