Applied Physics A

, Volume 116, Issue 4, pp 1525–1539 | Cite as

Anti-graffiti nanocomposite materials for surface protection of a very porous stone

  • Maurizio Licchelli
  • Marco Malagodi
  • Maduka Weththimuni
  • Chiara Zanchi
Article
First Online:
Received:
Accepted:

Abstract

The preservation of stone substrates from defacement induced by graffiti represents a very challenging task, which can be faced by applying suitable protective agents on the surface. Although different anti-graffiti materials have been developed, it is often found that their effectiveness is unsatisfactory, most of all when applied on very porous stones, e.g. Lecce stone. The aim of this work was to study the anti-graffiti behaviour of new nanocomposite materials obtained by dispersing montmorillonite nanoparticles (layered aluminosilicates with a high-aspect ratio) into a fluorinated polymer matrix (a fluorinated polyurethane based on perfluoropolyether blocks). Polymeric structure was modified by inducing a cross-linking process, in order to produce a durable anti-graffiti coating with enhanced barrier properties. Several composites were prepared using a naturally occurring and an organically modified montmorillonite clay (1, 3, and 5 % w/w concentrations). Materials were applied on Lecce stone specimens, and then their treated surfaces were soiled by a black ink permanent marker or by a black acrylic spray paint. Several repeated staining/cleaning cycles were performed in order to evaluate anti-graffiti effectiveness. Colorimetric measurements were selected to assess the anti-graffiti performance. It was found that the presence of 3 % w/w organically modified montmorillonite in the polymer coating is enough to induce a durable anti-graffiti effect when the stone surface is stained by acrylic paint. Less promising results are obtained when staining by permanent marker is considered as all the investigated treatments afford a reasonable protection from ink only for the first staining/cleaning cycle.

Keywords

Contact Angle Montmorillonite Nanocomposite Material Water Vapour Permeability Static Contact Angle 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
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References

