A novel material was developed using sol-gel chemistry and an environmental-friendly grafting process of clay nanoparticles. In a previous work of our group, highly compact coatings had been generated using silicon alkoxides, as tetraethoxysilane (TEOS) and 3-glycidoxypropyl-trimethoxysilane (GPTMS), with the incorporation of silver ions and synthetic smectite-type clay nanoparticles, demonstrating antibacterial behaviour against Escherichia coli cultures. By controlling the loading, the exfoliation and the grafting processes of the clay nanoparticles, it was possible to control the migration kinetics of silver ions from the coating matrix to the surface. Morphological and structural studies, through SEM-FIB, revealed the effect of clay nanoparticles leading to the development of a homogeneous structure in 2-μm thickness coatings. Grazing incidence small angle X-ray scattering (GISAXS) experiments demonstrated that silver is distributed in a strongly anisotropic arrangement when clay nanosheets are absent. The size of the silver particles developed on the surface is rather different from that of those developed in the bulk of the coating. Scattering patterns also revealed that the incorporation of clay nanosheets promotes the development of less anisotropic structures. Electrochemical impedance spectroscopy (EIS) measurements confirmed the integrity of the material and the applicability of a physical model with normal distribution of resistive and capacitive elements.
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Miyoshi H, Ohno H, Sakai K, Okamura N, Kourai H (2010) Characterization and photochemical and antibacterial properties of highly stable silver nanoparticles prepared on montmorillonite clay in n-hexanol. J Colloid Interface Sci 345(2):433–441
Jones SA, Bowler PG, Walker M, Parsons D (2004) Controlling wound bioburden with a novel silver-containing Hydrofiber® dressing. Wound Repair Regen 12(3):288–294
Silver S, Phung LT (1996) Bacterial heavy metal resistance: new surprises. Annu Rev Microbiol 50(1):753–789
Sondi I, Salopek-Sondi B (2004) Silver nanoparticles as antimicrobial agent: a case study on E. coli as a model for gram-negative bacteria. J Colloid Interface Sci 275(1):177–182
Hofacker S, Mechtel M, Mager M, Kraus H (2002) Sol–gel: a new tool for coatings chemistry. Prog Org Coat 45(2-3):159–164
Saraidarov T, Levchenko V, Reisfeld R (2010) Synthesis of silver nanoparticles and their stabilization in different sol-gel matrices: optical and structural characterization. Phys Status Solidi C 11–12:2648
Gettler AO, Rhoades CP, Weiss S (1927) Contribution to the pathology of generalised argyria withdiscussion on the fate of silver in the human body. Am J Pathol 3:631
Gosheger G, Hardes J, Ahrens H, Streitburger A, Buerger H, Erren M, Gunsel A, Kemper FH, Winkelmann W, von Eiff C (2004) Silver-coated megaendoprostheses in a rabbit model--an analysis of the infection rate and toxicological side effects. Biomaterials 25(24):5547–5556
He W, Wu D, Li J, Zhang K, Xiang Y, Long L, Qin S, Yu J, Zhang Q (2013) Surface modification of colloidal silica nanoparticles: controlling the size and grafting process. Bull Kor Chem Soc 34(9):2747–2752
Wheeler PA, Wang J, Baker J, Mathias LJ (2005) Synthesis and characterization of covalently functionalized laponite clay. Chem Mater 17(11):3012–3018
Santana I, Pepe A, Schreiner W, Pellice S, Ceré S (2015) Hybrid sol-gel coatings containing clay nanoparticles for corrosion protection of mild steel. Electrochim Acta 203:396
Deflorian F, Rossi S, Fedel M, Motte C (2010) Electrochemical investigation of high-performance silane sol–gel films containing clay nanoparticles. Prog Org Coat 69(2):158–166
Liu C, Bi Q, Leyland A, Matthews A (2003) An electrochemical impedance spectroscopy study of the corrosion behaviour of PVD coated steels in 0.5 N NaCl aqueous solution: part I. establishment of equivalent circuits for EIS data modelling. Corros Sci 45(6):1243
Procaccini R, Bouchet A, Pastore JI, Studdert C, Ceré S, Pellice S (2016) Silver-functionalized methyl-silica hybrid materials as antibacterial coatings on surgical-grade stainless steel. Prog Org Coat 97:28–36
ZView 3.4e©, Scribner Associates, Inc.
