Skip to main content
SpringerLink
Log in

Hollow mesoporous silica nanoparticles loaded with phosphomolybdate as smart anticorrosive pigment

  • Published:
Journal of Coatings Technology and Research Aims and scope Submit manuscript

Abstract

Recent developments in surface science and technology open up new opportunities for the development of smart pigments through the integration of nanoscale containers loaded with active components into coatings. Regarding the external factor to trigger the inhibitor release, a change in pH is a very interesting stimulus since corrosion activity leads to local changes in pH. Although several types of nanocontainers and encapsulation approaches have been proposed and studied to meet this goal, mesoporous silica nanoparticles (MSNs) are especially interesting as they retain their solid properties as long as pH of the surrounding medium does not exceed ~11. On the other hand, the use of hollow mesoporous silica nanoparticles (HMSNs) with a large cavity inside each original mesoporous silica nanoparticle has recently gained increasing interest due to the higher loading capacity. In the present work, an environmentally friendly corrosion inhibitor with good anticorrosive behavior when applied on steel substrates, sodium phosphomolybdate, has been successfully loaded and encapsulated on HMSNs. The pH-dependent release of the corrosion inhibitor from the loaded/encapsulated HMSNs has been confirmed. In addition, an improved anticorrosive behavior of the coatings formulated with loaded/encapsulated HMSNs has been observed by Scanning Kelvin Probe (SKP).

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. Wang, H, Presuel, F, Kelly, RG, “Computational Modelling of Inhibitor Release and Transport from Multifunctional Organic Coatings.” Electrochim. Acta, 49 (2) 239–255 (2004)

    Article  Google Scholar 

  2. Katz, SA, Salem, H, “The Toxicology of Chromium with Respect to Its Chemical Speciation: A Review.” J. Appl. Toxicol., 13 217–224 (1993)

    Article  Google Scholar 

  3. Occupational Safety and Health Administration U.S. Department of Labor, “Small Entity Compliance Guide for the Hexavalent Chromium Standards”, OSHA 3320-10N (2006)

  4. Andreeva, DV, Shchukin, G, “Smart Self-repairing Protective Coatings.” Mater. Today, 11 (10) 24–30 (2008)

    Article  Google Scholar 

  5. Slowing, II, Trewyn, BG, Giri, S, Lin, VSY, “Mesoporous Silica Nanoparticles for Drug Delivery and Biosensing Applications.” Adv. Funct. Mater., 17 (8) 1225–1236 (2007)

    Article  Google Scholar 

  6. Kapoor, MP, Vinu, A, Fujii, W, Kimura, T, Yang, Q, Kasama, Y, Yanagi, M, Juneja, LR, “Self-assembly of Mesoporous Silicas Hollow Microspheres Via Food Grade Emulsifiers for Delivery Systems.” Micropor. Mesopor. Mat., 128 187–193 (2010)

    Article  Google Scholar 

  7. Zhao, Y, Zhang, J, Li, W, Zhang, C, Han, B, “Synthesis of Uniform Hollow Silica Spheres with Ordered Mesoporous Shells in a CO2 Induced Nanoemulsion.” Chem. Commun., 2009 (17) 2365–2367 (2009)

    Article  Google Scholar 

  8. Yeh, YQ, Chen, BC, Lin, HP, Tang, CY, “Synthesis of Hollow Silica Spheres with Mesostructured Shell Using Cationic–Anionic–Neutral Block Copolymer Ternary Surfactants.” Langmuir, 22 (1) 6–9 (2006)

    Article  Google Scholar 

  9. Botterhuis, NE, Sun, Q, Magusin, PCMM, van Santen, RA, Sommerdijk, NAJM, “Hollow Silica Spheres with an Ordered Pore Structure and Their Application in Controlled Release Studies.” Chem. Eur. J., 12 1448–1456 (2006)

    Article  Google Scholar 

  10. Slowing, II, Trewyn, BG, Lin, VS, “Mesoporous Silica Nanoparticles for Intracellular Delivery of Membrane-Impermeable Proteins.” J. Am. Chem. Soc., 129 8845–8849 (2007)

    Article  Google Scholar 

  11. Zhao, W, Chen, H, Li, Y, Li, L, Lang, M, Shi, J, “Uniform Rattle-Type Hollow Magnetic Mesoporous Spheres as Drug Delivery Carriers and Their Sustained-Release Property.” Adv. Funct. Mater., 18 (18) 2780–2788 (2008)