  1. 1.
    E. Doehne, C.A. Price, Stone Conservation: an Overview of Current Research, 2nd edn. (The Getty Conservation Institute, Los Angeles, 2010)Google Scholar
  2. 2.
    R. Fort, M. Alvarez de Buergo, M. Gomez-Heras, C. Vazquez-Calvo, Heritage, Weathering and Conservation Two Volume Set, Proceedings of the International Heritage, Weathering and Conservation Conference (HWC-2006) (Taylor & Francis, London, 2006)Google Scholar
  3. 3.
    H.R. Sasse, R. Snethlage (eds.), Saving Our Architectural Heritage: The Conservation of Historic Stone Structures (Wiley, NY, 1997), pp. 223–243Google Scholar
  4. 4.
    Methods of Evaluating Products for the Conservation of Porous Building Materials in Monuments (ICCROM, Rome, 1995)Google Scholar
  5. 5.
    K. Manczyk, K. Manczyk, B. Trzebicka, A. Dworak, Polimery 53, 830–835 (2008)Google Scholar
  6. 6.
    A. Zielnik, J. Archit. Coat. 1, 70–73 (2005)Google Scholar
  7. 7.
    T. Bengtsson, in Proceedings of the European Coatings Conference “Antigraffiti Coatings” (Berlin, Germany, December 2–3, 1999) pp. 169–189Google Scholar
  8. 8.
    G. Alessandrini, M. Aglietto, V. Castelvetro, F. Ciardelli, R. Peruzzi, L. Toniolo, J. Appl. Polym. Sci. 76, 962–977 (2000)Google Scholar
  9. 9.
    R. Stadler, A. Maier, N. Steidl, Eur. Coat. J. 7–8, 63 (2003)Google Scholar
  10. 10.
    J. Scheerder, N. Visscher, T. Nabuurs, A. Overbeek, J. Coat. Tech. Res. 2, 617–625 (2005)Google Scholar
  11. 11.
    A. Tarnowski, X. Zhang, C. McNamara, S.T. Martin, R. Mitchell, J. ACCR (Association canadienne pour la conservation et la restauration) 32, 3–16 (2007)Google Scholar
  12. 12.
    P.M. Carmona-Quiroga, S. Martínez-Ramírez, M.T. Blanco-Varela, Materiales de Construccion 58, 233–246 (2008)Google Scholar
  13. 13.
    P.M. Carmona-Quiroga, S. Martínez-Ramírez, S. Sánchez-Cortés, M. Oujja, M. Castillejo, M.T. Blanco-Varela, J. Cult. Herit. 11, 297–303 (2010)Google Scholar
  14. 14.
    D. Sianesi, G. Marchionni, R.J. De Pasquale, in Organo-Fluorine Chemistry: Principles and Commercial Applications, ed. by R.E. Banks (Plenum Press, New York, 1994), pp. 431–461Google Scholar
  15. 15.
    F. Piacenti, F. Ciampelli, A. Pasetti, US Patent 4,499,146 (1981)Google Scholar
  16. 16.
    P. Frediani, C. Manganelli del Fa, U. Matteoli, P. Tiano, Stud. Conserv. 27, 31–37 (1982)Google Scholar
  17. 17.
    F. Piacenti, Sci. Total Environ. 143, 113 (1994)Google Scholar
  18. 18.
    G. Moggi, A. Scala, A. Pasetti, F. Piacenti, in Proceedings of VI International Congress on Deterioration and Conservation of Stone (Torun, Poland, September 12–14, 1988), pp. 673–679Google Scholar
  19. 19.
    F. Piacenti, C. Manganelli Del Fà, G. Moggi, A. Pasetti, A. Scala, U.S. Patent 4,902,538 (1990)Google Scholar
  20. 20.
    U. Matteoli, A. Pasetti, F. Piacenti, E. Strepparola, U.S. Patent 4,475,009Google Scholar
  21. 21.
    E. Strepparola, G. Caporiccio, A. Pasetti, F. Piacenti, U.S. Patent 4,746,550 (1988)Google Scholar
  22. 22.
    F. Piacenti, M. Camaiti, E. Strepparola, G. Moggi, J. Fluor. Chem. 58, 220 (1992)Google Scholar
  23. 23.
    F. Federici, E. Cozzi, P. Parrini, US Patent 5,064,926 (1991)Google Scholar
  24. 24.
    E. Cozzi, F. Federici, P. Parrini, US Patent 5,189,135 (1993)Google Scholar
  25. 25.
    T. Trombetta, P. Iengo, S. Turri, J. Appl. Polym. Sci. 98, 1364–1372 (2005)Google Scholar
  26. 26.
    M. Licchelli, S.J. Marzolla, A. Poggi, C. Zanchi, J. Cult. Herit. 12, 34–43 (2011)Google Scholar
  27. 27.
    S. İşçi, F.S. Güner, Ö. Işık Ece, N. Güngör, Prog. Org. Coat. 54, 28 (2005)Google Scholar
  28. 28.
    K.G. Bhattacharyya, S.S. Gupta, Adv. Coll. Int. Sci. 140, 114 (2008)Google Scholar
  29. 29.
    J. Xiong, Z. Zheng, H. Jiang, S. Ye, X. Wang, Compos. A 38, 132 (2007)Google Scholar
  30. 30.
    C. Su, Y. Shen, J. Coll. Int. Sci. 332, 11 (2009)Google Scholar
  31. 31.
    L. D’Arienzo, P. Scarfato, L. Incarnato, J. Cult. Herit. 9, 253–260 (2008)Google Scholar
  32. 32.
    S.S. Ray, M. Okamoto, Prog. Polym. Sci. 28, 1539 (2003)Google Scholar
  33. 33.
    S.A. Madbouly, J.U. Otaigbe, Prog. Polym. Sci. 34, 1283 (2009)Google Scholar
