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Materials and Structures

, 51:156 | Cite as

Consolidation effectiveness of modified Si-based nanocomposites applied to limestones

  • E. Ksinopoulou
  • A. BakolasEmail author
  • A. Moropoulou
Original Article
  • 125 Downloads

Abstract

One of the main issues in the field of Monument Protection is the degradation of limestones as a result of the action of various weathering mechanisms. The modification of widely used silicon-based materials for stone consolidation is intended to overcome the well-known drawbacks of these materials, such as shrinkage and cracking tendency during drying. The addition of nano-dispersions into a silica matrix aims to enhance their effectiveness in several ways, by improving their properties and their viscoelastic behavior. The objective of the current research was the application and evaluation of Si-based modified nanocomposites of optimized composition. The materials were applied to two types of porous stone and the assessment of their compatibility and performance was carried out by using both laboratory techniques and methods (SEM, MIP, TMA, Water Absorption by Capillarity, determination of Water Vapor Permeability) and non-destructive techniques (Ultrasound Velocity determination, Colorimetry). To study the resistance of the treated samples to soluble salt crystallization, accelerated aging tests were performed in sodium sulfate cycles. The modified consolidants consist of an ethyl silicate matrix reinforced with colloidal silica (SiO2) nano-particles and titania (TiO2) particles. Based on the results, the consolidating material does not significantly alter the characteristics of the microstructure and the appearance of stones, allowing the passage of water vapor, while increasing their mechanical properties. Furthermore, the accelerated ageing tests revealed that the treated samples have a higher resistance to the action and crystallization of soluble salts in comparison to untreated.

Keywords

Nanoparticles Stone consolidation Nanosilica Stone conservation Salt cycles 

Notes

Acknowledgements

This research has been co-financed by the European Union (European Social Fund—ESF) and Greek national funds through the Operational Program “Education and Lifelong Learning” of the National Strategic Reference Framework (NSRF)—Research Funding Program: Heracleitus II. Investing in knowledge society through the European Social Fund.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

