Progress in Organic Coatings 113 (2017) 90–109

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Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Review

Conservation strategies against graffiti vandalism on Cultural Heritage MARK

stones: Protective coatings and cleaning methods
⁎
Vera Gomesa, Amélia Dionísiob, , J. Santiago Pozo-Antonioc
a
Conservation and Restoration Department, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516, Monte de Caparica, Portugal
b
CERENA, DECIVIL, Instituto Superior Técnico, Lisbon University, Av. Rovisco Pais, 1049-001 Lisbon, Portugal
c
Departamento de Enxeñaría dos Recursos Naturais e Medio Ambiente, Escola de Enxeñaría de Minas e Enerxía, Universidade de Vigo, Campus Lagoas-Marcosende,
36310, Vigo, Spain

A R T I C L E I N F O A B S T R A C T

Keywords: Graffiti paintings, as an act of vandalism, are one of the most severe threats to stone applied in Cultural Heritage.
Cultural Heritage Their cleaning is expensive and in most of the cases, also induce stone damage, such as chemical contamination,
Stone by-products and physical changes. In the recent years, the application of anti-graffiti products has been carried
Anti-graffiti out in order to preserve the valuable substrate. Despite the research lines have been focused on the evaluation of
Graffiti spray paints
cleaning procedures and anti-graffiti products, it is necessary to lead a critical study of the recently reported
Coatings
Cleaning methods
results, considering the type of stone and the composition of the other key stakeholders, namely the anti-graffiti
Effectiveness protective coatings, the paints and the cleaning agents. A brief description of the composition of the most
Harmfulness common spray paints used by graffiti-writers in Cultural Heritage stones is also presented.
The protective effectiveness of anti-graffiti coatings and the most remarkable findings on stone graffiti
cleaning methods are listed and discussed. Anti-graffiti coatings may facilitate the removal of graffiti compared
to untreated surfaces, however this efficacy may be compromised on more porous substrates. Moreover, in
almost all of the analysed scientific papers, it was possible to remove graffiti without inducing any damage to the
substrate.
This review paper will allow to help conservator-restores to achieve the optimization of the graffiti cleaning
procedures on stones in Cultural Heritage. Finally, some futures research lines are pointed out.

1. Introduction characteristics of the protective coatings to be applied in materials of

historical monuments: Low surface energy; Permanent under outdoor
The term graffiti is derived from the Italian word graffiare (to conditions; Reversible to specially designed mild cleaning systems;
scratch) and can be defined as writing or drawings scribbled, scratched, Permeable to water vapour; Impermeable to liquid wate and; Trans-
drawn or painted, on a wide range of materials and substrates, mainly parent [2].
located in public accessible places, as result of a vandalism act [1]. However, in many cases, graffiti is done in historic surfaces (Fig. 1)
Around 3,500,000 protected monuments in European cities are affected without anti-graffiti protection and in real practice, they are not shortly
by this threat and many cities worldwide spend huge amounts of money removed after their execution, i.e., most of the times they are cleaned
in cleaning campaigns to tackle graffiti vandalism [2]. The European after long environmental exposure. This leads the graffiti to interact
Commission (EC) has financed projects to develop sustainable anti- with the environmental agents (e.g. rain and atmospheric pollutants)
graffiti products that ensure the satisfactory graffiti extraction without and also with the stone substrate. Thus, the graffiti paint may suffer
induce damages on the substrate (GRAFFITAGE, 2005–2008) [2] and physical and chemical alterations and subsequently the stone may be
on support urban environment policies to prevent and eliminate graffiti affected not only by the application of graffiti but also by its alteration
(GRAFFOLUTION, 2014–2016) [3]. During the last decade, some re- process. Along with the previously mentioned consequences it must be
search centres and universities worldwide have been testing commer- added the damages associated to cleaning, such as surface abrasion,
cial anti-graffiti coatings and developing new formulations that intend chemical contamination, mineralogical alterations [4,5], which are
to avoid/reduce the interaction of the cleaning procedure with the related with the intrinsic properties of the stone, the composition of the
valuable substrate [2]. As a matter of fact, the EC established the main paint and the cleaning agents used [4].

⁎
Corresponding author.
E-mail address: [email protected] (A. Dionísio).

http://dx.doi.org/10.1016/j.porgcoat.2017.08.010
Received 29 June 2017; Received in revised form 17 August 2017; Accepted 25 August 2017
Available online 06 October 2017
0300-9440/ © 2017 Elsevier B.V. All rights reserved.
V. Gomes et al. Progress in Organic Coatings 113 (2017) 90–109

Fig. 1. A: Graffiti cans MOTIP® and Montana Colours®. B-D: Graffiti vandalism paintings in stone monuments: B: Venetian fortress in Heraklion (Crete, Greece); C: Castel dell'Ovo (Naples,
Italy); D: Roman bridge in Ourense (Spain). Sources: A and B: the authors; C: Cristina Montojo and D: Alberto Pereira.

Therefore, in order to optimize the strategies to minimize the dan- chemical reaction with oxygen, a hardener, moisture and coalescence of
gerous effect of graffiti on Cultural Heritage stones, an evaluation of the an emulsion [1]. While the ones that harden by evaporation of the
more recent researches on the graffiti cleaning and anti-graffiti coatings solvent can be dissolved thru re-application of the solvent [1], the ones
is imperious. So this review presents a state-of-the-art over the com- that harden by polymerization cannot be easily returned to the pre-
position of the most common graffiti paints, anti-graffiti protective viously liquid state [6]. Moreover, the paint may penetrate to various
coatings and their cleaning procedures (chemical, mechanical, laser and depths on the substrate depending on factors like a high solvent content
biological methods). The cleaning performances are critically evaluated (that implies a higher flow rate) and the interfacial tension solid sur-
considering the stone type, the binder composition of the paints and the face/liquid [9].
cleaning agent. This review concludes with a discussion of emerging From the universe of graffiti materials like spray paints, markers
issues and new research directions. and inks covered by the literature, it is important to highlight some
brands that were specially developed for the graffiter’s market.
2. Graffiti materials Montana Colors® (Fig. 1) introduced in the market the first spray paint
made specifically for graffiters and it is now spread worldwide across
The range of materials used by graffiti-writers to scribble monu- 60 countries. It was founded in Barcelona in 1994 by Jordi Rubio [10]
ments and historic facades is fairly extent and they can be found in who started at Felton®, which is a paint production company also in
multiple layers superimposed requiring a sequence of methods/pro- Barcelona [11]. The international Krink® started with handmade paints
ducts to be removed [6,7]. for personal use by KR (founder) in Brooklyn in 1993 [12]. Nero
Spray paint outlines as the main material used by graffiti-writers D’inferno ® was originally developed for use as a leather dye, however
due to its visual impact and quick and easy application [5,8]. They are later it became established as one of the common choices of ink for
composed of pigments that provide colour and opacity, additives that artists. Brands with a larger market, not only focused on graffiti ma-
improve certain properties (e.g. plasticity, fluidity, thickness, etc.), a terials are also reported in the literature e.g. MOTIP
binder that holds all the ingredients together and a solvent that allows HOME & HOBBYLACQUER® group (Fig. 1), Trans-color®, Herpe, Ham-
this mixture to flow [9]. Paints may harden by evaporation of the sol- merite, Trimetal Nobel, Akzo Nobel Coatings AG, European Aerosols,
vent or through polymerization. The polymerization can occur by De Keyn Paint, Intergamma, Auto-K.

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V. Gomes et al. Progress in Organic Coatings 113 (2017) 90–109

Fig. 2. Micrographs taken with stereomicroscopy and scanning electron microscopy (SEM). A-B: Stereomicroscopy micrographs of Albero granite (NW Spain) coated with a permanent
water based fluoralkyl siloxane (A) and Rosa Porriño granite (NW Spain) with a sacrificial water based crystalline micro wax (B). C-D: SEM micrographs of A and B respectively.
Source: the authors.

White pigments are the main component of all paints (white and dissolved in the same solvent [19]. Almost half of 51 red spray paints
coloured); titanium confers whiteness, brightness and opacity to graffiti analysed by Govaert & Bernard by optical microscopy, Fourier trans-
in Montana Colors® [13–16], Trans-color® [17,18], Felton® [17,18] and form infrared spectrometry and X-ray fluorescence, are composed of
Motip-Dupli®. Black colour is often obtained by adding carbon, silver alkyd-nitrocellulose-based binders [26]. Samolik et al. also detected in
colour by adding aluminium and gold colour by the introduction of zinc Motip-Dupli® Montana Gold an acrylic resin along with nitrocellulose
and copper (Montana Colors® in [13–16] and Trans-color® in [17,18]). [22].
Additives may be also present in small amounts: plasticizers or The main spray paint solvents are hydrocarbons (aliphatic, naph-
dispersants to increase plasticity or fluidity, surfactants and wetting thenic and aromatic-toluene and xylene), oxygenated (ketones, esters,
agents to disperse pigments, thickeners, pH buffers to stabilize the pH glycol esters and alcohols-especially n-butanol) and water [5,8].
range, anti-foaming agents to alter the surface tension of a paint, It is barely impossible to distinguish the type of paint without
freeze–thaw agents, biocides and sequestering agents to remove metal proper analysis [1]. Germinario et al. carried out a multi-technique
ions [5,8]. characterization focused on the identification of the binders, pigments
The main synthetic binders in twentieth-century paints are acrylic, and additives of 45 spray paints of diverse brands [27]. Fourier
alkyd and nitrocellulosic [19]. Transform Infrared spectroscopy was used for a first approach to
Acrylic resins are based on the esters of acrylic and methacrylic characterize binders, pigments, andextenders and it was able to detect
acids [19] and can be found in Krink® and Nero D’inferno® cutting edge nitrocellulose in the alkyd-based paints. Then, μ-Raman spectroscopy
paints [20,21]. This paint may be purely acrylic or copolymerized with allowed the characterization of inorganic pigments, extenders and some
other vinyl species, such as styrene which is present in low-cost paints azo and polycyclic pigments. Moreover, pyrolysis-gas chromatography/
and also in artist quality paints, like Trans-color® and Felton® [17,18]. mass spectrometry allowed to confirm main and minor binders, several
Alkyd resins are polyesters formed by a polyalcohol and a di- azo and polycyclic pigments, presence of acrylic and alkyd resins in the
carboxylic acid [19]. Its drying mechanism is similar to oil paint, i.e. same formulation, and the identification of acrylic monomers and in-
complex oxidative polymerization reactions resulting in a cross-linked dividual fatty acids and polyols of alkyd resins. The usefulness of pyr-
insoluble film [19]. These resins were identified in Motip-Dupli® Mon- olysis-gas chromatography/mass spectrometry has also been reported
tana Black [22], Montana Colours® [13–16] and MOTIP by Milczarek & Zieba-Palus to detect and characterize diverse spray
HOME & HOBBYLACQUER® [9,23,24]. Burns & Doolan found that paints on mineral-based plaster. However, for the acrylic copolymer-
through pyrolysis gas chromatography/mass spectrometry, contrary to based, silicone-based and silicate-based plasters the presence of plaster
Fourier transform infrared spectroscopy, is possible to differentiate strong background peaks hid the paints signal [28]. The analytic
modified alkyd resins on the basis of their modifier [25]. methods are expensive and time consuming, leading, in most of the
Nitrocellulosic resins are composed of cellulose nitrate, a second times to the performance of different on-site trials to decide the most
resin (usually alkyd) and large quantities of plasticizers (mainly dibutyl suitable method to achieve the optimal cleaning [1]. Usually the spe-
and dioctyl phthalate).It is formulated as a solution that can be re- cific chemical composition of the graffiti paints is unknown. Despite,

