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Preventing colour fading in artworks with graphene veils

Abstract

Modern and contemporary art materials are generally prone to irreversible colour changes upon exposure to light and oxidizing agents. Graphene can be produced in thin large sheets, blocks ultraviolet light, and is impermeable to oxygen, moisture and corrosive agents; therefore, it has the potential to be used as a transparent layer for the protection of art objects in museums, during storage and transportation. Here we show that a single-layer or multilayer graphene veil, produced by chemical vapour deposition, can be deposited over artworks to protect them efficiently against colour fading, with a protection factor of up to 70%. We also show that this process is reversible since the graphene protective layer can be removed using a soft rubber eraser without causing any damage to the artwork. We have also explored a complementary contactless graphene-based route for colour protection that is based on the deposition of graphene on picture framing glass for use when the direct application of graphene is not feasible due to surface roughness or artwork fragility. Overall, the present results are a proof of concept of the potential use of graphene as an effective and removable protective advanced material to prevent colour fading in artworks.

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Fig. 1: Graphene deposition onto artworks.
Fig. 2: Ageing of mock-ups with graphene veils.
Fig. 3: Mechanism of protection against photo-fading of colours.
Fig. 4: Ageing of an artwork with graphene.
Fig. 5: The removal of the graphene membrane from an artwork.
Fig. 6: The protection of colour underneath the graphene layer.

Data availability

The data that supports the findings of this study are available from the corresponding authors on reasonable request.

References

  1. 1.

    Dümcke, C. & M. Gnedovsky. The Social and Economic Value of Cultural Heritage: Literature Review (European Expert Network on Culture, 2013).

  2. 2.

    Jablonski, E., Learner, T., Hayes, J. & Golden, M. Conservation concerns for acrylic emulsion paints: a literature review. Tate Papers 2 https://www.tate.org.uk/research/publications/tate-papers/02/conservation-concerns-for-acrylic-emulsion-paints-literature-review (2004).

  3. 3.

    Sterflinger, K.& Pinzari, F. The revenge of time: fungal deterioration of cultural heritage with particular reference to books, paper and parchment. Environ. Microbiol. 14, 559–566 (2012).

  4. 4.

    Vanmeert, F., Van Der Snickt, G. & Janssens, K. Plumbonacrite identified by X-ray powder diffraction tomography as a missing link during degradation of red lead in a Van Gogh painting. Angew. Chem. Int. Ed. Engl. 1889, 3607–3610 (2015).

  5. 5.

    Baglioni, P., Carretti, E. & Chelazzi, D. Nanomaterials in art conservation. Nat. Nanotechnol. 10, 287–290 (2015).

    CAS  Article  Google Scholar 

  6. 6.

    Tsoukleri, G. et al. Subjecting a graphene monolayer to tension and compression. Small 5, 2397–2402 (2009).

  7. 7.

    Androulidakis, C. et al. Graphene flakes under controlled biaxial deformation. Sci. Rep. 5, 18219 (2015).

    CAS  Article  Google Scholar 

  8. 8.

    Berry, V. Impermeability of graphene and its applications. Carbon N.Y. 62, 1–10 (2013).

    CAS  Article  Google Scholar 

  9. 9.

    Su, Y. et al. Impermeable barrier films and protective coatings based on reduced graphene oxide. Nat. Commun. https://doi.org/10.1038/ncomms5843 (2014).

  10. 10.

    Spitz Steinberg, R., Cruz, M., Mahfouz, N. G. A., Qiu, Y. & Hurt, R. H. Breathable vapor toxicant barriers based on multilayer graphene oxide. ACS Nano 11, 5670–5679 (2017).

    CAS  Article  Google Scholar 

  11. 11.

    Reina, A. et al. Large area, few-layer graphene films on arbitrary substrates by chemical vapor deposition. Nano Lett. 9, 30–35 (2009).

    CAS  Article  Google Scholar 

  12. 12.

    Cho, D. H. et al. Effect of surface morphology on friction of graphene on various substrates. Nanoscale 5, 3063–3069 (2013).

    CAS  Article  Google Scholar 

  13. 13.

    Taherian, F., Marcon, V., Van Der Vegt, N. F. A. & Leroy, F. What is the contact angle of water on graphene? Langmuir 29, 1457–1465 (2013).

    CAS  Article  Google Scholar 

  14. 14.

    Mak, K. F., Ju, L., Wang, F. & Heinz, T. F. Optical spectroscopy of graphene: from the far infrared to the ultraviolet. Solid State Commun. 152, 1341–1349 (2012).

    CAS  Article  Google Scholar 

  15. 15.

    Zhong, G. et al. Growth of continuous graphene by open roll-to-roll chemical vapor deposition. Appl. Phys. Lett. 109, 193103 (2016).

  16. 16.

    Lee, W. H. et al. Simultaneous transfer and doping of CVD-grown graphene by fluoropolymer for transparent conductive films on plastic. ACS Nano 6, 1284–1290 (2012).

  17. 17.

    Chandrashekar, B. N. et al. Roll-to-roll green transfer of CVD graphene onto plastic for a transparent and flexible triboelectric nanogenerator. Adv. Mater. 27, 5210–5216 (2015).

