journal article·2024-04-14Open access

Removing Aged Polymer Coatings from Porous Stone Surfaces Using the Gel Cleaning Method

Maduka Weththimuni, Giacomo Fiocco, Alessandro Girella, Barbara Vigani, Donatella Sacchi, Silvia Rossi, Maurizio Licchelli

Coatings· Volume 14· Issue 4

Abstract

Acrylic polymers were extensively used in past restoration practices, usually as consolidants or protecting agents. Their removal is often required because polymer coatings can improve some decay processes of stone substrates and, after ageing, may generate undesirable materials on the surface of artifacts. Therefore, the removal of old polymer coating from the surface of artifacts has become a common operation in the conservation of cultural heritage. As with other cleaning operations, it is a delicate process that may irreversibly damage the artifacts if not correctly carried out. The main aim of this study was to determine the appropriate cleaning procedure for efficiently removing old acrylic polymers (e.g., Paraloid B-72) from the surface of historical buildings. For this purpose, a polymer was applied to two different porous stone substrates (bio-calcarenite and arenaria stone). The hydrogel cleaning approach was used for the present study, as preliminary results suggested that it is the most promising polymer-removing method. The considered hydrogel (based on a semi-interpenetrating polymer network involving poly(2-hydroxyethyl methacrylate) and polyvinylpyrrolidone) was prepared and characterized using different techniques in order to assess the gel’s properties, including the gel content, equilibrium water content, retention capability, hardness, Young’s modulus, and morphology. After that, the hydrogel was loaded with appropriate amounts of nano-structured emulsions (NSEs) containing a surfactant (EcoSufTM), organic solvents, and H2O, then applied onto the coated surfaces. Moreover, plain EcoSurfTM in a water emulsion (EcoSurf/H2O) was also used to understand the polymer-removing behavior of the surfactant without any organic solvent. A comparative study was carried out on artificially aged and unaged polymer-coated samples to better understand the cleaning effectiveness of the considered emulsions for removing decayed polymer coatings. The experimental results showed that the NSE-loaded hydrogel cleaning method was more effective than other common cleaning procedures (e.g., cellulose pulp method). In fact, only one cleaning step was enough to remove the polymeric material from the stone surfaces without affecting their original properties.
Source: crossref · Quality: baseline

Research context

OpenAlex topics: Building materials and conservation · Cultural Heritage Materials Analysis · Pickering emulsions and particle stabilization

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Department of Chemistry, University of Pavia, Via Taramelli 12, 27100 Pavia, Italy

Research Centre for Cultural Heritage (CISRiC), University of Pavia, Via Ferrata 1, 27100 Pavia, Italy

Arvedi Laboratory of Non-Invasive Diagnostics, Research Centre for Cultural Heritage (CISRiC), University of Pavia, Via Bell’Aspa, 26100 Cremona, Italy

Department of Musicology and Cultural Heritage, University of Pavia, Corso Garibaldi, 178, 26100 Cremona, Italy

Department of Drug Sciences, University of Pavia, Via Taramelli 14, 27100 Pavia, Italy

Funding

Ministero dell’Università e della Ricerca (MUR) · University of Pavia through the program “Dipartimenti di Eccellenza 2023–2027”

References (70)

