Hollow mesoporous zirconia nanocontainers for storing and controlled releasing of corrosion inhibitors

Abstract Release of inhibitor molecules on demand from nanocontainers dispersed in a passive barrier coatings offer great promise for active corrosion protection coatings of metals and alloys with self healing ability. In the present study, hollow mesoporous zirconia nanospheres ( hm -ZrO 2 ) with a hollow core / porous shell structure are proposed as effective containers for corrosion inhibitor loading and releasing. Hollow mesoporous zirconia nanocontainers were synthesized using solid silica nanoparticles as templates. The morphology and phase of zirconia nanocontainers were studied using high resolution transmission electron microscopy and laser Raman spectroscopy. 2-Mercaptobenzothiazole was selected as the model corrosion inhibitor for the encapsulation. The storage and release properties of hm -ZrO 2 were investigated using UV–visible spectroscopy. The encapsulation efficiency of hm -ZrO 2 was 63% and we observed a faster and higher release of 2-MBT from hm -ZrO 2 when the pH was shifted from neutral value.

[1]  Helmuth Möhwald,et al.  Self-repairing coatings containing active nanoreservoirs. , 2007, Small.

[2]  H. Möhwald,et al.  Mesoporous silica nanoparticles for active corrosion protection. , 2011, ACS nano.

[3]  S. Ramya,et al.  Self-Healing Corrosion Resistive Coatings Based on Inhibitor Loaded TiO2 Nanocontainers , 2012 .

[4]  João Tedim,et al.  Silica nanocontainers for active corrosion protection. , 2012, Nanoscale.

[5]  E. Teller,et al.  ADSORPTION OF GASES IN MULTIMOLECULAR LAYERS , 1938 .

[6]  K. Dam-Johansen,et al.  Anticorrosive coatings: a review , 2009 .

[7]  B. Zeng,et al.  Electrochemical Characteristic of 2-Mercaptobenzothiazole Self-Assembled Monolayer on Gold , 2000 .

[8]  Mikhail L. Zheludkevich,et al.  “Smart” coatings for active corrosion protection based on multi-functional micro and nanocontainers , 2012 .

[9]  E. Barrett,et al.  (CONTRIBUTION FROM THE MULTIPLE FELLOWSHIP OF BAUGH AND SONS COMPANY, MELLOX INSTITUTE) The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms , 1951 .

[10]  Helmuth Möhwald,et al.  Layer‐by‐Layer Assembled Nanocontainers for Self‐Healing Corrosion Protection , 2006 .

[11]  F. Schüth,et al.  Highly Monodisperse Zirconia-Coated Silica Spheres and Zirconia/Silica Hollow Spheres with Remarkable Textural Properties , 2006 .

[12]  Xiaolan Chen,et al.  Hollow Mesoporous Zirconia Nanocapsules for Drug Delivery , 2010 .

[13]  Mikhail L. Zheludkevich,et al.  Anticorrosion Coatings with Self-Healing Effect Based on Nanocontainers Impregnated with Corrosion Inhibitor , 2007 .

[14]  Mohsen Khosravi Babadi,et al.  Comparative electrochemical study of self-assembled monolayers of 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, and 2-mercaptobenzimidazole formed on polycrystalline gold electrode , 2007 .

[15]  M. Comotti,et al.  High-temperature-stable catalysts by hollow sphere encapsulation. , 2006, Angewandte Chemie.

[16]  P. Bouvier,et al.  Raman spectra and vibrational analysis of nanometric tetragonal zirconia under high pressure , 2000 .

[17]  Sviatlana V. Lamaka,et al.  “SMART” protective ability of water based epoxy coatings loaded with CaCO3 microbeads impregnated with corrosion inhibitors applied on AA2024 substrates , 2012 .

[18]  Y. Lvov,et al.  Interfacial modification of clay nanotubes for the sustained release of corrosion inhibitors. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[19]  E. Koumoulos,et al.  Incorporation of ceramic nanocontainers into epoxy coatings for the corrosion protection of hot dip galvanized steel , 2012 .

[20]  Helmuth Möhwald,et al.  Active Anticorrosion Coatings with Halloysite Nanocontainers , 2008 .

[21]  H. Hahn,et al.  Nanocrystalline Zirconia Surface‐Doped with Alumina: Chemical Vapor Synthesis, Characterization, and Properties , 2001 .

[22]  Zhongxin Wen.  SPECTRO ELECTROCHEMICAL STUDIES OF THE CORROSION INHIBITION OF COPPER BY MERCAPTOBENZOTHIAZOLE , 1999 .

[23]  G. Kordas,et al.  Encapsulation and release of corrosion inhibitors into titania nanocontainers. , 2010, Journal of nanoscience and nanotechnology.

[24]  W. Suëtaka,et al.  Spectro-electrochemical studies of the corrosion inhibition of copper by mercaptobenzothiazole , 1979 .

[25]  E. Barrett,et al.  The Determination of Pore Volume and Area Distributions in Porous Substances. II. Comparison between Nitrogen Isotherm and Mercury Porosimeter Methods , 1951 .

[26]  S. Ramya,et al.  Corrosion inhibitor storage and release property of TiO2 nanotube powder synthesized by rapid breakdown anodization method , 2013 .

[27]  G. Kordas,et al.  Encapsulation of the corrosion inhibitor 8-hydroxyquinoline into ceria nanocontainers , 2008 .

[28]  M. Montemor,et al.  Oxide nanoparticle reservoirs for storage and prolonged release of the corrosion inhibitors , 2005 .

[29]  W. Stöber,et al.  Controlled growth of monodisperse silica spheres in the micron size range , 1968 .

[30]  D. Shchukin,et al.  Smart self-repairing protective coatings , 2008 .