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V. Gomes et al. Progress in Organic Coatings 113 (2017) 90–109

Fig. 3. A-B: Circular graphs showing the percentage of studies focused on the different stone type (limestone, marble, sandstone, granite and others) considering the researches based on
the evaluation of anti-graffiti studies (A) and the percentage of studies on each stone type (the same showed in A) among those focused on graffiti removal without any previous
application of anti-graffiti product (B). C: Circular graph showing the percentage of studies focused on different cleaning procedures (chemical, mechanical, lasers and biological) among
researches about graffiti removal in stones without any previous application of anti-graffiti product.

currently, part of the scientific community started to be concerned anti-graffiti under SO2 exposure [35]. Ormosil reduced the graffiti ad-
about the unveiling of the graffiti composition, the scientific works are hesion to the substrates and prevented the formation of sulphur com-
mainly focused only in the cleaning evaluation. pounds on limestone. In a later research, they also noticed that by in-
creasing the anti-graffiti concentration, a more effective reduction of
stone surface energy was achieved [31]. In a recent article, they con-
3. Anti-graffiti protective coatings cluded that in limestone, both mentioned coatings: Protectosil and
Ormosil, remained stable under photo-oxidising conditions [36]. It was
Since the graffiti cleaning can induce stone damage, there was a also detected that under freeze-thaw cycles limestone showed an ac-
need to develop coatings to protect the stone’s surface from graffiti and celerated decay, while the granite samples did not exhibit decay signs
facilitate its removal (Fig. 2) [29]. The EC took a step forward by en- [36].
couraging a new anti-graffiti formulation, suitable for historical Gardei et al. used diverse commercial AGS anti-graffiti agents with
monuments, based on ancient protein coatings, a complexation of different formulations on Villamayor, Galdacano, Strterica and
polyampholytes with polymeric amines modified by fluorocarbon re- Baumberg sandstones and Balegem, Belgian blue, and Roman travertine
sidues (GRAFFITAGE). The first scientific paper to focus the effect of limestones: a sacrificial one (AGS2 based on wax/paraffin), and six
anti-graffiti on stone is dated back 2008. Since then many protective permanent others: AGS1 (Copolymer), AGS3 (Polyurethane), AGS4
coatings arrived on the market. Nowadays there are about 19 scientific (Methacrylate), in comparison to three versions of the newly designed
papers published about this theme [30], more than 50% focused on agent AGS5, (1, 2 and 3) (2-C-Polymer) [32]. It was reported that
carbonated stones (Fig. 3). surface became smoother, and a reduction of water uptake and decrease
In Table 1, a summary of all the researches focused on anti-graffiti of water evaporation after the coatings application was achieved. It was
products, lithotypes, graffiti paints and cleaning methods is presented obtained a satisfactory cleaning, with few paint residues, using a pH
and will discussed in the next paragraphs. neutral commercial cleaner. The highest reductions of capillarity water
Anti-graffiti products generate low surface energies which limit the absorption were achieved with AGS3, the lowest with AGS2 and AGS4.
graffiti adhesion to the surface, thereby facilitating their removal and AGS3 also produced the minor colour and gloss changes while AGS2
also waterproofing the stone material [31]. There are two main types of altered the colour of the less porous substrates. Garcia et al. in its
anti-graffiti coatings: the so-called sacrificial (or temporary) and per- comparative study of 4 anti-graffiti (an acrylate copolymer; an emul-
manent. sion of paraffin, a polyurethane and an ethyl methacrylate), reported
The sacrificial coatings are removed during the cleaning process and that the graffiti penetration is more influenced by the pore sizes than by
are generally based on waxes and silicones. Therefore they have a the porosity of the stone substrate [37]. Later, Meng et al. exposed these
limited durability under intense environmental conditions [32]. same coatings to artificial and natural ageing tests and concluded that
The permanent coatings which can theoretically resist several the newly designed agent (AGS5) was the most suitable to historical
cleaning cycles, are usually polyurethanes, fluorocarbon, alkyl alkoxy surfaces. The coating offered a satisfactory compromise between water
silanes. These are also known by hindering the moisture transport from transport, visual alterations and cleaning effectiveness for all the tested
the substrate through the atmosphere [32]. substrates: Villamayor sandstone, Strtenica sandstone, Balegem lime-
Both types of anti-graffiti coatings can be removed by hot pressur- stone and Belgian blue limestone [38]. Mueller et al. also tested both
ized water or dissolved by chemical agents [29]. García & Malaga de- AGS1 and AGS2 on Flossenbürg granite, Selters Trachyte, Mayern ba-
veloped a list of tests to determine the criteria for the acceptance or salt lava, Lindlar greywacke, Anröchte green sandstone, Postaer sand-
rejection of an anti-graffiti on historical porous substrates, with stone, Treuchtlinger limestone, Crailshaim limestone and Thüster
minimum acceptable values for relevant properties [33]. The anti- limestone, [39]. The porosity of the stones has proved to be the factor
graffiti protective coatings were tested by the scientific community with that mainly influences the cleaning performance and to a lesser extent,
various graffiti materials, namely spray paints and markers, the in- the superficial roughness. The water absorption coefficient and water
formation concerning the type of graffiti material is given across the vapour permeability were considerably reduced but not equally for all
chapter individually for each study. substrates. While the colour changes were acceptable for all the sub-
Several alkyd enamel spray paints were tried to remove on Gris strates, the gloss changes were notable in some of them, namely on the
Quintana granite and Branco Paloma limestone after the application of low porosity substrates were AGS2 was applied.
the permanent coating Protectosil Anti-graffiti (fluoralkyl siloxane) Malaga & Bengtsson tested the removal of tectyl rust protection (a
with chemical solvent cyclohexanone [34]. The nanometric coating mixture of wax and tar), leather dye aniline, felt tip pens and spray
nature slightly changed the porosity and lowered the permeability, paints with high pressurized water on granite, sandstone, limestone and
however the cleaning was not completely effective in the limestone, the marble coated with a microcrystalline wax under artificial weathering
more porous material studied by these authors. Later, Carmona-Quiroga [29]. As results, the coating maintained its colour, gloss,
et al. compared Ormosil organically modified silicate with Protectosil

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 Table 1
Anti-graffiti studies carried out by several authors. The lithotypes and their nature, the graffiti paints and their composition, the anti-graffiti applied and the cleaning methods used to extract the graffiti are reported. n.p.: not performed, n.a.; not
applied.
V. Gomes et al.

Reference Lithotype Nature Graffiti Graffiti composition Anti-graffiti Cleaning method

Gardei et al. [29] Villamayor’s Siliceous Unknown paints n.p. - AGS 1 (Wax/Paraffin) Unknown pH neutral commercial solvent
(sandstone) - AGS 2: (Copolymer) (chemical method)
Galdacano’s Siliceous - AGS 3 (Polyurethane)
(sandstone) - AGS 4 (Methacrylate)
Strterica (sandstone) Siliceous - Three versions of AGS 5 (2-C-Polymer)
Baumberg (sandstone) Siliceous
Balegem’s (sandstone) Siliceous
Belgian blue Calcareous
(limestone)
Roman travertine Calcareous
(limestone)
Carmona-Quiroga Gris Quintana Siliceous Red, green and black enamel spray paints Alkyd based binders - Degussas’s Protectosil Antigraffiti (fluoralkyl siloxane) Unknown solvent (chemical method)
et al. [31] (granite)
Branco Paloma Calcareous
(limestone)
Malaga and Two unknown Siliceous - Tectyl rust protection (mixture of wax n.p. Microcrystalline wax High-pressure hot water cleaning (mechanical
Bengtsson [26] granites and tar) method)
Two unknown marble Calcareous - Black, red and blue spray paints
One unknown Calcareous - Black and blue felt tip pens
limestone - Red and blue leather dye aniline
One unknown Siliceous
sandstone
Carmona-Quiroga One unknown Calcareous Red, green and black enamel spray paints Alkyd based binders - Degussas’s Protectosil Antigraffiti (fluoralkyl siloxane) n.p.
et al. [32] limestone - Ormosil (organically modified silicate)

94
One unknown granite Siliceous
Brick Artificial
Lime mortar Artificial
Cement mortar Artificial
García et al. [34] Villamayor’s Siliceous n.a. n.a. - Anti-graffiti 1 (Acrilate copolymer) n.p.
(sandstone) - Anti-graffiti 2 (paraffin polymers)
Galdacano’s Siliceous - Anti-graffiti 3 (Polyurethane)
(sandstone) - Antigraffiti 4 (Ethyl methacrylate)
Strterica (sandstone) Siliceous
Baumberg (sandstone) Siliceous
Balegem’s (sandstone) Siliceous
Belgian blue Calcareous
(limestone)
Roman travertine Calcareous
(limestone)
Mueller and Malaga Flossenbürg (granite) Siliceous Unknown paints n.p. - AGS1 (fluorinated silane) Unknown AGS 1 cleaning agent (chemical
[36] Selters Trachyte Siliceous - AGS2 (micro crystalline wax) method)
Mayerner Basalt Lava Siliceous
Lindlar er Greywacke Siliceous
(sandstone)
Anröchter green Siliceous
(sandstone)
Postaer (sandstone) Siliceous
Treuchtlinger Calcareous
(limestone)
Crailshaim Calcareous
(limestone)
Thüster (limestone) Calcareous
Thüster (limestone) Calcareous
(continued on next page)
Progress in Organic Coatings 113 (2017) 90–109
 Table 1 (continued)

Reference Lithotype Nature Graffiti Graffiti composition Anti-graffiti Cleaning method

V. Gomes et al.

Clinker masonry panel Artificial

Concrete paving panel Artificial
Licchelli et al. [37] Carrara (marble) Calcareous BIC® black permanent marker n.p. - Fluorolink® P56 (anionic fluorinated polyurethane) - Remover® AC (mixture of -butyrolactone,
Pietra Serena Siliceous - Xama® 7 (pentaerythrytol tris [3-(1-aziridinyl) dipropy-leneglycol monomethylether)
(sandstone) propionate]) - Triton® (chemical methods)
Pietra di Lecce Calcareous
(limestone)
Carmona-Quiroga Gris Quintana Siliceous Red, green and black enamel spray paints Alkyd based binders - Degussas’s Protectosil Antigraffiti (fluoralkyl siloxane) Cyclohexanone (chemical method)
et al. [28] (granite) - Ormosil (organically modified silicate)
Branco Paloma Calcareous
(limestone)
Licchelli et al. [38] Lecce stone Calcareous Unknown paints n.p. Tecnoflon® (vinyli- dene fluoride, hexafluoropropene, n.p.
(limestone) tetrafluoroethene
Lettieri and Masieri Lecce stone Calcareous Briolux® orange-coloured spray paint n.p. - AG1 (polymer waxes) - Hot water and brushing (mechanical
[39] (limestone) - AG2a (acrylic- fluorinated copolymers) the primer of method)
AG2b (waxes and acrylic-fluorinated resins). - R1 (glycol ether-based solution) for surfaces
cleaned with AG1
- R2 (surfactants and solvents) for surfaces
cleaned with AG2
Licchelli et al. [44] Lecce stone Calcareous - BASIC OFFICE® black ink permanent ROLMACRYL® black paint has - Fluorolink® P56 (fluorinated polyurethane) with - 2-Propanol (isopropyl alcohol, IPA)
(limestone) marker acrylic based binders Dellite® HPS (naturally occurring Na-montmorillonite) - 2-butanone (methyl ethyl ketone, MEK)
- ROLMACRYL® black paint RAL9005 - Dellite® 43B (naturally occurring purified (chemical method)-
montmorillonite, modified with ammonium salt)
Meng et al. [35] Villamayor Siliceous - DUPLI COLOR®, Aerosol ART yellow- - DUPLI COLOR® has acrylic - AGS 1 (Acrilate copolymer) Brush cleaned with a special apparatus and
(sandstone) green spray paint based binders - AGS 2 (paraffin wax) unknown chemical cleaning agent (chemical
Brick Artificial - Classic alueffectlack® metallic grey spray - Classic alueffectlack® has - AGS 3 (Polyester) method)