References

  1. 1.
    Verges-Belmin V et al (2008) Illustrated glossary on stone deterioration patterns, Monuments and Sites. XV. ICOMOS International Scientific Committee for Stone (ISCS), ParisGoogle Scholar
  2. 2.
    Steiger M, Charola AE, Sterflinger K (2011) Weathering and Deterioration. In: Siegesmund S, Snethlage R (eds) Stone in Architecture. Springer, Berlin, pp 227–316CrossRefGoogle Scholar
  3. 3.
    Sassoni E, Graziani G, Franzoni E (2016) An innovative phosphate-based consolidant for limestone. Part 2: durability in comparison with ethyl silicate. Constr Build Mater 102:931–942CrossRefGoogle Scholar
  4. 4.
    Ruedrich J, Siegesmund S (2007) Salt and ice crystallisation in porous sandstones. Environ Geol 52:225–249CrossRefGoogle Scholar
  5. 5.
    Moropoulou A, Haralampopoulos G, Tsiourva T, Auger F, Birginie JM (2003) Artificial weathering and non-destructive tests for the performance evaluation of consolidation materials applied on porous stones. Mater Struct 36(4):210–217CrossRefGoogle Scholar
  6. 6.
    Ferreira Pinto P, Delgado Rodriques J (2008) Stone Consolidation: the role of treatment Procedures. J Cult Herit 9:38–53CrossRefGoogle Scholar
  7. 7.
    Franzoni E, Graziani G, Sassoni E, Bacilieri G, Griffa M, Lura P (2015) Solvent-based ethyl silicate for stone consolidation: influence of the application technique on penetration depth, efficacy and pore occlusion. Mater Struct 48(11):3503–3515CrossRefGoogle Scholar
  8. 8.
    Ksinopoulou E, Bakolas A, Moropoulou A (2016) Modifying Si-based consolidants through the addition of colloidal nanoparticles. Appl Phys A 122(4):1–10CrossRefGoogle Scholar
  9. 9.
    ASTM E2167-01 (2008) Standard guide for selection and use of stone consolidants. ASTM International, West ConshohockenGoogle Scholar
  10. 10.
    Normal 20/85 (1985) Conservazione dei materiali lapidei: Manutenzione ordinaria e straordinaria. Istituto Centrale per il Restauro (ICR), RomeGoogle Scholar
  11. 11.
    Snethlage R, Sterflinger K (2011) Stone conservation. In: Siegesmund S, Snethlage R (eds) Stone in architecture. Springer, Berlin, pp 477–478Google Scholar
  12. 12.
    Laurenzi-Tabasso Μ, Simon S (2006) Testing methods and criteria for the selection/evaluation of products for the conservation of porous building materials. Rev Conserv 7:67–82Google Scholar
  13. 13.
    Delgado Rodrigues J, Grossi A (2007) Indicators and ratings for the compatibility assessment of conservation actions. J Cult Herit 8:32–43CrossRefGoogle Scholar
  14. 14.
    Commission 25-PEM Protection et Erosion des Monuments (1980) Recommended tests to measure the deterioration of stone and to assess the effectiveness of treatment methods. Mater Struct 13:175–253Google Scholar
  15. 15.
    Delgado-Rodriguez J (2001) Consolidation of decayed stones. A delicate problem with few practical solutions. In: Lourenço PB, Roca P (eds) Historical constructions. University of Minho, Guimarães, pp 3–14Google Scholar
  16. 16.
    Price CA, Doehne E (2010) Stone conservation an overview of current research. The Getty Conservation Institute, Los AngelesGoogle Scholar
  17. 17.
    Scherer GW, Wheeler GS (2009) Silicate consolidants for stone. Key Eng Mater 391:1–25CrossRefGoogle Scholar
  18. 18.
    Horrie CV (1999) Materials for conservation: organic consolidants, adhesives and Coatings. Butterworth-Heinemann, OxfordGoogle Scholar
  19. 19.
    Clifton JR (1980) Stone consolidating materials: a status report. National Bureau of Standards, WashingtonCrossRefGoogle Scholar
  20. 20.
    Wheeler G (2005) Alkoxysilanes and the Consolidation of Stone. Getty Conservation Institute, Los AngelesGoogle Scholar
  21. 21.
    Zárraga R, Cervantes J, Salazar-Hernandez C, Wheeler G (2010) Effect of the addition of hydroxyl terminated polydimethylsiloxane to TEOS-based stone consolidants. J Cult Herit 11:138–144CrossRefGoogle Scholar
  22. 22.
    Boos M, Grobe J, Hilbert G, Müller-Rochholz, J (1996) Modified elastic silicic acid ester applied on natural stone and tests of their efficiency. In Proceedings of the 8th international congress on deterioration and conservation of stone, pp 1179–1185. BerlinGoogle Scholar
  23. 23.
    Kim EK, Won J, Kim JJ, Kang YS, Kim SD (2008) TEOS/GPTMS/silica nanoparticle solutions for conservation of Korean heritage stones. In Proceedings of the 11th international congress on deterioration and conservation of stone, pp 915–923. PolandGoogle Scholar
  24. 24.
    Maravelaki-Kalaitzaki P, Kallithrakas-Kontos N, Agioutantis Z, Maurigiannakis S, Korakaki D (2008) A comparative study of porous limestones treated with silicon-based strengthening agents. Progress Org Coat 62(1):49–60CrossRefGoogle Scholar
  25. 25.
    Mosquera MJ, de los Santos DM, Montes A (2005) Producing New Stone Consolidants for the Conservation of Monumental Stones. Mater. Res Soc Symp Proc, vol 852. Materials Research SocietyGoogle Scholar
  26. 26.
    Miliani C, Velo-Simpson ML, Scherer GW (2007) Particle-modified consolidants: a study on the effect of particles on sol–gel properties and consolidation effectiveness. J Cult Herit 8:1–6CrossRefGoogle Scholar
  27. 27.