    CAS  Article  Google Scholar 

  18. 18.

    Chen, X. D. et al. High-quality and efficient transfer of large-area graphene films onto different substrates. Carbon N.Y. 56, 271–278 (2013).

    CAS  Article  Google Scholar 

  19. 19.

    Martins, L. G. P. et al. Direct transfer of graphene onto flexible substrates. Proc. Natl Acad. Sci. USA 110, 17762–17767 (2013).

    CAS  Article  Google Scholar 

  20. 20.

    Kumar, S., Kaushik, S., Pratap, R. & Raghavan, S. Graphene on paper: a simple, low-cost chemical sensing platform. ACS Appl. Mater. Interfaces 7, 2189–2194 (2015).

    CAS  Article  Google Scholar 

  21. 21.

    Bae, S. et al. Roll-to-roll production of 30-inch graphene films for transparent electrodes. Nat. Nanotechnol. 5, 574–578 (2010).

    CAS  Article  Google Scholar 

  22. 22.

    Kim, S. J. et al. Ultraclean patterned transfer of single-layer graphene by recyclable pressure sensitive adhesive films. Nano Lett. 15, 3236–3240 (2015).

    CAS  Article  Google Scholar 

  23. 23.

    Malard, L. M., Pimenta, M. A., Dresselhaus, G. & Dresselhaus, M. S. Raman spectroscopy in graphene. Phys. Rep. 473, 51–87 (2009).

    CAS  Article  Google Scholar 

  24. 24.

    Schuessler, Z. Delta E. 101. zschuessler.github.io/DeltaE/ (2020).

  25. 25.

    Keuch, P. Kinetics: Fading of Triphenylmethanes Dyes—Pseudo First Order Reaction (Univ. Regensburg, Institute of Organic Chemistry, 2004).

  26. 26.

    Dos Santos, T. C. et al. Assessment of the breakdown products of solar/UV induced photolytic degradation of food dye tartrazine. Food Chem. Toxicol. 68, 307–315 (2014).

    Article  Google Scholar 

  27. 27.

    Das, S. R. et al. Single-layer graphene as a barrier layer for intense UV laser-induced damages for silver nanowire network. ACS Nano 9, 11121–11133 (2015).

    CAS  Article  Google Scholar 

  28. 28.

    Sarno, M., Rossi, G., Cirillo, C. & Incarnato, L. Cold wall chemical vapor deposition graphene-based conductive tunable film barrier. Ind. Eng. Chem. Res. 57, 4895–4906 (2018).

    CAS  Article  Google Scholar 

  29. 29.

    Wang, M. et al. Graphene-draped semiconductors for enhanced photocorrosion resistance and photocatalytic properties. J. Am. Chem. Soc. 139, 4144–4151 (2017).

    CAS  Article  Google Scholar 

  30. 30.

    Choi, K. et al. Reduced water vapor transmission rate of graphene gas barrier films for flexible organic field-effect transistors. ACS Nano 9, 5818–5824 (2015).

    CAS  Article  Google Scholar 

  31. 31.

    Nam, T. et al. A composite layer of atomic-layer-deposited Al2O3 and graphene for flexible moisture barrier. Carbon N.Y. 116, 553–561 (2017).

    CAS  Article  Google Scholar 

  32. 32.

    Nair, R. R. et al. Fine structure constant defines visual transparency of graphene. Science 320, 1308 (2008).

    CAS  Article  Google Scholar 

  33. 33.

    Kim, D. J. et al. Degradation protection of color dyes encapsulated by graphene barrier films. Chem. Mater. 31, 7173–7177 (2019).

    CAS  Article  Google Scholar 

  34. 34.

    Seethamraju, S. et al. Million-fold decrease in polymer moisture permeability by a graphene monolayer. ACS Nano 10, 6501–6509 (2016).

    CAS  Article  Google Scholar 

  35. 35.

    Seo, H. K. et al. Laminated graphene films for flexible transparent thin film encapsulation. ACS Appl. Mater. Interfaces 8, 14725–14731 (2016).

    Article  Google Scholar 

  36. 36.

    Kim, H. W. et al. Selective gas transport through few-layered graphene and graphene oxide membranes. Science 342, 91–95 (2013).

    CAS  Article  Google Scholar 

  37. 37.

    Guo, F. et al. Graphene-based environmental barriers. Environ. Sci. Technol. 46, 7717–7724 (2012).

    CAS  Article  Google Scholar 

  38. 38.

    Paraense, M. O., da Cunha, T. H. R., Ferlauto, A. S. & de Souza Figueiredo, A. S. Monolayer and bilayer graphene on polydimethylsiloxane as a composite membrane for gas-barrier applications. J. Appl. Polym. Sci. 134, https://doi.org/10.1002/app.45521 (2017).

  39. 39.

    Kidambi, P. R. et al. Assessment and control of the impermeability of graphene for atomically thin membranes and barriers. Nanoscale 9, 8496–8507 (2017).

    CAS  Article  Google Scholar 

  40. 40.