95
Strtenica (sandstone) Siliceous paint alkyd based binders with - AGS 4 (Ethyl methacrylate)
Balegem (limestone) Calcareous - MULTONA® car paint Henna red 1977 aluminium pigments - AGS 5 (2-C-Polymer)
Belgian blue Calcareous - Renovo® silk black matt spray paint - MULTONA® has nitrocellulose
(limestone) - Edding® 850 black permanent marker based binders
- Renovo® has acrylic based
binders
- Edding® is an organic dye.
Carmona-Quiroga Blanco Paloma Calcareous n.a. n.a. - Fluoroalkylsiloxane-Ormosil (organically modified n.p.
et al. [33] (limestone) silicate)
Gris Quintana Siliceous
(granite)
Cocco et al. [42] Biancone Tirreno Calcareous Montana Colors® mtn94 black and red spray Alkyd based binders - AG1 (paraffin waxes) Hot water and dichloromethane (chemical
(wakestone) paints - AG2 (composed by a primer with amino- method)
Pietra Cantone Calcareous functionalized polysiloxane and a base with alkyl
(limestone) fluoride functionalized silane monomer and a
lyophobic polymer)
A. Moura et al. [46] Moleanos (limestone) Calcareous Unknown paint Based on potassium silicate and - Ssilox (organosiloxane) n.p.
Lime-based mortar Artificial pigmented with rutile titanium - Snano (coating with SiO2 nanoparticles)
Lime-based mortar Artificial dioxide - Pfluor (fluoroalkylsiloxane)
with silicate paint
Kronlund et al. [45] Carrara (marble) Calcareous Montana-Cans®: Montana Black and - Montana black has Capstone FS-63 (fluorosurfactant) mixed with ethanol, Pressurized water (mechanical method)
Montana White, both black coloured nitrocellulose and alkyd based ethyleneglycol and water
resins
- Montana white has alkyd
based resins
Ana Moura et al. Moleanos (limestone) Calcareous Montana Colors®: Mtn 94 fluor blue Based on potassium silicate and - Ssilox (organosiloxane) - Rdecap (paint striper)
[47] Lime-based mortar Artificial (14R71067) and grey (11R15908) and a blue pigmented with rutile titanium - Snano (coating with SiO2 nanoparticles) - Rsolv (Organic solvent) (chemical methods)
Lime-based mortar Artificial felt marker (code bar: 8 427744 107536) dioxide - Pfluor (fluoroalkylsiloxane)
with silicate paint - Psilic (silicon-based molecules)
(continued on next page)
Progress in Organic Coatings 113 (2017) 90–109
V. Gomes et al. Progress in Organic Coatings 113 (2017) 90–109

hydrophobicity and water uptake. They provided satisfactory extraction

- R2 (surfactants and solvents) for surfaces

followed by brushing or high pressurized
- Dupli-Color® Graffiti-Ex spray detergent
of the tested stains except of leather dyes which penetrated through the

- R1 (glycol ether) for surfaces treated

- Hot water and brushing (mechanical
coating.
Water (mechanical method) Licchelli et al. used a mixture of two anti-graffitis: Fluorolink® P56
(anionic fluorinated polyurethane) and Xama® 7 (pentaerythrytol tris
[3-(1-aziridinyl)propionate]) to protect Carrara marble, Pietra Serena
sandstone and Pietra di Lecce limestone. Afterwards Remover® AC

treated with AG2

(mixture of γ-butyrolactone, dipropy-leneglycol monomethylether) and
Cleaning method

Triton® were used to clean a BIC® black permanent marker [40]. Despite
- with AG1
method)

both cured and uncured coatings showed high contact angles, the
protective effectiveness was only satisfactory at the shortest times to-
wards water penetration (30 min of water capillarity absorption). The
ink penetration was related to the cured/uncured polymer features (the
- AG2 (polymer waxes and acrylic-fluorinated resins)

cured samples exhibited better performance) and to the stone proper-

ties (after few cleaning cycles, traces of unremoved ink started to be
- AG1 (polyurethane with a perfluoropolyether

perceptible in the porous Pietra di Lecce). Later, they used Tecnoflon®

TN (terpolymer of difluoroethene vinylidene fluoride, hexa-
fluoropropene, and tetrafluoroethene) on Pietra di Lecce [41]. The
samples coated by capillary absorption showed an acceptable reduction
- AG2 (crystalline micro wax)

of vapour permeability contrary to the brushing application. The ca-

pillary absorption allowed the polymer to penetrate into the stone
- AG1 (polymer waxes)

structure, however when applied in higher amounts, a formation of a

film was detected [41].
Lettieri & Masieri applied on Pietra di Lecce an AG1 (water emulsion
backbone)

of polymer waxes), an AG2a (water emulsion of acrylic-fluorinated

Anti-graffiti

copolymers) and an AG2b (polymer waxes added to acrylic-fluorinated

resins in water emulsion) to protect the stone from Briolux® spray paint
[42]. The paint was tried to remove with R1 (glycol ether-based solu-
tion) and R2 (surfactants and solvents specific for cleaning surfaces
Based on methyl-methacrylate

protected with AG2). The unprotected surfaces exhibited significant

residual stains after the cleaning, due to the previously mentioned high
penetration rate of the paint. The best results were obtained when a
Graffiti composition

thinner polymer coating was applied and namely with the AG2 and its
primer since it avoided the penetration of the paint. The threshold
values for the evaluation of the colour changes were indicative of ac-
ceptable cleaning actions [42]. Later the same authors tested the same
resin
n.p.

stone and referred anti-graffiti, paint and cleaning agents [43]. The
paint penetrated through the coating, due to the low glass transition
Montana Colors spray paints: Madrid red,

Briolux Spray® orange-coloured (RAL code

temperature (Tg). After repeated cleaning cycles with hot water, me-
pistachio green, electric blue, black and

chanical action and the chemical removers R1 (glycol ether) and R2

(surfactants and solvents), the complete removal of the paints and
protective coatings was not achieved, especially with AG1. Later, it was
found that a thin film of anti-graffiti protective coating achieved a
silver and a black marker

lower percentage of residues (with a new proposed method to estimate

the graffiti remains) after cleaning in comparison with a thicker coating
®

[43].
Cocco et al. tested on Biancone Tirreno (wakestone) and Pietra
Graffiti

Cantone (limestone) an AG1 (paraffin waxes in water) and an AG2 (a

2005)

primer with amino-functionalized polysiloxane water emulsion, and a

base with alkyl fluoride functionalized silane monomer plus a lyo-
Calcareous

Calcareous

phobic polymer) anti-graffiti products. It was achieved a good water

Siliceous
Nature

repellence, wettability decrease and negligible colour variations. AG2

had a limited durability of one cleaning cycle [44].
In a recent study, Carmona-Quiroga et al. applied on Portland
Woodkirk (sandstone)
Portland (limestone)

limestone and Wood-kirk sandstone two anti-graffiti coatings: an AG1

(water dispersion of polyurethane with a perfluoropolyether backbone)
Lecce stone

and an AG2 (water based crystalline micro wax) [45]. Both coatings
(limestone)
Lithotype

improved the graffiti removal without significant colour and gloss

changes. However, both anti-graffiti products underwent colour
changes after artificial and natural weathering conditions (UV-B ra-
Masieri and Lettieri
Table 1 (continued)

diation was more aggressive than marine conditions during 1 year).

Carmona-Quiroga
et al. [43]

Although the water repellence remained inalterable for both surfaces,

AG1 decreased the water vapour permeability on both stones and AG2
Reference

[40]

decreased the contact angles.

Licchelli et al. tested anti-graffiti systems composed of montmor-
illonite nanoparticles on Pietra di Lecce [46]. These products were

