Progress in Organic Coatings 154 (2021) 106180

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Progress in Organic Coatings

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Resistance to artificial daylight of paints used in urban artworks. Influence

of paint composition and substrate
E.M. Alonso-Villar a, b, *, T. Rivas a, b, J.S. Pozo-Antonio a, b
a
Depto. de Enxeñaría dos Recursos Naturais e Medio Ambiente, Escola de Enxeñaría de Minas e Enerxía, Universidade de Vigo, 36310, Spain
b
CINTECX, Universidade de Vigo, 36310, Spain

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

Keywords: Solar radiation is one of the deterioration factors par excellence of modern urban artworks, as among other
Paint manifestations, it causes loss of colour. This deterioration can compromise the durability of the works, although
Urban artwork it is not known to what extent this durability can vary depending on the substrate supporting the paint. We
Contemporaneous murals
evaluated the susceptibility to sunlight of 10 paints of differing compositions as typically used by urban artists,
Conservation
Cultural heritage
by exposing them, applied to concrete and brick, to artificial sunlight ageing test in laboratory conditions. Colour
Acrylic paints changes over time were studied, along with mineralogical (x-ray diffraction), chemical (scanning electron
Alkyd paints microscopy-energy dispersive x-ray spectroscopy) and physical (contact angle and peeling tests) changes. The
durability of the paints on these substrates depends mainly on the paint composition (base, pigment and filler)
but also on the type of substrate, as this influences paint adhesion capacity. The greatest colour modification was
detected in fluorescent paints, which lose colour due to degradation of the organic phase, and with aggravation
of defects during drying, eventually detach from the substrate.

1. Introduction abundant, even including a glossary of terms related to alteration forms

Contemporaneous murals are artistic creations that are increasingly
present in urban spaces. Whether independent or commissioned art­
works, they are created by applying modern materials in different ways
(paint, dabber, spray graffiti, etc) to a wide variety of substrates (brick,
metal, concrete, wood, etc) and structures (stationary urban furniture,
building walls and civil structures, etc). As with ancient mural artworks,
interactions between the paints and deterioration agents (rainwater, sun
irradiation, pollutants, etc) lead to different alteration patterns that
affect both aesthetics (e.g., colour changes such as fading and yellowing)
and integrity (loss of cohesion and of material), compromising their
durability. Although the ephemeral nature of many independently
created artworks in modern urban spaces is recognized [1], there is also
a certain interest in the creation of more durable artworks, as evidenced
in commissions by local authorities and other administrative bodies.
Ideally, both the artists and the commissioners should have the best
possible guidance in selecting the best materials and optimal physical
conditions that ensure durability (substrate type, pre-treatment of the
surfaces, minimization of weathering and anthropic agent impacts, etc).
While the literature on the deterioration of ancient mural paintings is
and agents [2], the deterioration processes that affect contemporary
urban artworks is little documented and no conservation guidelines are
as yet available.
A main conservation issue for contemporary urban artworks is the
fact that they are composed using modern paints, whose formulation
makes them very susceptible to solar radiation and colour loss [3]. Like
ancient paint, modern paint is composed by a binder and pigments, but
it also contains extenders, solvents and additives [3–6]. The variety of
binders, which was limited in ancient paints (natural oils and fats,
casein, collagen and egg), is much greater in modern paints, and in­
cludes low molecular resins (alkyd, polyurethane, phenolic, epoxy and
polyester resins) and/or high molecular resins (acrylic, vinyl and
nitrocellulose type). Pigments in modern paints are mainly of organic
nature, the most frequent being phthalocyanines and anthraquinone
derivatives and especially azo-type chromophores (R-N=N-R) such as
monoazo, diazo and azo-polycyclic compounds. Extenders, e.g., tita­
nium oxide (TiO2, used mainly as a white pigment), calcium carbonate
(CaCO3), kaolinite (Al2Si2O5(OH)4), talc (Mg3Si4O10(OH)2) and barite
(BaSO4) influence on the coating properties such as density, flow,
hardness and permeability [6]. Solvents, which are organic, facilitate

* Corresponding author.
E-mail address: enalonso@uvigo.es (E.M. Alonso-Villar).