Show source-provided references
1. Nanoparticles for conservation of bio-calcarenite stone10.1007/s00339-013-7973-z ↗
2. Evaluation of commercial consolidating agents on very porous biocalcarenite
3. Innovative Hydrogel Based on Semi-Intrepenetrating p(HEMA)/PVP Networks for the Cleaning of Water-Sensitive Cultural Heritage Artifacts10.1021/la3048664 ↗
4. Removing Polymeric Coatings with Nanostructured Fluids: Influence of Substrate, Nature of the Film, and Application Methodology10.3389/fmats.2019.00311 ↗
5. Brajer, I., Rouzic, M.F., Shashoua, Y., Taube, M., Chelazzi, D., Baglioni, M., Giorgi, R., and Baglioni, P. (2014, January 15–19). The Removal of Aged Acrylic Coatings from Wall Paintings using Microemulsions. Proceedings of the ICOM-CC, 17th Triennial Conference 2014, Melbourne, Australia.
6. Advanced methodologies for the cleaning of works of art10.1007/s11431-022-2348-7 ↗
7. Highly biocidal poly(vinyl alcohol)-hydantoin/starch hybrid gels: A “Trojan Horse” for Bacillus subtilis10.1016/j.jcis.2023.11.142 ↗
8. A Review on Polymeric Hydrogel Membranes for Wound Dressing Applications: PVA-Based Hydrogel Dressings10.1016/j.jare.2017.01.005 ↗
9. Nanofluids and chemical highly retentive hydrogels for controlled and selective removal of overpainting and undesired graffiti from street art10.1007/s00216-017-0357-z ↗
10. Weththimuni, M.L., Girella, A., Ferretti, M., Sacchi, D., and Licchelli, M. (2023). Nanostructured Emulsions as Smart Cleaning Materials for Removing Aged Polymer Coatings from Stone Substrates. Sustainability, 15.10.3390/su15108117 ↗
11. Gel architectures and their complexity10.1039/C4SM00208C ↗
12. Lee, C., Volpi, F., Fiocco, G., Weththimuni, M.L., Licchelli, M., and Malagodi, M. (2022). Preliminary Cleaning Approach with Alginate and Konjac Glucomannan Polysaccharide Gel for the Surfaces of East Asian and Western String Musical Instruments. Materials, 15.10.3390/ma15031100 ↗
13. Synthesis, swelling and adsorption studies of a responsive sodium alginate–poly(acrylic acid) superabsorbent hydrogel10.1007/s00289-018-2287-0 ↗
14. Djabourov, M. (2024, April 13). Book Chapter; Chapter 1: Gels, Series: New Developments in NMR, NMR and MRI of Gels, Edited by Yves De Deener, ISBN: 978-1-78801-317-8, The Royal Society of Chemistry 2020, Published by the Royal Society of Chemistry. Available online: https://books.rsc.org/books/edited-volume/756/chapter/475969/Gels.
15. Diferentiation of physical and chemical cross-linking in gelatin methacryloyl hydrogels10.1038/s41598-021-82393-z ↗
16. Static Inhomogeneities in Physical Gels: Comparison of Temperature-Induced and Concentration-Induced Sol-Gel Transition10.1021/ma000563v ↗
17. Nanomaterials for the cleaning and pH adjustment of vegetable-tanned leather10.1007/s00339-015-9553-x ↗
18. Chemical semi-IPN hydrogels for the removal of adhesives from canvas paintings10.1007/s00339-013-8150-0 ↗
19. Hernandez-Martinez, A.R. (2021). Poly(2-Hydroxyethyl methacrylate-co-N,Ndimethylacrylamide)-Coated Quartz Crystal Microbalance Sensor: Membrane Characterization and Proof of Concept. Gels, 7.10.3390/gels7040151 ↗
20. Synthesis and swelling behaviors of poly(2-hydroxyethyl methacrylate-co-itaconic acid) and poly(2-hydroxyethylmethacrylate-co-sodium itaconate) hydrogels as potential drug carriers10.1016/j.rechem.2023.100917 ↗
21. Twin-chain polymer networks loaded with nanostructured fluids for the selective removal of a non-original varnish from Picasso’s “L’Atelier” at the Peggy Guggenheim Collection, Venice10.1186/s40494-020-00420-0 ↗
22. Baglioni, M., Poggi, G., Chelazzi, D., and Baglioni, P. (2021). Advanced Materials in Cultural Heritage Conservation. Molecules, 26.10.3390/molecules26133967 ↗
23. Hydrogels as Contact Lens Materials
24. Biomedical Applications of Poly(2-Hydroxyethyl Methacrylate) and its Copolymers