    Article  Google Scholar 

  12. Zhu, YF, Kockrick, E, Ikoma, T, Hanagata, N, Kaskel, S, “An Efficient Route to Rattle-Type Fe3O4@SiO2 Hollow Mesoporous Spheres Using Colloidal Carbon Spheres Templates.” Chem. Mater., 21 (12) 2547–2553 (2009)

    Article  Google Scholar 

  13. Chen, F, Hong, H, Shi, S, Goel, S, Valdovinos, HF, Hernandez, R, Theuer, CP, Barnhart, TE, Cai, W, “Engineering of Hollow Mesoporous Silica Nanoparticles for Remarkably Enhanced Tumor Active Targeting Efficacy.” Sci. Rep., 4 5080 (2014)

    Article  Google Scholar 

  14. Yang, Y, Chen, F, Shi, S, Graves, S, Nickles, R, Cai, W, “In Vivo Tumor Targeting of CD146 with Antibody-Conjugated Hollow Mesoporous Silica Nanoparticles.” J. Nucl. Med., 56 (3) 117 (2015)

    Google Scholar 

  15. Jiao, J, Li, X, Zhang, S, Liu, J, Di, D, Zhang, Y, Zhao, O, Wang, S, “Redox and pH Dual-Responsive PEG and Chitosan-Conjugated Hollow Mesoporous Silica for Controlled Drug Release.” Mater. Sci. Eng. C-Mater. Biol. Appl., 67 26–33 (2016)

    Article  Google Scholar 

  16. Suarez, FJ, Sevilla, M, Alvarez, S, Valdes-Solis, T, Fuertes, AB, “Synthesis of Highly Uniform Mesoporous Sub-Micrometric Capsules of Silicon Oxycarbide and Silica.” Chem. Mater., 19 3096–3098 (2007)

    Article  Google Scholar 

  17. Fowler, CE, Khushalani, D, Mann, S, “Interfacial Synthesis of Hollow Microspheres of Mesostructured Silica.” Chem. Commun., 2001 2028–2029 (2001)

    Article  Google Scholar 

  18. Wang, JG, Li, F, Zhou, HJ, Sun, PC, Ding, DT, Chen, TH, “Silica Hollow Spheres with Ordered and Radially Oriented Amino-Functionalized Mesochannels.” Chem. Mater., 21 612–620 (2009)

    Article  Google Scholar 

  19. Tan, B, Lehmler, HJ, Vyas, SM, Knutson, BL, Rankin, SE, “Fluorinated-Surfactant-Templated Synthesis of Hollow Silica Particles with a Single Layer of Mesopores in Their Shells.” Adv. Mater., 17 (19) 2368–2371 (2005)

    Article  Google Scholar 

  20. Rana, RK, Mastai, Y, Gedanken, A, “Acoustic Cavitation Leading to the Morphosynthesis of Mesoporous Silica Vesicles.” Adv. Mater., 14 (19) 1414–1418 (2002)

    Article  Google Scholar 

  21. Guo, X, Deng, Y, Tu, B, Zhao, D, “Facile Synthesis of Hierarchically Mesoporous Silica Particles with Controllable Cavity in Their Surfaces.” Langmuir, 26 (2) 702–708 (2010)

    Article  Google Scholar 

  22. Danumah, C, Vaudreuil, S, Bonneviot, L, Bousmina, M, Giasson, S, Kaliaguine, S, “Synthesis of Macrostructured MCM-48 Molecular Sieves.” Microporous Mesoporous Mater., 44 (1) 241–247 (2001)

    Article  Google Scholar 

  23. Blas, H, Save, M, Pasetto, P, Boissiere, C, Sanchez, C, Charleux, B, “Elaboration of Monodisperse Spherical Hollow Particles with Ordered Mesoporous Silica Shells Via Dual Latex/Surfactant Templating: Radial Orientation of Mesopore Channels.” Langmuir, 24 (22) 13132–13137 (2008)

    Article  Google Scholar 

  24. Guo, X, Kim, YS, Kim, GJ, “Fabrication of SiO2, Al2O3, and TiO2 Microcapsules with Hollow Core and Mesoporous Shell Structure.” J. Phys. Chem. C, 113 (19) 8313–8319 (2009)