    Ksinopoulou E, Bakolas A, Kartsonakis IA, Charitidis CA, Moropoulou A (2012) Particle modified consolidants in the consolidation of porous stones In: Proceedings of 12th international congress on the deterioration and conservation of stone, Columbia University, New YorkGoogle Scholar
  28. 28.
    Mosquera MJ, de los Santos DM, Montes A, Valdez-Castro L (2008) New nanomaterials for consolidating stone. Langmuir 24:2772–2778CrossRefGoogle Scholar
  29. 29.
    Liu R, Han X, Huang X, Li W, Luo H (2013) Preparation of three component TEOS-based composites for stone conservation by sol-gel process. J Sol Gel Sci Technol 68:19–30CrossRefGoogle Scholar
  30. 30.
    Kapridaki C, Maravelaki NP (2015) TiO2–SiO2–PDMS nanocomposites with self-cleaning properties for stone protection and consolidation. Geol Soc Lond Spec Publ 416:SP416-6Google Scholar
  31. 31.
    Ksinopoulou E, Bakolas A, Moropoulou A (2014) Modification of Si-based consolidants by the addition of colloidal nanoparticles: application in porous stones. J Nano Res 27:143–152CrossRefGoogle Scholar
  32. 32.
    Kapridaki C, Pinho L, Mosquera MJ, Maravelaki-Kalaitzaki P (2014) Producing photoactive, transparent and hydrophobic SiO2-crystalline TiO2 nanocomposites at ambient conditions with application as self-cleaning coatings. Appl Catal B 156:416–427CrossRefGoogle Scholar
  33. 33.
    Stober W, Fink A (1968) Controlled growth of monodisperse silica spheres in the micron size range. J Colloid Interface Sci 26:62–69CrossRefGoogle Scholar
  34. 34.
    Franzoni E, Sassoni E, Graziani G (2015) Brushing, poultice or immersion? The role of the application technique on the performance of a novel hydroxyapatite-based consolidating treatment for limestone. J Cult Herit 16(2):173–184CrossRefGoogle Scholar
  35. 35.
    Leroux L, Verges-Belmin V, Costa D, Delgado Rodrigues J, Tiano P, Snethlage R, Singer B, Massey S, De Wi E (2000) Measur.ing the penetration depth of consolidating products: Comparison of six methods. In: Proceedings of the IX international congress on the deterioration and conservation of stone, vol 2, pp 361–370. VeniceGoogle Scholar
  36. 36.
    Lopez-Arce P, Gomez-Villalba LS, Pinho L, Fernandez-Valle ME, Alvarez de Buergo M, Fort R (2010) Influence of porosity and relative humidity on consolidation of dolostone with calcium hydroxide nanoparticles: effectiveness assessment with non-destructive techniques. Mater Charact 61:168–184CrossRefGoogle Scholar
  37. 37.
    Skoulikidis T, Vassiliou P, Tsakona K (2005) Surface consolidation of pentelic marble—criteria for the selection of methods and materials—the acropolis case. Environ Sci Pollut Res 12:28–33CrossRefGoogle Scholar
  38. 38.
    Moropoulou A, Kouloumbi N, Haralampopoulos G, Konstanti A, Michailidis P (2003) Criteria and methodology for the evaluation of conservation interventions on treated porous stone susceptible to salt decay. Progress Org Coat 48:259–270CrossRefGoogle Scholar
  39. 39.
    EN 15886 (2010) Conservation of cultural property. Test methods. Colour measurement of surfacesGoogle Scholar
  40. 40.
    EN 15801 (2010) Conservation of cultural property—Test methods-determination of water absorption by capillarityGoogle Scholar
  41. 41.
    ASTM E96 / E96M-16 (2016) Standard test methods for water vapor transmission of materials. ASTM International, West ConshohockenGoogle Scholar
  42. 42.
    Siegesmund S, Ullemeyer K, Weiss T, Tschegg EK (2000) Physical weathering of marbles caused by anisotropic thermal expansion. Int J Earth Sci 89:170–182CrossRefGoogle Scholar
  43. 43.
    ASTM D2845-08 (2008) Standard test method for laboratory determination of pulse velocities and ultrasonic elastic constants of rock. ASTM International, West ConshohockenGoogle Scholar
  44. 44.
    ASTM E831-05 (2005) Standard test method for linear thermal expansion of solid materials by thermomechanical analysis. ASTM International, West ConshohockenGoogle Scholar
  45. 45.
    DIN 52111-03 (1990) Testing of natural stone and mineral aggregates; crystallization test with sodium sulfateGoogle Scholar
  46. 46.
    Graziani G, Sassoni E, Franzoni E (2015) Consolidation of porous carbonate stones by an innovative phosphate treatment: mechanical strengthening and physical-microstructural compatibility in comparison with TEOS-based treatments. Heritage Science 3(1):1CrossRefGoogle Scholar
  47. 47.
    Franzoni E, Graziani G, Sassoni E (2015) TEOS-based treatments for stone consolidation: acceleration of hydrolysis–condensation reactions by poulticing. J Sol-Gel Sci Technol 74(2):398–405CrossRefGoogle Scholar
  48. 48.
    Sassoni E, Franzoni E, Graziani G, Sagripanti F (2014) Limestone resistance to sodium sulfate degradation after consolidation by hydroxyapatite and TEOS. In Proceedings of the international conference on salt weathering of buildings and stone sculptures (SWBSS 2014), Aedificatio Publishers, Brussels (335-345)Google Scholar

Copyright information

© RILEM 2018

Authors and Affiliations

  1. 1.Department of Materials Science and Engineering, School of Chemical EngineeringNational Technical University of AthensAthensGreece

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