96
V. Gomes et al. Progress in Organic Coatings 113 (2017) 90–109

Dellite® HPS (natural Na-montmorillonite) and Dellite®43B (natural A brief summary of the diverse cleaning methods is shown in
purified montmorillonite) dispersed in Fluorolink® P56 (fluorinated Table 3 and are discussed in the following sections.
polyurethane). The nanoclay structural features and its concentration
influenced the coating behaviour. Dellite®43B exhibited a higher water 4.1. Chemical cleaning methods
repellence and better barrier effect against acrylic spray paint
(ROLMACRYL) than Dellite® HPS, which could be easily removed by Chemical cleaning is due to the reaction between the chemical
MEK solvent without induce significant alterations. However, the per- product applied and the paint, achieving its dissolution and extraction
manent marker diffused into the polymer matrix. [53]. Chemical agents are available in a variety of compositions and
Kronlund et al. tried to remove Montana Cans: Montana Black (ni- consistencies (e.g. gels and poultices) to be adapted to different sub-
trocelluloic and alkyd resins) and Montana White (alkyd resins with strates [1,54]. Already in 1999, Urquhart reported the ghosting due to
oxidising drying) from Carrara marble after apply Capstone FS-63 graffiti penetration, mainly in porous stones [6]. Later, this was cor-
protective coating [47]. The coating formulations containing ethylene roborated by other authors that tried to remove spray paints (markers,
glycol showed better penetration results, due to the slow evaporation black Krink® and Nero d’inferno inks) from dolomitic white marble with
rate. Despite Montana Black was slightly harder to wash away, there Elephant Snot® followed by Graffipaste® [20,21].
were no remarkable differences in the cleaning effectiveness achieved The traditional solvents recommended for limestone, marble,
for the different coatings tested. sandstone, slate and granite are usually based on organic solvents like
Moura et al. used on Moleanos limestone two sacrificial coatings: a methylene and acetone or alkali caustic removers [55]. The solvent-
Ssilox (water-based organosiloxane emulsion with additives) and a Snano based removers work by weakening the adhesion between the paint and
(with SiO2 nanoparticles) and a permanent Pfluor (water-based fluor- the stone, while caustic removers broke down alkyd based paints by
oalkylsiloxane) coatings after painting with a silicate-based paint [48]. saponification [1,6], i.e., interaction of fats and oils from the trigly-
The sacrificial anti-graffiti Snano had the best physical performance, cerides with a strong nucleophilic base – that attacks polar bonds, ac-
highly reducing the water absorption without significantly influence on celerating the cleavage of the ester bonds and releasing fatty acids salts
the drying behaviour, water vapour permeability and colour. The per- and glycerol. In Avebury Neolithic sandstones and Stonehenge Heel,
manent anti-graffiti Pfluor had also shown an optimal drying perfor- methylene dichloride and acetone, prior to laser, was successfully
mance. Ssilox produced the lowest colour variations [48]. Those authors tested to remove the remaining paint [56]. More recently Samolik et al.
attested that the cleaning effectiveness depends on the composition of used a mixture of ethanol, acetone and xylene to successfully remove
the graffiti painting, the anti-graffiti and the substrate characteristics nitrocellulosic acrylic and alkyd based paint (Montana Gold from
[49]. The cleaning of grey paint was more successful in samples treated Motip-Dupli®) on limestone, sandstone, plaster and brick. However, it
with Ssilox and for the blue paints the best results were achieved with did not succeed in removing the alkyd black paint Montana Black from
Snano and Pfluor. Most of the paints was removed with high-pressurized Motip-Dupli® [22]. Carvalhão & Dionísio used a solution based on po-
cold water and some residues were detected. The highest colour change tassium hydroxide and surfactants (AGS 60™) to remove MOTIP
was observed in samples without anti-graffiti protection. HOME & HOBBYLACQUER® paints and achieved a homogeneous
In Table 2 are highlighted the methods used to evaluate the per- cleaning of the Portuguese Branco marble, while for Lioz limestone an
formance of anti-graffiti effectiveness, harmfulness and durability. extra-accumulation on stilolytes was registered [23]. The surface
From the critical analysis performed one verified that 30 different lightness also increased and dissolution of grain boundaries and loss of
techniques/methods were used in that evaluation. The most used are crystals was detected. Pozo-Antonio et al. tested both organic solvents
colorimetry, contact angle measurement, scanning electron microscopy, and caustic removers Wendrox® and Eligraf® based in dichloro-methane,
water vapour permeability and capillarity water absorption. organic acids, solvents and anionic surfactants and QuitaGraffi
200®–QuitaSombras 60® (QG + QS) rich in potassium hydroxide. These
4. Graffiti removal procedures were tested on less studied substrates, two granites: Silvestre and Rosa
Porriño, with satisfactory results for various alkyd Montana Colors®.
Graffiti removal procedures, despite apparently simple, are poten- The silver graffiti required a subsequently application of TS-99 paint
tially harmful and irreversible. Therefore, it is crucial to adequate the stripper [15]. However, chemical contamination was detected for
decision-making process to achieve satisfactory results. In the selection cleanings performed with Wendrox® and QG + QS.
of a graffiti removal method, several aspects must be considered,
namely the chemical composition of the paint and the intrinsic char- 4.2. Mechanical cleaning methods
acteristics of the stone (texture, mineralogical composition, petrophy-
sical properties, weathering degree, etc.). Several recommendations for The mechanical cleaning acts through an abrasive process of the
the cleaning of Cultural Heritage stones have been proposed in the past surface. This kind of technique based on pressurized projection of water
decades [50,51] as well as methods for assessment the cleaning results and abrasives is frequently associated with an inhomogeneous cleaning,
[52]. several substrate damages and an increase of the susceptibility to retain
Although the traditional procedures applied by professionals are the soiling by the substrate [1,54]. The pressure applied may have an
chemical and mechanical methods (Fig. 4), scientific publications based abrasive effect and cause damage to the valuable surfaces [1], as ver-
on the evaluation of their cleaning effectiveness are scarce.The first ified by different authors in dolomitic marble [20,21]. Later, Samolik
scientific paper focused on graffiti removal on stone is dated of 2000. et al. also found this abrasive effect on several construction materials
Nowadays there are about 22 papers published in scientific journals (limestone, sandstone, plaster and brick) using high-pressure water jet
about this theme [30], not involving the use of anti-graffiti protection. and blast cleaning with sand and glass particles [22]. Recently, Car-
Most of these papers (60%) are focused on carbonate stones (Fig. 3), eddu & Akkoyun studied the efficiency of the application of water-jet
which are also the most studied stones for anti-graffiti coatings (Fig. 3). with different operational conditions on painted Carrara marble sur-
Concerning the graffiti cleaning methods, the most studied are un- faces, finding by means of image analysis and roughness tests, that the
doubtedly the lasers (Fig. 3), corresponding almost 50% of the analysed best cleaning operating conditions for this stone were an inter-distance
papers. between passes of 0.5 mm, a 200 MPa-water pressure, and a
Biological methods correspond to 8% of the analysed papers, but it 12.0 m min−1-travel speed [57].
must the mentioned that none of these papers are specifically applied to In order to counteract the detected damages due to abrasive tech-
stone substrata. In fact correspond to laboratorial studies involving the niques, micro-blasting has been proved to minimize them [1]. In the
biodegradation of paints over glass surfaces. last years, low pressure projection methods have been developed with

97
 Table 2
Analytical techniques used in different researches focused on the evaluation of the anti-graffiti effectiveness on stones. Symbols show the different evaluation performed in each work with the different techniques; ■ shows that the previous
characterization of the stone was carried out; ● the graffiti paints by themselves were evaluated; ▲ the anti-graffiti coatings were characterized and △ shows the techniques used to evaluate the protection level of the coated surfaces after graffiti
cleaning.
V. Gomes et al.

Reference Optic microscopy Colorimetry Gloss meter FTIR XRD Raman Spectrophotometer Differential scanning SEM Contact
for liquids calorimetry angle

Gardei et al. [29] ■

▲
△
Carmona-Quiroga et al. [31] ■ ■ ■ ■ ■
▲ ▲ ▲ ▲
△
Malaga and Bengtsson [26] ■ ■
▲ ▲
Carmona-Quiroga et al. [32] ■ ■
▲ ▲
García et al. [34] ■ ■
▲ ▲
Mueller and Malaga [36] ■ ■
▲ ▲
Licchelli et al. [37] ■ ■ ■ ■
▲ ▲ ▲ ▲
△
Carmona-Quiroga et al. [28] ■
▲
Licchelli et al. [38] ■ ■ ■ ■ ■
▲ ▲ ▲ ▲ ▲
Lettieri and Masieri [39] ● ● ● ● ●

98
▲ ▲ ▲ ▲ ▲
Licchelli et al. [44] ■ ■ ■
▲ ▲ ▲
△ △ △
Meng et al. [35] ■ ■
● ● ●
▲ ▲ ▲
△ △
Carmona-Quiroga et al. [33] ■
▲
Cocco et al. [42] ■ ■ ■ ■
● ● ●
▲ ▲ ▲ ▲ ▲
△ △ △ △
A. Moura et al. [46] ■ ■
▲ ▲
Kronlund et al. [45] ■ ■
● ●
▲ ▲
△ △
Ana Moura et al. [47] ■ ■ ■
● ● ●
▲ ▲ ▲
△ △ △
Carmona-Quiroga et al. [43] ■ ■ ■ ■
● ●
▲ ▲ ▲ ▲ ▲
△ △ △ △

(continued on next page)

Progress in Organic Coatings 113 (2017) 90–109
 Table 2 (continued)

Reference Optic microscopy Colorimetry Gloss meter FTIR XRD Raman Spectrophotometer Differential scanning SEM Contact
for liquids calorimetry angle
V. Gomes et al.

Masieri and Lettieri [40] ■ ■

● ●
▲ ▲
△ △

Reference Capillary water Drying Water vapour Air Water absorption at Water saturation Water-accessible Apparent Specific
absorption behaviour permeability permeability atmospheric pressure coefficient porosity density gravity

Gardei et al. [29] ■ ■ ■

▲ ▲ ▲
△ △ △
Carmona-Quiroga et al. [31] ■ ■ ■ ■
▲ ▲ ▲

Malaga and Bengtsson [26]

Carmona-Quiroga et al. [32]

García et al. [34] ■ ■ ■ ■

▲ ▲ ▲ ▲
Mueller and Malaga [36] ■ ■ ■ ■ ■
▲ ▲ ▲ ▲
Licchelli et al. [37] ■
▲

99
Carmona-Quiroga et al. [28]

Licchelli et al. [38] ■ ■

▲ ▲
Lettieri and Masieri [39]

Licchelli et al. [44] ■

▲
△
Meng et al. [35] ■
●
▲
△
Carmona-Quiroga et al. [33]

Cocco et al. [42]

A. Moura et al. [46] ■ ■ ■ ■

▲ ▲ ▲ ▲
Kronlund et al. [45]

Ana Moura et al. [47]

(continued on next page)

Progress in Organic Coatings 113 (2017) 90–109
 Table 2 (continued)

Reference Capillary water Drying Water vapour Air Water absorption at Water saturation Water-accessible Apparent Specific
absorption behaviour permeability permeability atmospheric pressure coefficient porosity density gravity
V. Gomes et al.

Carmona-Quiroga et al. [43]

Masieri and Lettieri [40]

Reference Low pressure water Mercury intrusion Karsten testing pipe Roughness Confocal Structured light Photogrammetry Petrographic Polarized Viscosimeter Inverse gas
absorption porosity microscopy scanning microscopy microscopy chromatography

Gardei et al. [29] ■

▲
△
Carmona-Quiroga et al. [31] ■ ■ ■ ■
▲ ▲ ▲

Malaga and Bengtsson [26] ■

▲
Carmona-Quiroga et al. [32]

García et al. [34]

100
Mueller and Malaga [36] ■ ■ ■ ■ ■
▲ ▲ ▲ ▲
Licchelli et al. [37]

Carmona-Quiroga et al. [28] ■

▲
Licchelli et al. [38]

Lettieri and Masieri [39]

Licchelli et al. [44]

▲

Meng et al. [35] ■

●
▲
△
Carmona-Quiroga et al. [33]

Cocco et al. [42] ■

▲
△
A. Moura et al. [46]

Kronlund et al. [45]

(continued on next page)

Progress in Organic Coatings 113 (2017) 90–109
V. Gomes et al. Progress in Organic Coatings 113 (2017) 90–109

the objective to avoid the substrate damage. Low pressure steam was
used to remove a water soluble white paint from Avebury Neolithic
Sandstone [56]. Carvalhão & Dionísio tested Sponge-Jet® (a dry soft-
chromatography

abrasive blasting media with a sponge-like urethane polymer involving

spherical calcium carbonate particles) and Exastrip® (pure spherical
Inverse gas

calcium carbonate particles) to clean Branco marble and Lioz limestone

[23]. Despite their successful level of cleaning, punctual paint traces

as
were found in Lioz stilolytes. The topography changes were reduced
Viscosimeter

comparatively to those registered in the surface cleaned with an alka-

line cleaner. However hydrophobicity increased, probably due to un-
removed polymers in the pores and also a significant global colour
changes were detected. Pozo-Antonio et al. tested Hydrogommage®
which is based on a circular projection of a mixture of air–water–micro
microscopy
Polarized

grained abrasive (99% SiO2 content, 0.5–0.1 mm grain size) at low-

pressure (0.5–1.5 bar) to clean alkyd spray graffiti paints (black, blue,
red and silver of Montana Colours® S.L.) on Rosa Porriño and Silvestre
granites with satisfactory results. However, an increase around 10 μm
on the average roughness (Ra) for both substrates was reported [15]. In
Petrographic
microscopy

a later work [58], the same authors used hyperspectral imaging tech-
nique to characterize the cleaning performances, being Hydro-
gommage® and Nd:YVO4 laser the more suitable techniques. This con-
clusions are in accordance with optical microscopy and SEM
Photogrammetry

observations.