    Calculating the Energy from Sunlight over a 12-Hour Period (NASA, 2012); https://www.grc.nasa.gov/www/k-12/Numbers/Math/Mathematical_Thinking/sun12.htm

  41. 41.

    National Optical Astronomy Observatory (NOAO). Recommended light levels. NOAO. https://www.noao.edu/education/QLTkit/ACTIVITY_Documents/Safety/LightLevels_outdoor+indoor.pdf (2015).

  42. 42.

    Singh, S. P. A comparison of different methods of paper surface smoothness evaluation. BioResources 3, 503–516 (2008).

    Google Scholar 

  43. 43.

    Goyal, H. Physical properties. Properties of Paper https://paperonweb.com/paperpro.htm#PhysicalProperties (2015).

  44. 44.

    Han, G. H. et al. Poly(ethylene co-vinyl acetate)-assisted one-step transfer of ultra-large graphene. Nano 6, 59–65 (2011).

    CAS  Article  Google Scholar 

  45. 45.

    Wyszecki, G. & Stiles, W. S. Color Science: Concepts and Methods, Quantitative Data and Formulae 2nd edn (Wiley Classics Library, 2000).

Download references

Acknowledgements

We acknowledge support from the European Research Council (ERC) through the GraphenART (779985) Proof-of-Concept project, and the APACHE (814496) project funded from the European Union’s Horizon 2020 research and innovation programme. The painter M. Stavropoulou is sincerely thanked for donating original artworks for our experiments. C. Malliaris (FORTH/ICEHT) is thanked for designing and developing the roll-to-roll transfer system. G. A. Voyiatzis and G. Mathioudakis (FORTH/ICEHT) are thanked for performing the water vapour permeability measurements. D. Vroulias, V. Dracopoulos and T. Ioannides (FORTH/ICEHT) are thanked for performing the oxygen permeability measurements. Finally, the Laser, Non-Linear and Quantum Optics Laboratory of the Physics Department, University of Patras is acknowledged for the surface roughness measurements and the Plasma Technology Laboratory of the Chemical Engineering Department, University of Patras for the contact angle measurements.

Author information

Affiliations

Authors

Contributions

M.K., G.G., M.G.P.C., G. Pa., G. Po. and G.T. designed and performed the experiments. M.K., G.A. and A.M. interpreted the data. M.G.P.C., G.G. and G. Po. drafted the manuscript. C.G. and P.B. conceived the work, participated in its design and coordination, supervised all experimental procedures and revised the manuscript.

Corresponding author

Correspondence to C. Galiotis.

Ethics declarations

Competing interests

A patent has been granted from the Hellenic Industrial Property Organisation (No. 1009757) while two applications (Nos. PCT/EP2019/085993 and EP21155800) have been submitted to the European Patent Office (EPO). The following authors are involved in the patents: M.K., G.G., M.G.P.C., G.A., G.Pa., G.Po., P.B. and C.G. The remaining authors (A.M. and G.T.) declare no competing interests.

Additional information

Peer review information Nature Nanotechnology thanks Gary Cheng, Jun Zhang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Extended data

Extended Data Fig. 1 Comparison of graphene veils with commercial products adopted in prevention of colour fading.

Reflectance spectra before (a) and during ageing for 4 weeks (b to e) with Neon Light for mockups dyed with methyl blue (MB), coated with mono-, bi- and tri-layer graphene (1LG, 2LG and 3LG) and coated with commercial spray (UV1) and commercial varnish (UV2). Pictures of the specimens before (i) and after ageing (ii) are shown in F. PF for UV1 and UV2 after ageing are, respectively, 25.7% and 46.6%.

Extended Data Fig. 2 Protection factors (%) for all the investigated coloured mockups.

Glossy paper (a), cardboard (b) and canvas paper (c) upon UV light exposure; glossy paper upon white/visible light exposure (d); Tartrazine on cardboard paper upon UV light exposure (e); cardboard/filter paper upon neon light exposure (f).

Extended Data Fig. 3 Graphene-enhanced picture framing glasses.

a, Typical Raman spectra of graphene transferred on “museum” glass. b, Statistical analysis of 2D/G intensity ratio from analysis of Raman mapping. c, Representative AFM topography of monolayer CVD graphene transferred on glass. d, Ultraviolet and visible transmittance spectra for “museum” glass with and without monolayer graphene. e, Pictures of commercial glass (FLABEG ARTControl UV60) and of the same glass coated in the central area with a single graphene layer. As shown, graphene is imperceptible and the glass transparency is not lost after graphene deposition. f, Protection factors for the commercial museum glass and the same coated with single layer graphene. Graphene coating offers an enhancement by ca. 40%.

Supplementary information

Supplementary Information

Supplementary Figs. 1–14, Methods, Discussion and Tables 1–5.

Supplementary Video 1

Graphene-based solutions for innovative coatings.

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Kotsidi, M., Gorgolis, G., Pastore Carbone, M.G. et al. Preventing colour fading in artworks with graphene veils. Nat. Nanotechnol. 16, 1004–1010 (2021). https://doi.org/10.1038/s41565-021-00934-z

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