    Article  Google Scholar 

  25. Zhao, Y, Wang, H, Liu, Y, Ye, J, Shen, S, “Hollow MCM-41 Microspheres Derived from P(St-MMA)/MCM-41 Core/Shell Composite Particles.” Mater. Lett., 62 (27) 4254–4256 (2008)

    Article  Google Scholar 

  26. Tartaj, P, Gonzalez-Carreno, T, Serna, CJ, “Single-Step Nanoengineering of Silica Coated Maghemite Hollow Spheres with Tunable Magnetic Properties.” Adv. Mater., 13 (21) 1620–1624 (2001)

    Article  Google Scholar 

  27. Hah, HJ, Kim, JS, Jeon, BJ, Koo, SM, Lee, YE, “Simple Preparation of Monodisperse Hollow Silica Particles Without Using Templates.” Chem. Commun., 2003 1712–1713 (2003)

    Article  Google Scholar 

  28. Wang, Q, Liu, Y, Yan, H, “Mechanism of a Self-Templating Synthesis of Monodispersed Hollow Silica Nanospheres with Tunable Size and Shell Thickness.” Chem. Commun., 2007 2339–2341 (2007)

    Article  Google Scholar 

  29. Zhang, T, Zhang, Q, Ge, J, Goebl, J, Sun, M, Tan, Y, Liu, Y, Chang, C, Guo, J, Yin, Y, “A Self-templated Route to Hollow Silica Microspheres.” J. Phys. Chem. C, 113 (8) 3168–3175 (2009)

    Article  Google Scholar 

  30. Hao, N, Jayawardana, KW, Chen, X, Yan, M, “One-Step Synthesis of Amine-Functionalized Hollow Mesoporous Silica Nanoparticles as Efficient Antibacterial and Anticancer Materials.” ACS Appl. Mater. Interfaces, 7 (2) 1040–1045 (2015)

    Article  Google Scholar 

  31. Zuo, S, Liu, W, Yao, C, Li, X, Luo, S, Wu, F, Kong, Y, Liu, X, “One-Pot Template-Free Fabrication of Hollow Mesoporous Sodalite Nanospheres for Drug Release.” Appl. Clay Sci., 119 (Part 1) 170–174 (2016)

    Article  Google Scholar 

  32. Li, ZZ, Wen, LX, Shao, L, Chen, JF, “Fabrication of Porous Hollow Silica Nanoparticles and Their Applications in Drug Release Control.” J. Control. Release, 98 (2) 245–254 (2004)

    Article  Google Scholar 

  33. Chen, JF, Ding, HM, Wang, JX, Shao, L, “Preparation and Characterization of Porous Hollow Silica Nanoparticles for Drug Delivery Application.” Biomaterials, 25 (4) 723–727 (2004)

    Article  Google Scholar 

  34. Sharma, RK, Das, S, Maitra, A, “Enzymes in the Cavity of Hollow Silica Nanoparticles.” J. Colloid Interface Sci., 284 (1) 358–361 (2005)

    Article  Google Scholar 

  35. Wang, J, Ding, H, Tao, X, Chen, J, “Storage and Sustained Release of Volatile Substances from a Hollow Silica Matrix.” Nanotechnology, 18 (24) 245705 (2007)

    Article  Google Scholar 

  36. Zhu, YF, Shi, JL, Chen, HR, Shen, WH, Dong, XP, “A Facile Method to Synthesize Novel Hollow Mesoporous Silica Spheres and Advanced Storage Property.” Microporous Mesoporous Mater., 84 (1–3) 218–222 (2005)

    Article  Google Scholar 

  37. Li, ZZ, Xu, SA, Wen, LX, Liu, F, Liu, AQ, Wang, Q, Sun, HY, Yu, W, Chen, JF, “Controlled Release of Avermectin from Porous Hollow Silica Nanoparticles: Influence of Shell Thickness on Loading Efficiency, UV-Shielding Property and Release.” J. Controlled Release, 111 (1–2) 81–88 (2006)