4.3. Laser cleaning

The mechanism responsible for laser cleaning is the ablation; the

undesired layers are removed by the beam irradiation when the fluence
Structured light

(energy deposited per unit area) exceeds a critical threshold which is an

intrinsic property of the material to be extracted [59,60]. The most used
scanning

lasers in stone cleaning are the different harmonics-wavelengths of

neodymium-based systems (Fig. 5), i.e. Nd:YAG or Nd:YVO4 [4]. Sev-
eral advantages can be pointed out regarding laser cleaning namely the
microscopy
Confocal

non-mechanical contact, its selective action since it provides a located

and accurate cleaning and the adjustment of the cleaning conditions in
real time [4]. The specific application of laser to extract graffiti on
Cultural Heritage stones is rather reduced comparatively to other al-
teration forms, such as biological colonization, black crust, encrusta-
Roughness

tions, etc. [4]. In 2003, Costela et al., were the pioneers to apply this
technology to remove paints on marble obtaining satisfactory results
without damage by using the wavelength of 355 nm whereas 532 nm
Karsten testing pipe

radiation left remnants of polymeric base [17]. Later Gómez et al. used
the same paints and stone to compare Nd:YAG at 1064 nm with XeCl
excimer at 308 nm. While Nd:YAG left remains and darkened the sur-
face, XeCl satisfactorly cleaned without damage [18]. Daurelio tested
three laser protocols for graffiti removal on Bisceglie dolmen with a
Nd:YAG working at 1064 nm and 532 nm [61]. The first protocol in-
volving a laser beam in air or via a guiding fibre glass, removed sa-
Mercury intrusion

tisfactorily black paint. In the second methodology, a rectangular-

shaped laser beam removed ink, graphite and spray paints. Then, in the
porosity

third procedure, a rectangular-shaped laser beam with a mixture of

water and red-brown earth removed indelible and fluorescent paint
markers. Later, Andriani et al. tested three different modes of a Nd:YAG
Low pressure water

laser (normal mode, short free running and Q-switched) using the dif-
ferent Daureliós techniques. The inks of markers and pens (no spray
absorption

graffiti paintings) were successfully removed from Travertino, Sabbie,

Tufo Carparo and Chianca Pugliese with the Q-switch mode with the
▲
△
■
●

third protocol and with the second one with water [62]. The previously
Carmona-Quiroga et al. [43]

tested spray paints and markers were characterized by pyrolysis-gas

Masieri and Lettieri [40]

chromatography/mass spectroscopy and Fourier transform infrared

Ana Moura et al. [47]

spectroscopy and alkyd, styrene-acrylic resins were found in some of

Table 2 (continued)

them. The laser cleaning parameters for Q-switched Nd:YAG laser were
optimized [63]. As reported before, Ortiz et al. cleaned different paints
Reference

on dolomitic white marble; despite a complete extraction with Nd:YAG

laser working at 266 nm was detected, damage was induced. At
1064 nm it was only achieved the removal of black spray but with

101
V. Gomes et al. Progress in Organic Coatings 113 (2017) 90–109

Fig. 4. A and B: Graffiti cleaning procedures performed for laboratory evaluations. A: Chemical cleaning with Graffiti GR3 3M® of silver graffiti paint (Montana Colours®) on Rosa Porriño
granite (NW Spain); B: Mechanical cleaning with IBIX® of silver graffiti paint (Montana Colours®) on Vilachan granite (NW Spain). C and D: Graffiti cleaning procedures performed in
monuments: C: Chemical cleaning in Acção Virtuoza statue of Palácio da Ajuda (Lisbon); D: Mechanical cleaning with Sponge-Jet® in Adamastor statue in miradouro de Santa Catarina
(Lisbon). Sources: A: the authors; B: Alberto Pereira; C: Maria Inês Gomes and D: Miguel Carvalhão.

yellowing effect [21]. Authors working on laser cleaning of black en- cleaning. In the later research, laser also caused melting of the biotite
crustations on marble also reported this dramatic colour-change grains, fracturing of the quartz grains and in case of the cleanings of
working with Nd:YAG at 1064 nm, which were attenuated by moist- black and silver paints, a possible change in the hydration state of iron
urizing the stone surface [60]. Samolik et al. also reported yellowing oxides and oxyhydroxides covering fissures was found. Pozo et al. also
with 1064 nm, darkening with 355 nm and satisfactory results with applied the same laser in the removal of the same paints over Rosa
532 nm [22]. While with MotipDupli® Montana Black paints were not Porriño and Silvestre granites [15]. The laser was satisfactory for all the
possible to be successfully removed, acceptable results were obtained paints except silver. In fact, under SEM, these samples present a surface
for MotipDupli® Montana Gold [22]. completely covered by a carbon film rich in aluminium particles. De-
Fiorucci et al. studied different fluencess (from 0.1 J cm−2 to spite the results obtained for silver paint, in a later study [58], the
1.2 J cm−2) of Nd:YVO4 laser at 355 nm applied on Rosa Porriño Nd:YVO4 laser at 355 nm proved by means of hyperspectral imaging
granite finding optimal results with 0.1 J cm−2. Undesirable damages, technique to be one of the most suitable cleaning techniques. More
such as melting of the biotite and loss of the pink coloration of the recently, Ramil et al. studied the optimal laser fluence ranges to clean
potassium feldspar grains occurred in cleanings at 0.3 J cm−2 [13]. graffiti on silicates with the previously used Nd:YVO4 laser at 355 nm
Researches on laser cleaning of other kind of deterioration forms, on Rosa Porriño granite painted with the referred Montana Colors®
concluded that Fe compounds are very sensitive in response to 1064 nm paints. The cleaning effectiveness was found to be influenced by the
laser irradiation [64,65]. Urones-Garrote et al. after the laser irradia- polymineralic characteristic of the granite since the four main minerals
tion of an uncoated granite with Nd:YAG at 355 nm assigned the de- presented different behaviours. For quartz and K-feldspar grains the
colouration effect of the pinkish Rosa Porriño granite to the induced higher cleaning effectiveness levels were achieved with 0.1–0.2 J cm−2,
thermal effects in the microstructure and composition of potassium regardless of the graffiti colour. For plagioclase, the cleaning effec-
feldspar grains [66]. Rivas et al. working with Nd:YVO4 at 355 nm to tiveness was achieved from 0.1 to 1.0 J cm−2depending on the graffiti
clean several colour graffiti on granite confirmed the influence of the colour. Finally, biotite started to be cleaned with 0.06 J cm−1 (with
chemical composition of the graffiti on the cleaning effectiveness; the melting occurrence at the lowest fluence). Textural characteristics of
cleaning of red, blue and black paints from Montana Colors® had similar the stone such as fissural system and cleavage also interfere in the
satisfactory results, while the surface cleaned of silver graffiti showed a graffiti penetration and consequently in the cleaning performance [67].
translucid film easily visible under naked eye [16]. Moreover paint High Power Diode Laser (HPDL) was tested for the first time by
penetration into the granite fissures was reported and remained after Salimbeni et al. with a Rofin-Sinar mod. DLO25S emitting up to 2.5kW

102
 Table 3
Graffiti cleaning procedures carried out by several authors. The lithotypes and their nature, the graffiti paints and their composition and the cleaning procedures used to extract the graffiti are reported. n.p.: not performed, n.a.; not applied.

Reference Lithotype Nature Graffiti Graffiti composition Cleaning method

V. Gomes et al.

Chapman [56] Sarsen Stone in West Siliceous Black gloss and white emulsion water soluble paint n.p. - Low pressure steam (mechanical method)
Kennet Avenue at Avebury - Laser: Quantel Q-switched Nd:YAG at 1064 nm.
(sandstone) - Combination of methylene dichloride (chemical method) with
Quantel Q-switched Nd:YAG at 1064 nm.
Sarsen Stone in Heel stone Siliceous Spray paint • Acetone
at Stonehenge (sandstone) • Laser: Quantel Q-switched Nd:YAG at 1064 nm and 532nm
Salimbeni et al. Travertine Calcareous Black spray paint n.p. - Laser HPDL at 808–940 nm
[66] Carrara (marble) Calcareous
Daurelio [59] Bisceglie Dolmen Calcareous Black spray paint, markers and pens: fluorescent, n.p. - Laser: Nd:YAG at 1064 nm and 532 nm.
(limestone) permanent
Costela et al. [17] One unknown marble Calcareous - Trans-colour®: white, yellow, pink, green, black, Acrylic or styrenic−based binders. - Laser: Q-switch Nd:YAG at 532 nm and 355 nm.
golden, and silvery spray paints.
- Felton®: blue spray paint.
Gómez et al. [18] One unknown marble Calcareous Same as (Costela et al., 2003) Acrylic or styrenic−based binders. - Laser: Q-switch Nd:YAG at 1064 nm
- Laser: XeCl excimer at 308 nm
Andriani et al. [60] Chianca Pugliese Calcareous Markers and pens: fluorescent, permanent, water-based, n.p. - Lasers: two Nd:YAG systems: Palladio by QUATA SYSTEM
(limestone) acrylic tempera, metallic paint, waterproof and SMART CLEAN II by EL·EN in N-Mode, Q-Switch and
Sabbie (limestone, quartz Artificial SRF at 1064 nm
and silica)
Tufo Carparo or Piera Calcareous
leccese (limestone)
Travertino (limestone) Calcareous
Sanjeevan et al. Mortar Artificial n.a. n.p. - Laser: Nd:YAG at 1064 nm
[61]
Fiorucci et al. [13] Rosa Porriño (granite) Siliceous Mtn®classic: ultramarine blue (RAL code R-5002), devil Red and blue paints have alkyd −based binders, - Laser: Nd:YVO4 at 355 nm

103
red (R-3027), grafite black (R-9011) and silver chrome. black also contains a polyester resin and silver a
mineral oil likely a polyolefin (polyalkene).
Antúnez et al. [20] Dolomitic white marble Calcareous Black, green and red spray paints; Black, green and red Black, green and red spray paints have acrylic - Elephant Snot plus Graffipaste (chemical agents)
markers and black Krink® and Nero d’inferno inks −based binders. - Pressurized water (mechanical agent)
Rivas et al. [16] Rosa Porriño (granite) Siliceous Same as (Fiorucci et al., 2011) Same as (Fiorucci et al., 2011) Same as (Fiorucci et al., 2011)
Vilachán (granite) Siliceous
Fiorucci et al. [14] One unknown granite Siliceous Same as (Fiorucci et al., 2011) Same as (Fiorucci et al., 2011) Same as (Fiorucci et al., 2011)
Ortiz et al. [21] Dolomitic white marble Calcareous Same as (Antúnez et al., 2012) Same as (Antúnez et al., 2012) - Lasers: Same as (Antúnez et al., 2012) plus two Q-switched
Nd:YAG systems Art Light II by CTS Srl at 1064 nm and
Minilite by Continuum Inc. at 266 nm
Penide et al. [67] Pink Morelia Quarry Siliceous Yellow, red, green, blue, grey and black spray paints. n.p. - Laser: HPLD at 940 nm
(reolitic stone)
Carvalhão and Lioz (limestone) Calcareous MOTIP HOME & HOBBYLACQUER®: Carmine red (RAL Alkyd and polyester −based binders. - Dry soft-abrasive blasting media MC1 spherical calcium
Dionísio [23] Branco (marble) Calcareous 3002), Gentian Blue (RAL 5010) and Jet black (RAL 9005) carbonate particles involved in sponge-like urethane
polymer
- Dry soft-abrasive blasting media MC2 pure spherical calcium
carbonate particles (mechanical methods)
- AGS 60™ based on a solution of potassium hydroxide
(chemical method).
Samolik et al. [22] One unknown limestone Calcareous Montana Black® and Montana Gold® from MotipDupli®: Montana Gold® has nitrocellulose, acrylics and - For both Montana Black® and Montana Gold® Pressure water
One unknown sandstone Siliceous white, red and black spray paints alkyd − based binders. jet and blast cleaning with sand and glass particles
Plaster Artificial (mechanical methods) and Nd:YAG at 1064 nm, 532 nm
Brick Artificial and 355 nm.
- For Montana Gold® a mixture of ethanol, acetone and xylene
(chemical methods)
- For Montana Black® a mixture of ethanol, acetone and naphtha
(chemical methods).
Pozo-Antonio et al. Rosa Porriño (granite) Siliceous Same as (Fiorucci et al., 2011) Same as (Fiorucci et al., 2011) - AGS − Anti-graffiti Systems: Wendrox® and Eligraf® both
[15] Silvestre (granite) Siliceous based organic acids,
(continued on next page)
Progress in Organic Coatings 113 (2017) 90–109
V. Gomes et al. Progress in Organic Coatings 113 (2017) 90–109

cleaning solution with no information about the composition,

for silver chrome the paint stripper TS-9 was subsequently
with a black paint on Carrara marble [68]. In comparison with modu-

- QuitaGraffi 200® − QuitaSombras 60® two phase graffiti

air–water–micro grained abrasive (mechanical method).

lated waves, continuous waves of a high power diode laser system

- Hydrogommage® based on the circular projection of

HPDL successfully extracted paint in a Mexican Pink Morelia Quarry
due to its two steps process: the first low irradiance pass leads to
combustion–carbonization of the paint and the second pass removes it
[69].