ZSimpWin 3.21© EChem Software
Giraldo Mejía HF, Yohai L, Pedetta A, Herrera Seitz K, Procaccini RA, Pellice SA (2017) Epoxy-silica/clay nanocomposite for silver-based antibacterial thin coatings: synthesis and structural characterization. J Colloid Interface Sci 508:332–341
Hu S, Rieger J, Roth SV, Gehrke R, Leyrer RJ, Men Y (2009) GIUSAXS and AFM studies on surface reconstruction of latex thin films during thermal treatment. Langmuir 25(7):4230–4234
Huber P, Bunk O, Pietsch U, Textor M, Geue T (2010) Grazing incidence small angle X-ray scattering on colloidal crystals. J Phys Chem B 39:12473
Weast RC (ed) (1989) CRC Handbook of Chemistry and Physics, 70th edn. CRC press, Boca Raton
Wolf AV (1966) Aqueous Solutions and Body Fluids. Harper and row, New York
Brug GJ, van den Eeden ALG, Sluyters-Rehbach M, Sluyters JH (1984) The analysis of electrode impedances complicated by the presence of a constant phase element. J Electroanal Chem 176(1-2):275–295
Hirschron B, Orazem ME, Tribollet B, Vivier V, Frateur I, Musiani M (2010) Determination of effective capacitance and film thickness from constant-phase-element parameters. Electrochim Acta 55(21):6218–6227
Figueiredo M, Gomes C, Costa R, Martins A, Pereira CM, Silva F (2009) Differential capacity of a deep eutectic solvent based on choline chloride and glycerol on solid electrodes. Electrochim Acta 54(9):2630–2634
Pell WG, Zolfaghari A, Conway BE (2002) Capacitance of the double-layer at polycrystalline Pt electrodes bearing a surface-oxide film. J Electroanal Chem 532(1–2):13–23
Jovic VD, Jovic BM (2003) EIS and differential capacitance measurements onto single crystal faces in different solutions: part II: Cu(111) and Cu(100) in 0.1 M NaOH. J Electroanal Chem 541:13–21
Jurczakowski R, Hitz C, Lasia A (2004) Impedance of porous Au based electrodes. J Electroanal Chem 572(2):355–366
Zalewska T, Lisowska-Oleksiak A, Biallozor S, Jasulaitiene V (2000) Polypyrrole films polymerised on a nickel substrate. Electrochim Acta 45(24):4031–4040
Harrington SP, Devine TM (2008) Analysis of electrodes displaying frequency dispersion in Mott-Schottky tests. J Electrochem Soc 155:C381
Harrington SP, Devine TM (2009) Relation between the semiconducting properties of a passive film and reduction reaction rates. J Electrochem Soc 156(4):C154
Hsu CH, Mansfeld F (2001) Concerning the conversion of the constant phase element parameter Y0 into a capacitance. Corrosion 57(9):747–748
Young HD, Freedman RA, Sandin TR, Lewis Ford A (1982) Sears & Zemansky´s University Physics, 6th edn. Addison-Wesley series
Musiani M, Orazem ME, Pébère N, Tribollet B, Vivier V (2011) Constant-phase-element behavior caused by coupled resistivity and permittivity distributions in films. J Electrochem Soc 158:C424
Lavaert L, Cock MD, Moors M, Wettinck E (2000) Influence of pores on the quality of a silicon polyester coated galvanised steel system. Prog Org Coat 38(3-4):213–221
Mr. Martin Lere (CONICET, Argentina) is acknowledged by the technical support. Dr. Antonio Gasperini (CNPEM, Brazil) and Dr. Silvia Ceré (CONICET-UNMdP) are greatly acknowledged for their helpful assistances with GISAXS and electrochemical interpretation respectively. Finally, the authors express their appreciation to Dr. Marcela Vázquez (CONICET-UNMdP) for providing assistance with the English grammar of the manuscript.
Authors want to acknowledge the Argentine National Council of Scientific and Technical Research (CONICET, PIP 2014-0175), the ANPCyT (PICTs 2017-3762 and 2017-1594) and to the National Synchrotron Light Laboratory (LNLS, Brazil; Project 6780/10—Proposal 20160216) for financial supports.
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Mejía, H.F.G., Jiménez-Piqué, E., Valdés, M. et al. Epoxy-silica/clay nanocomposite for silver-based antibacterial thin coatings: structure and ionic mobility. J Solid State Electrochem 24, 2451–2460 (2020). https://doi.org/10.1007/s10008-020-04784-y
- Ionic mobility