  34. 34.
    J. Yeh, K. Chang, J. Ind. Eng. Chem. 14, 275 (2008)Google Scholar
  35. 35.
    A. Pegoretti, A. Dorigato, M. Brugnara, A. Penati, Eur. Polym. J. 44, 1662 (2008)Google Scholar
  36. 36.
    R.P. Moraes, T.S. Valera, A.M.C. Pereira, N.R. Demarquette, A.M. Santos, J. Appl. Polym. Sci. 119, 3658 (2011)Google Scholar
  37. 37.
    O. Yilmaz, C.N. Cheaburu, D. Durraccio, G. Gulumser, C. Vasile, Appl. Clay Sci. 49, 288 (2010)Google Scholar
  38. 38.
    S. Subramani, J. Lee, S. Choi, J.H. Kim, J. Polym. Sci., Part B: Polym. Phys. 45, 2747 (2007)ADSGoogle Scholar
  39. 39.
    X. Wu, R.P. Rosen, J.C.T. Coat. Tech. 5, 28–37 (2008)Google Scholar
  40. 40.
    S. Bugani, M. Camaiti, L. Morselli, E. Van de Casteele, K. Janssens, X-Ray Spectrom. 36, 316–320 (2007)Google Scholar
  41. 41.
    P. Croveri, M Chiavarini, in Proceedings of 9th International Congress on the Deterioration and Preservation of Stones, vol. 2, ed. by V. Fassina (Elsevier, Amsterdam, 2000), pp. 263–271Google Scholar
  42. 42.
    A. Calia, A.M. Mecchi, G. Quarta, in Proceedings of 9th International Congress on the Deterioration and Preservation of Stones, vol. 1, ed. by V. Fassina (Elsevier, Amsterdam, 2000), pp. 49–58Google Scholar
  43. 43.
    UNI 10921:2001, Beni culturali—Materiali lapidei naturali ed artificiali—Prodotti idrorepellenti—Applicazione su provini e determinazione in laboratorio delle loro caratteristiche (2001)Google Scholar
  44. 44.
    A.Z. Miller, M.A. Rogerio-Candelera, A. Dionisio, M.F. Macedo, C. Saiz-Jimenez, Materiales de Construccion 62, 411–424 (2012)Google Scholar
  45. 45.
    S. Bugani, Study of the Interactions Between Nitrogen Oxides (NOx) and Stone Materials Treated wiith Conservation Products, Thesis (University of Bologna, Italy, 2004)Google Scholar
  46. 46.
    A.Z. Miller, A. Dionisio, L. Laiz, M.F. Macedo, C. Saiz-Jimenez, Ann. Microbiol. 59, 705–713 (2009)Google Scholar
  47. 47.
    E. Vasanelli, M. Sileo, A. Calia, M.A. Aiello, Procedia Chem. 8, 35–44 (2013)Google Scholar
  48. 48.
    M. Licchelli, M. Malagodi, M.L. Weththimuni, C. Zanchi, Prog. Org. Coat. 76, 495–503 (2013)Google Scholar
  49. 49.
    UNI EN 15802:2010, Conservazione dei beni culturali—Metodi di prova—Determinazione dell’angolo di contatto statico (2010)Google Scholar
  50. 50.
    UNI EN 15801:2010, Conservazione dei beni culturali—Metodi di prova—Determinazione dell’assorbimento dell’acqua per capillarità (2010)Google Scholar
  51. 51.
    Italian Recommendation NORMAL 21/85: Permeabilità al Vapor d’Acqua, ICR-CNR, Rome, Italy (1985)Google Scholar
  52. 52.
    UNI EN 15886:2010, Conservazione dei Beni Culturali—Metodi di prova—Misura del colore delle superfici (2010)Google Scholar
  53. 53.
    S. J. Marzolla, Functionalised fluorinated polymers for the protection of stone substrates from graffiti, PhD Thesis, University of Pavia, Italy (2005)Google Scholar
  54. 54.
    M. Brugnara, C. Della Volpe, A. Penati, S. Siboni, T. Poli, L. Toniolo, Ann. Chim. 93, 881–888 (2003)Google Scholar
  55. 55.
    M. Brugnara, E. Degasperi, C. Della Volpe, D. Maniglio, A. Penati, S. Siboni, L. Toniolo, T. Poli, S. Invernizzi, V. Castelvetro, Colloid Surf A 241, 299–312 (2004)Google Scholar
  56. 56.
    A. Tsakalof, P. Manoudis, I. Karapanagiotis, I. Chryssoulakis, C. Panayiotou, J. Cult. Herit. 8, 69–72 (2007)Google Scholar
  57. 57.
    L. Toniolo, T. Poli, V. Castelvetro, A. Manariti, O. Chiantore, M. Lazzari, J. Cult. Herit. 3, 309–316 (2002)Google Scholar
  58. 58.
    E. Borrelli, B. Caballero Moreno, G. Vigliano, Axum project: testing of anti-graffiti products (ICCROM, Rome, 2000)Google Scholar
  59. 59.
    V. Massa, E. Falcone, V. Guidetti, M. Chiavarini, in Durability of building materials and components 7, vol. 2, ed. by C. Sjöström, (E & FN Spon, London, 1996), pp. 1273–1281Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  • Maurizio Licchelli
    • 1
  • Marco Malagodi
    • 1
  • Maduka Weththimuni
    • 1
  • Chiara Zanchi
    • 1
  1. 1.Dipartimento di ChimicaUniversità di PaviaPaviaItaly

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