Same as (Pozo-Antonio et al., 2016)

- Water-jet (mechanical method)

4.4. Biocleaning

- Laser: Nd:YVO4 at 355 nm.

- Laser. Nd:YVO4 at 355 nm

Biocleaning consists on the use of living organisms to remove en-

vironmental pollutants or other exogenous substances, such as graffiti
paints, through biodegradation due to their metabolic ability to use
Cleaning method

organic/inorganic compounds for growth [5]. The studies published

focused directly on biocleaning of graffiti spray paint are still scarce.
used.

Giacomucci et al. demonstrated that the sulphate-reducing bacterium

Desulfovibrio desulfuricans ATCC 13541 is able to degrade ni-
trocellulosic-based paint binder, however the complete elimination/
detachment of the paint layer from the glass substrate was not observed
[70]. Sanmartín et al. using culturable microorganisms gave another
step phylogenetically identifying nine bacterial and one fungal strains
with the capability to degrade alkyd and polyester spray paint resins
(Fig. 6) [71]. Germinario et al. used different lipases (a mixture of li-
Same as (Fiorucci et al., 2011)

Same as (Fiorucci et al., 2011)

pases from non-specified bacteria strains; lipase from Candida rugose

and lipase from Candida antarctica)to remove acrylic marker pen inks
Uni-posca®, Tratto® and Saratoga® from unglazed ceramic substrates.
Graffiti composition

The acrylic paints were removed with an oil in water micro emulsion
even without the enzyme, but in general terms, the cleaning perfor-
mance was enhanced by the addition of a lipase. Moreover, there was
not found a formulation to effectively remove all kinds of paints. A
n.p.

future research line is proposed to study these formulations on orna-

mental stones [72].

4.5. Effectiveness and harmfulness evaluation of the cleaning methods

The analytical techniques used to evaluate the cleaning effective-

ness and harmfulness are presented in Table 4. From the critical ana-
lysis performed one verified that 15 different techniques/methods were
used in that evaluation and among these, the most applied techniques/
Same as (Fiorucci et al., 2011)

Same as (Fiorucci et al., 2011)

methods are optical microscopy, colorimetry and scanning electron

microscopy. Back in 2007 Sansonetti et al. referred the risks associated
with the cleaning procedures and established some guidelines to be
followed by the scientific community. Briefly, step A involves the
evaluation of the potential harmfulness of the cleaning method and step
B the optimization of the cleaning parameters for each specific cleaning
Graffiti

procedure for a specimen in situ and for laboratory specimens [73]. The
n.a.

importance of long term observations are also highlighted. These

guidelines were created since a gap in the analytical characterization of
the cleaning performance was found. From the studied literature this
Same as (Pozo-
Antonio et al.,

problem can still be noticed, however as can be seen in Table 4, despite

Calcareous

Siliceous

not all the studies carry out an analytical characterization, most of the
Nature

2016)

ones that actually do it encompass the previous characterization of the

stone, of the graffiti paints and the techniques used to evaluate the
graffiti cleaning effectiveness.
Same as (Pozo-Antonio

Rosa Porriño (granite)

5. Final considerations and future research lines

Carrara (marble)
et al., 2016)

This review presents a state of art regarding: (i) the composition of

Lithotype

the graffiti spray paints commonly used by graffiti-writers in Cultural

Heritage stones, (ii) the protective effectiveness of anti-graffiti coatings
on different stones and (iii) the most remarkable findings on graffiti
Pozo-Antonio et al.
Table 3 (continued)

Akkoyun [57]

cleaning procedures on stone.

Ramil et al. [65]

Anti-graffiti protective coatings improve the graffiti removal effi-

Careddu and

cacy comparatively to uncoated surfaces, however it can be compro-

Reference

[56]

mised in more porous substrates, such as limestones. The impregnation

of the anti-graffiti coatings is highly influenced by the pore size, and the
porosity is the factor that mainly influences on the cleaning

104
V. Gomes et al. Progress in Organic Coatings 113 (2017) 90–109

Fig. 5. A and B: Laser equipment: A: a ns Nd:YVO4 laser working at 355 nm in Laboratorio de Aplicacións Industriais do Laser (LAIL) at Escola Politécnica Superior (Universidade da
Coruña, Spain). B: a ns Nd:YAG laser working at 1064 nm and 355 nm (single or simultaneously) at Institute of Electronic Structure and Laser-FORTH (Crete, Greece). C–F: Different
cleaning tests performed with the laser Nd:YAG previously showed in order to optimize the cleaning of blue graffiti on Vilachan granite (C: 1064 nm, 0.9 J cm−2; D: 355 nm, F
0.4 J cm−2) and also silver graffiti on Lioz limestone (E: 1064 nm, F: 1.1 J cm−2 and 6 pulses; F: 1064 nm, F: 1.1 J cm−2 and 20 pulses). Sources: the authors. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)

effectiveness. The application of the anti-graffiti by capillary absorption substrate. It is also possible to state that most of the researches, contrary
produces acceptable decreases in the vapour permeability. It has to be to those based on the anti-graffiti products, does not consider the effects
noticed that the ability of some inks/paints to penetrate through the of ageing in their effectiveness. Therefore, more researches addressed
protective coatings may be related to the cured/uncured polymer fea- on the effectiveness evaluation of cleaning of aged graffiti should be
tures; the uncured coating can more easily allow the migration of the performed.
ink/paint to the stone. The most successful procedures to extract different graffiti on stone
From a general overview, considering the type of substrate, most of were analysed taking into account the painting binder:
the references are focused on carbonate stones. Regarding to the graffiti
removal methods, more than half of the consulted studies are centred • For acrylic graffiti paintings the better cleaning results were ob-
on the application of lasers. The majority of the analysed researches tained with Nd:YAG laser at 355 nm and XeCl excimer at 308 nm
was not capable to remove graffiti without induce damage in the both in Trans-colour® and Felton® paints on marble.

Fig. 6. A: Sampling process of microorganisms with potential capacity to degrade graffiti, from car bodies found in junk yards in the Northeastern United States (Cambridge, MA), using
moistened swabs. B: Examples of the different strains with ability to remove and degrade graffiti spray paint, isolated from graffiti and associated environments [71]. C: Plastic test tube
containing one isolated colony [71] and a microscope slide which had one side coated with a uniform layer of graffiti paint [70], showing the biodeterioration due to microbial attack.
Sources: Patricia Sanmartín.

105
 Table 4
Analytical techniques used by several authors to evaluate the cleaning effectiveness achieved for different cleaning procedures to extract graffiti on stones. Symbols show the different evaluation performed in each work with the different
techniques; ■ shows that the previous characterization of the stone was carried out; ● the graffiti paints by themselves were evaluated and ○ shows the techniques used to evaluate the graffiti cleaning effectiveness.
V. Gomes et al.

Reference Optic Colorimetry FTIR XRF CHNS UV–vis/NIR XRD LIBS SEM Contact Roughness Interferometric Confocal Petrographic Hyperspectral imaging
microscopy spectrometer angle profilometry microscopy microscopy technique

Salimbeni et al. [66] ■ ■ ■

● ● ●
○ ○ ○
Costela et al. [17] ■ ■
● ●
○ ○
Gómez et al. [18] ■ ■ ■
● ● ●
○ ○ ○
Andriani et al. [60] ■
●
○
Sanjeevan et al. [61] ■ ■
● ●
○ ○
Fiorucci et al. [13] ■ ■ ■
● ● ● ● ● ● ●
○ ○ ○
Antúnez et al. [20] ■ ■ ■
● ● ●
○ ○ ○
Rivas et al. [16] ■ ■ ■ ■ ■
● ● ● ● ● ● ● ● ●

106
○ ○ ○ ○ ○
Fiorucci et al. [14] ■
●
○
Ortiz et al. [21] ■ ■ ■ ■ ■
● ●
○ ○
Penide et al. [67] ■ ■ ■
● ●
○ ○ ○
Carvalhão and ■ ■ ■ ■ ■ ■
Dionísio [23]
● ● ● ● ● ●
○ ○ ○ ○ ○ ○
Samolik et al. [22] ● ■
●
○
Pozo-Antonio et al. ■ ■ ■ ■ ■ ■
[15]
● ● ● ● ● ●
○ ○ ○ ○ ○ ○
Pozo-Antonio et al. ■ ■ ■ ■
[56]
● ● ● ●
○ ○ ○ ○
Careddu and Akkoyun ■
[57]
●
○
(continued on next page)
Progress in Organic Coatings 113 (2017) 90–109
V. Gomes et al. Progress in Organic Coatings 113 (2017) 90–109

Hyperspectral imaging • The best cleaning results for alkyd graffiti paints were obtained with
the chemical agents AGS 60™ and QuitaGraffi 200®–QuitaSombras
60® (rich in potassium hydroxide-a clear evidence of the satisfactory
cleaning effectiveness by saponification)-and paint stripper TS-99;
Nd:YVO4 laser at 355 nm; mechanical soft-abrasive blasting media
technique

Sponge-Jet®, Exastrip® and Hydrogommage®. This results were ob-

tained in Montana Colors® and MOTIP HOME & HOBBYLACQUER®
■
●
○

on limestone, marble and granite.

• For nitrocellulosic paints the best results were obtained with a
mixture of ethanol, acetone and xylene chemical agents, probably
Petrographic
microscopy

the same solvents used in the resin formulation, and with Nd:YAG at
1064 nm and 532 nm, for Motip-Dupli® Montana Gold on limestone
and sandstone [22].

The chemical methods are among the most economic solutions, al-
microscopy

though they may penetrate in the substrate and cause irreversible da-
Confocal

mages such as chemical contamination and shadows. Moreover they

represent a risk to the environment and to the conservator-restorer
■
●
○

health. It is important to highlight the current studies focused on the

hydrogel technology that achieves promising results in the extraction of
overpainting’s and undesired graffiti from street art [74]. Mechanical
Interferometric

methods allow a complete paint extraction and are also an economic

profilometry

solution but can damage the substrate and generate pollutants through
the release of fine dust particles. Despite the lasers do not allow me-
chanical contact, they provide a located and accurate cleaning with a
selective action and they can be adapted in real time. As chemical
Roughness

methods, lasers depend on the chemical characteristics of the paint that

lead their capacity of radiation absorption. Among their drawbacks,
lasers may alter the colour of the substrate, induce mineralogical al-
teration and are the most expensive alternative. Further studies in order
to optimize the laser cleaning of graffiti on different stones should be
Contact
angle

performed to minimize those disadvantages. Bioremediation for graffiti

removal is an interesting field in expansion, with the promise of of-
SEM

fering a friendly environmental low cost solution with a good public

■
●
○

acceptance however we must keep in mind that many graffiti paints

LIBS

have biocides as additives in their formulation.