https://doi.org/10.1016/j.porgcoat.2021.106180
Received 21 October 2020; Received in revised form 28 January 2021; Accepted 30 January 2021
Available online 3 March 2021
0300-9440/© 2021 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
E.M. Alonso-Villar et al.
the mixing and viscosity of paint components and are crucial for drying
and polymerizing organic components. Finally, additives may include
anti-settling agents, viscosity modifiers, surfactants or emulsifying
agents, anti-foaming agents, driers, plasticizers, ultraviolet stabilizers,
anti-skinning agents, biocides, flow-modifying agents, etc.
A consensus in the scientific community is that enhancing the
resistance of modern paints and coatings to the harmful effects of solar
and ultraviolet radiation is a key challenge. Organic polymers are pho­
todegraded through interactions between photons in sunlight and
organic bonds, with/without the participation of oxygen [3,7] by means
of photolysis, photooxidation and/or photoreduction. These reactions
lead to the formation of very reactive free radicals in the polymer,
which, in turn (and depending on polymer type, molecule length, tem­
perature and film thickness) cause chain cleavage, cross-linking and the
formation of low molecular weight intermediates. These processes can
affect any organic polymer in the pigment or in the binder. In the
pigment, resistance to photodegradation will depend on the chromo­
phore type and concentration; as for the binder, degradation can lead to
colour changes (because the degradation (loss) of binder leaves the
pigments more exposed to radiation) or to modifications of other optical
properties [3].
There is an extensive literature on the mechanisms that lead to
photodegradation processes in polymers, coatings and paints. In most
experimental work on paint photodegradation, polymer samples are
exposed to different levels of light irradiation (ultraviolet (UV) radiation
or artificial daylight) in accelerated ageing tests [8–18]. Most of those
experimental studies, as well as basic polymer studies [3–7], describe
the chemical reactions that define different photodegradation mecha­
nisms: bond cleavage, free-radical formation, chain scissions,
cross-linking and loss of volatile products (alcohols, aldehydes and
carboxylic acids). According to those studies, the mechanisms through
which an organic paint degrades when exposed to sunlight or UV radi­
ation depend on the type of paint (alkyd, acrylic, vinyl, polyurethane,
phenolic, epoxy, etc) and the structural complexity of the polymer
(chain length, unsaturation and aromatic or aliphatic compounds). Poly
(methyl methacrylate) (PMMA) resins are the most photostable, while
polyolefins, polystyrene, polyamides and polyurethanes are the least
photostable, with polyethylene and polyvinyl resins falling somewhere
in between [7]. Susceptibility to photodegradation is also influenced by
temperature, film thickness [10], the presence of extenders such as TiO2,
whose photocatalytic properties may accelerate degradation of organic
paint components [12] and binder-pigment interactions, with the
pigment itself, depending on the range of UV radiation absorbed,
potentially acting as a protector against binder photodegradation
[19–21].
The chemical and physical changes experienced by paints exposed to
ageing tests also depend on the type of light source used: UV radiation
(A, B and C), natural daylight, or artificial daylight. Photodegradation of
alkyd-based paints is slower in daylight than in UV-A radiation condi­
tions [22], degradation of acrylic paints (ethyl and methyl methacry­
late) is slower in UV-A than under UV-B radiation conditions [8], while
red and blue alkyd-based spray paints have recently been demonstrated
to deteriorate faster in response to UV-C compared to UV-B radiation
[18].
Urban artworks are potentially exposed to a risk of deterioration,
given their ongoing exposure to sunlight – although at variable in­
tensities depending on the geographical orientation of the surfaces.
From the point of view of the materials that make up urban artworks, it
would seem sensible not only to use sunlight-resistant paints, but also to
take into account the substrate type and possible interactions between
this substrate and the paint. Typical substrates for painted urban art­
works – concrete, wood, ornamental stone, metal, brick, glass, etc – are
compositionally very different, with their different properties and re­