    Article  Google Scholar 

  38. Zhou, J, Wu, W, Caruntu, D, Yu, MH, Martin, A, Chen, JF, O’Connor, CJ, Zhou, WL, “Synthesis of Porous Magnetic Hollow Silica Nanospheres for Nanomedicine Application.” J. Phys. Chem. C, 111 (47) 17473–17477 (2007)

    Article  Google Scholar 

  39. Chen, T, Fu, J, “pH-Responsive Nanovalves Based on Hollow Mesoporous Silica Spheres for Controlled Release of Corrosion Inhibitor.” Nanotechnology, 23 (23) 235605 (2012)

    Article  Google Scholar 

  40. Ge, C, Zhang, D, Wang, A, Yin, H, Ren, M, Liu, Y, Jiang, T, Yu, L, “Synthesis of Porous Hollow Silica Spheres Using Polystyrene–Methyl Acrylic Acid Latex Template at Different Temperatures.” J. Phys. Chem. Solids, 70 (11) 1432–1437 (2009)

    Article  Google Scholar 

  41. Agrawal, M, Pich, A, Gupta, S, Zafeiropoulos, NE, Simon, P, Stamm, M, “Synthesis of Novel Tantalum Oxide Sub-micrometer Hollow Spheres with Tailored Shell Thickness.” Langmuir, 24 (3) 1013–1018 (2008)

    Article  Google Scholar 

  42. Zea, C, Barranco-García, R, Chico, B, Díaz, I, Morcillo, M, de la Fuente, D, “Smart Mesoporous Silica Nanocapsules as Environmentally Friendly Anticorrosive Pigments.” Int. J. Corros., 2015 426397 (2015)

    Article  Google Scholar 

  43. Tumurova, LV, Kvashnina, EV, Mokhosoev, MV, “Passivation of a Corrosion-Resisting Chrome Steel in the Presence of a Mixture of Phosphate- and Molybdate-Ions.” Prot. Met. (Engl. Transl.), 26 347–349 (1990)

    Google Scholar 

  44. Kalendovà, A, Kalenda, P, Veselý, D, “Comparison of the Efficiency of Inorganic Nonmetal Pigments with Zinc Powder in Anticorrosion Paints.” Prog. Org. Coat., 57 (1) 1–10 (2006)

    Article  Google Scholar 

  45. Karekar, SE, Bhanvase, BA, Sonawane, SH, Deosarkar, MP, Pinjari, DV, Pandit, AB, “Synthesis of Zinc Molybdate and Zinc Phosphomolybdate Nanopigments by an Ultrasound Assisted Route: Advantage Over Conventional Method.” Chem. Eng. Process., 87 51–59 (2015)

    Article  Google Scholar 

  46. de Lima-Neto, P, de Araújo, AP, Araújo, WS, Correia, AN, “Study of the Anticorrosive Behaviour of Epoxy Binders Containing Non-toxic Inorganic Corrosion Inhibitor Pigments.” Prog. Org. Coat., 62 (3) 344–350 (2008)

    Article  Google Scholar 

  47. Shchukin, DG, Möhwald, H, “Surface-Engineered Nanocontainers for Entrapment of Corrosion Inhibitors.” Adv. Funct. Mater., 17 1451–1458 (2007)

    Article  Google Scholar 

Download references

Acknowledgments

The authors gratefully acknowledge financial support for this work from the Ministry of Economy and Competitiveness of Spain (MAT 2011-28178 and MAT 2014-59752R).

Author information

Authors and Affiliations

  1. National Centre for Metallurgical Research (CENIM/CSIC), Avda. Gregorio del Amo 8, 28040, Madrid, Spain

    C. Zea, R. Barranco-García, J. Alcántara, B. Chico, M. Morcillo & D. de la Fuente

  2. Institute of Polymer Science and Technology (ICTP/CSIC), C/Juan de la Cierva 3, 28006, Madrid, Spain

    R. Barranco-García

Authors
  1. C. Zea
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. R. Barranco-García
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. J. Alcántara
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. B. Chico
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. M. Morcillo
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. D. de la Fuente
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to D. de la Fuente.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zea, C., Barranco-García, R., Alcántara, J. et al. Hollow mesoporous silica nanoparticles loaded with phosphomolybdate as smart anticorrosive pigment. J Coat Technol Res 14, 869–878 (2017). https://doi.org/10.1007/s11998-017-9924-7

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11998-017-9924-7

Keywords

Search

Navigation