Despite some analytical techniques are employed in the evaluation
XRD

of the cleaning effectiveness, the complementarity use of more analy-

tical equipment should be applied in order to scientifically validate the
obtained results.
Further studies focused on the cleaning effectiveness of aged graffiti
spectrometer
UV–vis/NIR

paintings under different urban pollutants have been developed in

order to obtain more realistic simulations to the graffiti cleaning
practice.
CHNS

Acknowledgements
XRF

This work is co-funded by Fundação Calouste Gulbenkian

(Programa de Estímulo à Investigação 2016, P 202710) and by the
FTIR

Strategic project FCT- UID/ECI/04028/2013. J.S. Pozo-Antonio was

supported by a postdoctoral contract with the University of Vigo within
Colorimetry

the framework of the 2011–2015 Galician Plan for Research,

Innovation and Growth (Plan I2C) for 2014.
The authors acknowledge Cristina Montojo (Escola Superior de
Conservación e Restauración de Bens Culturais de Galicia, Spain),
Alberto Pereira (Clinarte S.L.), Miguel Carvalhão, Maria Inês Gomes
microscopy

(Laboratório José de Figueiredo – DGPC, Portugal) and Patricia

Sanmartin (Universidade de Santiago de Compostela, Spain) for some
Optic

■
●
○

photos courtesy.
The authors thank the two anonymous reviewers whose comments
Table 4 (continued)

and suggestions helped to improve and clarify this manuscript.

Ramil et al. [65]

References
Reference

[1] English Heritage, Graffiti on Historic Buildings and Monuments. Methods of

Removal and Prevention. English Heritage, 1999, pp. 1–12 http://www.english-

107
V. Gomes et al. Progress in Organic Coatings 113 (2017) 90–109

heritage.org.uk/. input.do?product=WOS&search_mode=GeneralSearch&SID=
[2] GRAFFITAGE, GRAFFITAGE: Development of a new anti-graffiti system, based on 4CYpM2h32MLpg2bD5ya&preferencesSaved (Accessed June 9, 2017).
traditional concepts, preventing damage of architectural heritage materials. SSP [31] P.M. Carmona-Quiroga, J. Rubio, M.J. Sánchez, S. Martínez-Ramírez, M.T. Blanco-
(Policy Oriented Research) of the Sixth European Programme of the European Varela, Surface dispersive energy determined with IGC-ID in anti-graffiti-coated
Commission. FP6-2003-SSP 3–513718, 2008. building materials, Prog. Org. Coat. 71 (2011) 207–212, http://dx.doi.org/10.
[3] GRAFFOLUTION, GRAFFOLUTION: Awareness and Prevention Solutions against 1016/j.porgcoat.2011.02.014.
Graffiti Vandalism in Public Areas and Transport. SSP (Policy Oriented Research) of [32] G. Gardei, O. Garcia, M. Riedl, I. Vanhellemond, J. Strupi Suput, M.-L. Santarelli,
the Seventh European Programme of the European Commission. FP7-SEC-2013-1, I. Rodríguez-Maribona, U. Müller, Performance and durability of a new antigraffiti
2016. system for cultural heritage ?The EC project GRAFFITAGE, 11th Int. Congr.
[4] J.S. Pozo-Antonio, T. Rivas, A.J. López, M.P. Fiorucci, A. Ramil, Effectiveness of Conserv. Deterior. Stone (2008) 889–897.
granite cleaning procedures in cultural heritage: a review, Sci. Total Environ. 571 [33] O. García, K. Malaga, Definition of the procedure to determine the suitability and
(2016) 1017–1028, http://dx.doi.org/10.1016/j.scitotenv.2016.07.090. durability of an anti-graffiti product for application on cultural heritage porous
[5] P. Sanmartín, F. Cappitelli, R. Mitchell, Current methods of graffiti removal: a re- materials, J. Cult. Herit. 13 (2012) 77–82, http://dx.doi.org/10.1016/j.culher.
view, Constr. Build. Mater. 71 (2014) 363–374, http://dx.doi.org/10.1016/j. 2011.07.004.
conbuildmat.2014.08.093. [34] P.M. Carmona-Quiroga, S. Martinez-Ramirez, M.T. Blanco-Varela, Protección de
[6] D. Urquhart, The treatment of graffiti on historic surfaces. Advice on graffiti re- piedras naturales con un antigraffiti fluorado Fluorinated anti-graffiti coating for
moval procedures, anti-graffiti coatings and alternative strategies. Historic Scotland natural stone, Mater. Constr. 58 (2008) 233–246.
technical advice note no.18., Historic Scotland, Edinburgh (1999). [35] P.M. Carmona-Quiroga, I. Panas, J.E. Svensson, L.G. Johansson, M.T. Blanco-
[7] ICOMOS, ICOMOS-ISCS: Illustrated glossary on stone deterioration patterns., Varela, S. Martínez-Ramírez, Protective performances of two anti-graffiti treatments
Champigny/Marne France (2008). towards sulfite and sulfate formation in SO2 polluted model environment, Appl.
[8] P. Sanmartín, R. Mitchell, F. Cappitelli, Evaluation of Cleaning Methods for Graffiti Surf. Sci. 257 (2010) 852–856, http://dx.doi.org/10.1016/j.apsusc.2010.07.080.
Removal, second ed., Imperial College Press (ICP), London, 2015. [36] P.M. Carmona-Quiroga, M.T. Blanco-Varela, S. Martínez-Ramírez, Freeze-Thaw and
[9] T. Ribeiro, A. Dionísio, L. Aires-Barros, Aerosol-paint graffiti: the effects on cal- UV Resistance in Building Stone Coated with Two Permanent Anti-graffiti
careous stone, Restor. Build. Monum. 15 (2009) 51–66. Treatments, (2015), pp. 1–584, http://dx.doi.org/10.1007/978-3-319-09054-2.
[10] Montana Colors web (2017) http://www.montanacolors.com/webapp/ (Accessed [37] O. García, I. Rz-Maribona, A. Gardei, M. Riedl, Y. Vanhellemont, M.L. Santarelli,
June 9, 2017). J.S. Suput, Comparative study of the variation of the hydric properties and aspect of
[11] Felton web (2017) http://www.felton.es/en/ (Accessed June 9, 2017). natural stone and brick after the appilcation of 4 types of anti-graffiti, Mater.
[12] Krink web, 2017 https://shop.krink.com/ (Accessed June 9, 2017). Constr. 60 (2010) 69–82, http://dx.doi.org/10.3989/mc.2010.45507.
[13] M.P. Fiorucci, J. Lamas, A.J. López, T. Rivas, A. Ramil, Laser cleaning of graffiti in [38] B. Meng, U. Mueller, O. Garcia, K. Malaga, Performance of a new anti-graffiti agent
Rosa Porriño granite, in: M.F.M. Costa (Ed.), Proc. SPIE – Int. Soc. Opt. Eng., SPIE used for immovable cultural heritage objects, Int. J. Archit. Herit. 8 (2014)
(2011) p. 80014A-80014A–8 10.1117/12.892158. 820–834, http://dx.doi.org/10.1080/15583058.2012.747116.
[14] M.P. Fiorucci, A.J. López, A. Ramil, S. Pozo, T. Rivas, Optimization of graffiti re- [39] U. Mueller, K. Malaga, Study on the application of anti-graffiti systems on natural
moval on natural stone by means of high repetition rate UV laser, Appl. Surf. Sci. stones and concrete, Hydrophobe VI 6th Int. Conf. Water Repel. Treat. Build. Mater.
278 (2013) 268–272, http://dx.doi.org/10.1016/j.apsusc.2012.10.092. (2011) 167–180.
[15] J.S. Pozo-Antonio, T. Rivas, M.P. Fiorucci, A.J. López, A. Ramil, Effectiveness and [40] M. Licchelli, S.J. Marzolla, A. Poggi, C. Zanchi, Crosslinked fluorinated poly-
harmfulness evaluation of graffiti cleaning by mechanical, chemical and laser urethanes for the protection of stone surfaces from graffiti, J. Cult. Herit. 12 (2011)
procedures on granite, Microchem. J. 125 (2016) 1–9, http://dx.doi.org/10.1016/j. 34–43, http://dx.doi.org/10.1016/j.culher.2010.07.002.
microc.2015.10.040. [41] M. Licchelli, M. Malagodi, M.L. Weththimuni, C. Zanchi, Water-repellent properties
[16] T. Rivas, S. Pozo, M.P. Fiorucci, A.J. López, A. Ramil, Nd:YVO4 laser removal of of fluoroelastomers on a very porous stone: effect of the application procedure,
graffiti from granite Influence of paint and rock properties on cleaning efficacy, Prog. Org. Coatg 76 (2013) 495–503, http://dx.doi.org/10.1016/j.porgcoat.2012.
Appl. Surf. Sci. 263 (2012) 563–572, http://dx.doi.org/10.1016/j.apsusc.2012.09. 11.005.
110. [42] M. Lettieri, M. Masieri, Surface characterization and effectiveness evaluation of
[17] A. Costela, I. García-Moreno, C. Gómez, O. Caballero, R. Sastre, Cleaning graffitis on anti-graffiti coatings on highly porous stone materials, Appl. Surf. Sci. 288 (2014)
urban buildings by use of second and third harmonic wavelength of a Nd:YAG laser: 466–477, http://dx.doi.org/10.1016/j.apsusc.2013.10.056.
a comparative study, Appl. Surf. Sci. 207 (2003) 86–99, http://dx.doi.org/10.1016/ [43] M. Masieri, M. Lettieri, Influence of the distribution of a spray paint on the efficacy
S0169-4332(02)01241-2. of anti-graffiti coatings on a highly porous natural stone material, Coatings 7 (2017)
[18] C. Gómez, A. Costela, I. García-Moreno, R. Sastre, Comparative study between IR 18, http://dx.doi.org/10.3390/coatings7020018.
and UV laser radiation applied to the removal of graffitis on urban buildings, Appl. [44] O. Cocco, M. Carboni, G. Carcangiu, P. Meloni, A. Murru, F. Persia, L. Solla, Crime
Surf. Sci. 252 (2006) 2782–2793, http://dx.doi.org/10.1016/j.apsusc.2005.04.051. art on the stone: graffiti Vandalism on cultural heritage and the anti-graffiti role in
[19] T. Learner, A review of synthetic binding media in twentieth-century paints, its surfaces protection, Period Di Miner. 84 (2015) 435–452, http://dx.doi.org/10.
Conservation 24 (2000) 96–103, http://dx.doi.org/10.1080/01410096.2000. 2451/2015PM0023.
9995156. [45] P.M. Carmona-Quiroga, R.M.J. Jacobs, S. Martínez-Ramírez, H.A. Viles, Durability
[20] V. Antúnez, P. Ortíz, J.-M. Martin, A. Gómez, R. Ortíz, Evaluación de Métodos de of anti-graffiti coatings on stone: natural vs accelerated weathering, PLoS One 12
Limpieza de Graffiti en Mármol, Macla 16 (2012) 68–69, http://dx.doi.org/10. (2017) 1–18, http://dx.doi.org/10.1371/journal.pone.0172347.
1002/col.20322. [46] M. Licchelli, M. Malagodi, M. Weththimuni, C. Zanchi, Anti-graffiti nanocomposite
[21] P. Ortiz, V. Antúnez, R. Ortiz, J.M. Martín, M.A. Gómez, A.R. Hortal, B. Martínez- materials for surface protection of a very porous stone, Appl. Phys. A Mater. Sci.
Haya, Comparative study of pulsed laser cleaning applied to weathered marble Process. 116 (2014) 1525–1539, http://dx.doi.org/10.1007/s00339-014-8356-9.
surfaces, Appl. Surf. Sci. 283 (2013) 193–201, http://dx.doi.org/10.1016/j.apsusc. [47] D. Kronlund, M. Lindén, J.H. Smatt, A sprayable protective coating for marble with
2013.06.081. water-repellent and anti-graffiti properties, Prog. Org. Coat. 101 (2016) 359–366,
[22] S. Samolik, M. Walczak, M. Plotek, A. Sarzynski, I. Pluska, J. Marczak, Investigation http://dx.doi.org/10.1016/j.porgcoat.2016.07.022.
into the removal of graffiti on mineral supports: comparison of nano-second [48] A. Moura, I. Flores-Colen, J. De Brito, Study of the effect of three anti-graffiti
Nd:YAG laser cleaning with traditional mechanical and chemical methods, Stud. products on the physical properties of different substrates, Constr. Build. Mater. 107
Conserv. 60 (2015) 58–64, http://dx.doi.org/10.1179/0039363015Z. (2016) 157–164, http://dx.doi.org/10.1016/j.conbuildmat.2015.12.181.
000000000208. [49] A. Moura, I. Flores-Colen, J. de Brito, A. Dionisio, Study of the cleaning effective-
[23] M. Carvalhão, A. Dionísio, Evaluation of mechanical soft-abrasive blasting and ness of limestone and lime-based mortar substrates protected with anti-graffiti
chemical cleaning methods on alkyd-paint graffiti made on calcareous stones, J. products, J. Cult. Herit. (2016), http://dx.doi.org/10.1016/j.culher.2016.04.004.
Cult. Herit. 16 (2015) 579–590, http://dx.doi.org/10.1016/j.culher.2014.10.004. [50] V. Fassina, General criteria for the cleaning of stone: theoretical aspects and
[24] A. Dionísio, T. Ribeiro, When graffiti is not art: the damage of alkyd sprays on methodology of application, Stone Mater Monum. Diagnosis Conserv. Sc. Univ. C.U.
calcareous stones employed in cultural heritage, Cult. Herit. (2013) 279–291. M. Conserv. Dei Monum. Heraklion, Crete, Mario Adda Ed. Bari (1993) 126–132.
[25] D.T. Burns, K.P. Doolan, A comparison of pyrolysis-gas chromatography-mass [51] R. Snethlage, K. Sterflinger, No Title, Stone Conserv. S. Durability, in: R.,
spectrometry and Fourier transform infrared spectroscopy for the analysis of a Siegesmund, Snethlage (Eds.), Stone Archit. Prop. Durability, Springer Berlin
series of modified alkyd paint resins, Anal. Chim. Acta. 422 (2000) 217–230, http:// Heidelb (2011) 411–544.
dx.doi.org/10.1016/S0003-2670(00)01073-4. [52] H.R. Sasse, R. Snethlage, Methods for evaluation of stone conservation treatments,
[26] F. Govaert, M. Bernard, Discriminating red spray paints by optical microscopy, in: N.S. Baer, R. Snethlage (Eds.), Dahlem Work. Rep. Sav. Our Archit. Herit.
Fourier transform infrared spectroscopy and X-ray fluorescence, Forensic Sci. Int. Conserv. Hist. Stone Struct, John Wiley Sons Ltd, West Sussex, 1996, pp. 223–243.
140 (2004) 61–70, http://dx.doi.org/10.1016/j.forsciint.2003.11.015. [53] L. Lazarini, M.L. Tabasso, Il restauro della pietra, CEDAM-Casa Editrice Dott A.
[27] G. Germinario, I.D. Van der Werf, L. Sabbatini, Chemical characterisation of spray Millani, Padova (1986).
paints by a multi-analytical (Py/GC–MS, FTIR, μ-Raman) approach, Microchem. J. [54] E. Doehne, C.A. Price, Stone Conservation: An Overview of Current Research, 2nd
(2015), http://dx.doi.org/10.1016/j.microc.2015.04.016. edition, (2011), http://dx.doi.org/10.1016/0006-3207(70)90031-5.
[28] J.M. Milczarek, J. Zieba-Palus, Examination of spray paints on plasters by the use of [55] A.E. Grimmer, Keeping It Clean: Removing Exterior Dirt, Paint, Stains and Graffiti
pyrolysis-gas chromatography/mass spectrometry for forensic purposes, J. Anal. from Historic Masonry Buildings, Library of Congress Cataloging-in-Publication
Appl. Pyrolysis 86 (2009) 252–259, http://dx.doi.org/10.1016/j.jaap.2009.06.009. Data, (1988), http://dx.doi.org/10.1017/CBO9781107415324.004.
[29] K. Malaga, T. Bengtsson, The Nordic method: performance tests for protective sa- [56] S. Chapman, Laser technology for graffiti removal, J. Cult. Herit. 1 (2000) 75–78,
crificial coatings on mineral surfaces, 5th Int. Conf. Water Repel. Treat. Build. http://dx.doi.org/10.1016/S1296-2074(00)00153-9.
Mater. (2008) 169–180. [57] N. Careddu, O. Akkoyun, An investigation on the efficiency of water-jet technology
[30] Web of Science web 2017 https://apps.webofknowledge.com/WOS_GeneralSearch_ for graffiti cleaning, J. Cult. Herit. 19 (2016) 426–434, http://dx.doi.org/10.1016/