25. Polymers of N-Vinylpyrrolidone: Synthesis, Characterization and Uses10.1295/polymj.17.143 ↗
26. Physicochemical characterization of acrylic polymeric resins coating porous materials of artistic interest10.1016/j.porgcoat.2003.10.011 ↗
27. Comparative evaluation of fluorinated and unfluorinated acrylic copolymers as water-repellent coating materials for stone10.1002/(SICI)1097-4628(20000509)76:6<962::AID-APP24>3.0.CO;2-Z ↗
28. Tailoring new fluorinated acrylic copolymers as protective coatings for marble10.1016/S1296-2074(02)01240-2 ↗
29. Analytical characterization of artist’s paint systems based on emulsion polymers and synthetic organic pigments10.1016/j.jaap.2018.09.001 ↗
30. Conservation concerns for acrylic emulsion paints
31. Learner, T.J.S., Patricia Smithen, J.W.K., and Michael, R.S. (2006, January 16–19). Modern Paints Uncovered. Proceedings of the Modern Paints Uncovered Symposium Organized by the Getty Conservation Institute, Tate and the National Gallery of Art, Tate Modern, London, UK.
32. Stoye, D., and Freitag, W. (1998). Paints, Coatings and Solvents, WILEY–VCH. [2nd ed.].10.1002/9783527611867 ↗
33. UV ageing studies: Evaluation of lightfastness declarations of commercial acrylic paints10.1007/s00216-011-5369-5 ↗
34. Characterization of additives of PVAc and acrylic waterborne dispersions and paints by analytical pyrolysis–GC–MS and pyrolysis–silylation–GC–MS10.1016/j.jaap.2015.04.011 ↗
35. Consolidation of Bio-Calcarenite Stone by Treatment Based on Diammonium Hydrogenphosphate and Calcium Hydroxide Nanoparticles10.1016/j.measurement.2018.06.007 ↗
36. Bergamonti, L., Potenza, M., Scigliuzzo, F., Meli, S., Casoli, A., Lottici, P.P., and Graiff, C. (2024). Hydrophobic and Photocatalytic Treatment for the Conservation of Painted Lecce stone in Outdoor Conditions: A New Cleaning Approach. Appl. Sci., 14.10.3390/app14031261 ↗
37. The Flight of Saint Mary Magdalene—A Case Study of the Dismantling, Repositioning and Restoration of a Votive Aedicule and Wall Painting in Nardò, Lecce, Italy10.3390/heritage6040182 ↗
38. Esposito, D., Vitarelli, F., Vita, L., and D’Onofrio, M. (2017). Conoscenza e progetto. Un caso di studio. Santa Maria di Cerrate. RPR, Rilievo, Progetto, Riuso, Maggioli.
39. De Pascalis, D.G., Leucci, G., De Giorgi, L., Giuri, F., and Scardozzi, G. (2019, January 4–6). The Basilica of Santa Caterina d’Alessandria in Galatina (Lecce, Italy): NDT surveys for the conservation project. Proceedings of the 2019 IMEKO TC-4 International Conference on Metrology for Archaeology and Cultural Heritage, Florence, Italy.
40. Applicazione di tecniche strumentali al controllo del degrado delle pietre nei monumenti: Il caso della Basilica di S. Michele in Pavia
41. Colloid and Materials Science for the Conservation of Cultural Heritage: Cleaning, Consolidation, and Deacidification10.1021/la304456n ↗
42. Simpson, W.G. (1995). Resins in the conservation of three-dimensional works of art. Plastics and Resin Compositions, The Royal Society of Chemistry.
43. (2001). Beni Culturali—Materiali Lapidei Naturali Ed Artificiali—Prodotti Idrorepellenti—Applicazione Su Provini e Determinazione in Laboratorio Delle Loro Caratteristiche (Standard No. UNI 10921:2001). Available online: https://www.biblio.units.it/SebinaOpac/resource/beni-culturali-materiali-lapidei-naturali-ed-artificiali-prodotti-idrorepellenti-applicazione-su-pro/TSA1388731?locale=eng.
44. Durable Polymer Coatings: A Comparative Study of PDMS-Based Nanocomposites as Protective Coatings for Stone Materials10.3390/chemistry4010006 ↗
45. Properties of PVA-AA Cross-linked HEMA-based Hydrogels10.1007/s10965-006-0087-y ↗
46. Spermidine Crosslinked Gellan Gum-Based “Hydrogel Nanofibers” as Potential Tool for the Treatment of Nervous Tissue Injuries: A Formulation Study10.2147/IJN.S368960 ↗