108
V. Gomes et al. Progress in Organic Coatings 113 (2017) 90–109

j.culher.2015.11.009. Mater. Sci. Process. 104 (2011) 95–101, http://dx.doi.org/10.1007/s00339-011-

[58] J.S. Pozo-Antonio, M.P. Fiorucci, T. Rivas, A.J. López, A. Ramil, D. Barral, 6344-x.
Suitability of hyperspectral imaging technique to evaluate the effectiveness of the [67] A. Ramil, J.S. Pozo-Antonio, M.P. Fiorucci, A.J. López, T. Rivas, Detection of the
cleaning of a crustose lichen developed on granite, Appl. Phys. A Mater. Sci. optimal laser fluence ranges to clean graffiti on silicates, Constr. Build. Mater. 148
Process. 122 (2016) 1–9, http://dx.doi.org/10.1007/s00339-016-9634-5. (2017) 122–130, http://dx.doi.org/10.1016/j.conbuildmat.2017.05.035.
[59] C. Fotakis, D. Anglos, V. Zafiropoulos, S. Georgiou, V. Tornari, Lasers in the [68] R. Salimbeni, R. Pini, S. Siano, F. Bachmann, F. Meyer, Diode laser potential in laser
Preservation of Cultural Heritage: Principles and Applications, Taylor & Francis cleaning of stones, in: Renzo Salimbeni (Ed.), Proc. SPIE, Laser Tech. Syst. Art
Group, London, 2006. Conserv. (2001) 18–24.
[60] P. Pouli, C. Fotakis, B. Hermosin, C. Saiz-Jimenez, C. Domingo, M. Oujja, [69] J. Penide, F. Quintero, A. Riveiro, A. Sánchez-Castillo, R. Comesaña, J. Del Val,
M. Castillejo, The laser-induced discoloration of stonework; a comparative study on F. Lusquiños, J. Pou, Removal of graffiti from quarry stone by high power diode
its origins and remedies, Spectrochim. Acta – Part A Mol. Biomol. Spectrosc. 71 laser, Opt. Lasers Eng. 51 (2013) 364–370, http://dx.doi.org/10.1016/j.optlaseng.
(2008) 932–945, http://dx.doi.org/10.1016/j.saa.2008.02.031. 2012.12.002.
[61] G. Daurelio, A Bronze Age pre-historic dolmen: laser cleaning techniques of [70] L. Giacomucci, F. Toja, P. Sanmartín, L. Toniolo, B. Prieto, F. Villa, F. Cappitelli,
paintings and graffiti (the Bisceglie Dolmen case study), Lasers Conserv. Artworks Degradation of nitrocellulose-based paint by Desulfovibrio desulfuricans ATCC
LACONA V Proceedings, Osnabrück, Germany, 2003, pp. 199–205. 13541, Biodegradation 23 (2012) 705–716, http://dx.doi.org/10.1007/s10532-
[62] S.E. Andriani, I.M. Catalano, G. Daurelio, A. Albanese, Marker and pen graffiti 012-9546-9.
cleaning on diverse calcareous stones by different laser techniques, Proc. SPIE 6346, [71] P. Sanmartín, A. DeAraujo, A. Vasanthakumar, R. Mitchell, Feasibility study in-
XVI Int. Symp. Gas Flow, Chem. Lasers, High-Power Lasers (2007), http://dx.doi. volving the search for natural strains of microorganisms capable of degrading
org/10.1117/12.739334 p. 634636-1/10. graffiti from heritage materials, Int. Biodeterior. Biodegrad. 103 (2015) 186–190,
[63] V. der W. Inez, A. Edoardo, A. Antonio, D. Giuseppe, M. Danilo, S. Luigia, C. Ida, http://dx.doi.org/10.1016/j.ibiod.2015.05.010.
Laser removal and chemical characterisation of graffiti varnish spray and felt-tip [72] G. Germinario, I.D. van der Werf, G. Palazzo, J.L. Regidor Ros, R.M. Montes-
markers on stone monuments, Conserv. Sci. Archetype Publications, Milan, Italy, Estelles, L. Sabbatini, Bioremoval of marker pen inks by exploiting lipase hydro-
2007, pp. 23–32. lysis, Prog. Org. Coat. 110 (2017) 162–171, http://dx.doi.org/10.1016/j.porgcoat.
[64] R. Esbert, C. Grossi, a Rojo, F. Alonso, M. Montoto, J. Ordaz, M. Pérez de Andrés, 2017.02.019.
C. Escudero, M. Barrera, E. Sebastián, C. Rodríguez-Navarro, K. Elert, Application [73] A. Sansonetti, A.M. Mecchi, P. Tommaso, R. Marco, Problems in drawing up stan-
limits of Q-switched Nd:YAG laser irradiation for stone cleaning based on colour dards to evaluate effectiveness and harmfulness cleaning operations, in: T. Joyce,
measurements, J. Cult. Herit. 4 (2003) 50–55, http://dx.doi.org/10.1016/S1296- T. Lucia, C. Francesca (Eds.), Conserv. Sci. Archetype Publications, Milan, Italy,
2074(02)01227-X. 2007, pp. 80–87.
[65] C.M. Grossi, F.J. Alonso, R.M. Esbert, A. Rojo, Effect of laser cleaning on granite [74] R. Giorgi, M. Baglioni, P. Baglioni, Nanofluids and chemical highly retentive hy-
color, Color Res. Appl. 32 (2007) 152–159, http://dx.doi.org/10.1002/col.20299. drogels for controlled and selective removal of overpaintings and undesired graffiti
[66] E. Urones-Garrote, A.J. López, A. Ramil, L.C. Otero-Díaz, Microstructural study of from street art, Anal. Bioanal. Chem. 409 (2017) 3707–3712, http://dx.doi.org/10.
the origin of color in Rosa Porriño granite and laser cleaning effects, Appl. Phys. A 1007/s00216-017-0357-z.

109