47. Improved Texture Analysis for Hydrogel Characterization: Gel Cohesiveness, Adhesiveness, and Hardness10.1002/app.35414 ↗
48. Hydrogels based on copolymers of 2-hydroxyethylmethacrylate and 2-hydroxyethylacrylate as a delivery system for proteins: Interactions with lysozyme10.1002/app.44768 ↗
49. Smułek, W., Grząbka-Zasadzi’nska, A., Kilian, A., Ciesielczyk, F., Borysiak, S., Baranowska, H.M., Walkowiak, K., Kaczorek, E., and Jarzębski, M. (2023). Design of vitamin-loaded emulsions in agar hydrogel matrix dispersed with plant surfactants. Food Biosci., 53.10.1016/j.fbio.2023.102559 ↗
50. (2010). Conservazione dei Beni Culturali, Metodi di Prova, Misura del Colore Delle Superfici (Standard No. UNI EN 15886:2010).
51. Ben Chobba, M., Weththimuni, M.L., Messaoud, M., Sacchi, D., Bouaziz, J., De Leo, F., Urzi, C., and Licchelli, M. (2021). Multifunctional and Durable Coatings for Stone Protection Based on Gd-Doped Nanocomposites. Sustainability, 13.10.3390/su131911033 ↗
52. (2010). Conservazione dei Beni Culturali—Metodi di Prova—Determinazione Dell’angolo di Contatto Statico (Standard No. UNI EN 15802:2010).
53. Weththimuni, M.L., Milanese, C., Licchelli, M., and Malagodi, M. (2021). Improving the Protective Properties of Shellac-Based Varnishes by Functionalized Nanoparticles. Coatings, 11.10.3390/coatings11040419 ↗
54. Tamburini, G., Canevali, C., Ferrario, S., Bianchi, A., Sansonetti, A., and Simonutti, R. (2022). Optimized Semi-Interpenetrated p(HEMA)/PVP Hydrogels for Artistic Surface Cleaning. Materials, 15.10.3390/ma15196739 ↗
55. Hydrogels based on 2-hydroxyethyl methacrylate: Synthesis, characterization and hydration capacity10.4067/S0717-97072020000104682 ↗
56. Bashir, S., Hina, M., Iqbal, J., Rajpar, A.H., Mujtaba, M.A., Alghamdi, N.A., Wageh, S., Ramesh, K., and Ramesh, S. (2020). Fundamental Concepts of Hydrogels: Synthesis, Properties, and Their Applications. Polymers, 12.10.3390/polym12112702 ↗
57. pH-Dependent Swelling and Solute Diffusion Characteristics of Poly (Hydroxyethyl Methacrylate–CO–Methacrylie Acid) Hydrogels10.1023/A:1015998131160 ↗
58. Recent advances in the synthesis of smart hydrogels10.1039/D1MA00193K ↗
59. Lee, C., Di Turo, F., Vigani, B., Weththimuni, M.L., Rossi, S., Beltram, F., Pingue, P., Licchelli, M., Malagodi, M., and Fiocco, G. (2023). Biopolymer Gels as a Cleaning System for Different Featured Wooden Surfaces. Polymers, 15.10.3390/polym15010036 ↗
60. Passaretti, A., Cuvillier, L., Sciutto, G., Guilminot, E., and Joseph, E. (2021). Biologically Derived Gels for the Cleaning of Historical and Artistic Metal Heritage. Appl. Sci., 11.10.3390/app11083405 ↗
61. New tool for sustainable treatments: Agar spray—Research and practice10.1186/s40494-022-00756-9 ↗
62. ZrO2-Doped ZnO-PDMS Nanocomposites as Protective Coatings for the Stone Materials10.21014/acta_imeko.v11i1.1078 ↗
63. Infrared Spectroscopy of Polymers X: Polyacrylates10.56530/spectroscopy.mi9381w4 ↗
64. Interactions between Nanostructured Calcium Hydroxide and Acrylate Copolymers: Implications in Cultural Heritage Conservation10.1021/la401883g ↗
65. Influence of Titanium Dioxide Pigments on the Photodegradation of Paraloid Acrylic Resin10.1179/sic.2003.48.1.57 ↗
66. Characterization of Limestone as Raw Material to Hydrated Lime10.1051/e3sconf/20183402042 ↗
67. Phase and morphology evolution of calcium carbonate precipitated by carbonation of hydrated lime10.1007/s10853-012-6535-7 ↗
68. Calcium carbonate in cholesterol gallstones: Polymorphism, distribution, and hypotheses about pathogenesis
69. Use of infrared spectrophotometry in the analysis of limestone10.1021/ed043p314 ↗
70. Spectroscopic characterization of natural calcite minerals10.1016/j.saa.2006.12.043 ↗