sponses to deterioration factors influencing adhesion between paint and
substrate (which depends on substrate absorption capacity and surface
properties) and resistance of both paint and substrate to environmental
2
Progress in Organic Coatings 154 (2021) 106180
exposure. This resistance, and consequently the durability, will depend
how well the paint and substrate are integrated and how each reacts to
deterioration factors. For instance, the alkalinity of concrete can influ­
ence the colloidal stability of the paint and lead to surface defects, while
the anisotropic deformation of wood due to humidity interferes with
adhesion. Paint adhesion will likely also be very different for, e.g.,
sandstone versus glass, while the absorption capacity of the substrate
will also influence the thickness of paint layers. The type and quality of
the substrate is not usually taken into account in selecting suitable paints
for urban artworks, possibly due to the scant research on substrate in­
fluence on paint durability. In the research into paints subjected to
accelerated ageing cited above, substrate was generally not taken into
account. The only exception [18] was a study of the resistance to pho­
todegradation of paints applied to three different rock types as
substrates.
In this work, we evaluated colour changes, after exposure to artificial
daylight for 7 months, in 10 types of paint of different compositions
widely used in urban artworks in Galicia (NW Spain). The paints were
applied to concrete and brick, substrates typically used in contemporary
mural art in this geographical region. After the exposure test, mineral­
ogical, chemical and physical changes in the specimens were studied in
order to evaluate paint durability in relation to the paint itself, the
substrate and the paint-substrate interaction. Our findings are expected
to inform artists and commissioners of urban artworks by guiding them
in their choice of paints and substrates in the interest of ensuring
artwork durability.
2. Materials and methods
2.1. Paints and substrates
Visited in a fieldwork phase were around 100 contemporary murals
in 4 cities/towns of NW Spain (Vigo, A Guarda, Ordes and Carballo),
commissioned by local entities with the aim of promoting urban art.
Selected were 10 widely used differently applied paints from different
commercial houses. Table 1 lists the selected paints along with repre­
sentative works; 4 were applied by brush (B-type) and 6 were applied by
spray (S-type), 2 of which were fluorescent (SF-type).
The 10 paints were applied to aluminium foil, left to dry for 1 month
under laboratory conditions (15 ± 5 ◦ C; RH 60 ± 10 %) and then scraped
and analysed as follows:
(1) X-ray diffraction (XRD), using a Siemens D5000 (Siemens,
Munich, Germany), applying the random powder method and
using Cu-Kα radiation with Ni filter. Each mineral phase was
identified using the X’Pert HighScore (Malvern Panalytical B.V.,
Almelo, Netherlands).
(2) Diamond crystal Attenuated total reflection (ATR)-Fourier
transform infrared spectroscopy (FTIR), using a Thermo Nicolet
6700 (Thermo Fisher Scientific, Waltham, MA, USA). Each
infrared (IR) spectrum was recorded at 2 cm− 1 resolution over 32
scans from 400 cm− 1 to 4000 cm− 1.
After initial characterization, the paints were applied to concrete and
brick (the most commonly used substrates in urban artworks in NW
Spain). The concrete was prepared using a granite aggregate of gran­
ulometry 20− 50 μm and Cosmos CEM-II/BM (VL) 32.5 N cement. Slabs
measuring 100 × 100 × 2 cm were prepared, left to set for 1 month (20
◦
C; RH 70 %), then cut into specimens measuring 7 × 7 × 2 cm for
painting and testing. Brick specimens measuring 7 × 7 × 2 cm were cut
from single 24 × 11 × 4 cm hollow bricks, washed and brushed to
remove particles adhering to the surface, dried in an oven at 40 ± 0.1 ◦ C
to constant weight and stored for 1 month under laboratory conditions
(15 ± 5 ◦ C; RH 60 ± 10 %). To identify the constituent mineral phases of
the 2 substrate types, these were analysed by XRD following the pro­
cedure described above.
E.M. Alonso-Villar et al. Progress in Organic Coatings 154 (2021) 106180

Table 1
Trade names and manufacturers of the 10 selected paints, urban artworks where applied and composition according to manufacturer (n.s, not supplied).
ID TRADENAME (MANUFACTURER) COLOUR ARTWORK COMPOSITION

BY P7-Reveproa Matte Silk Outdoor Primary Yellow Xestando – Lidia Cao (Ordes, 2018) PY138 (quinophthalone yellow)
Yellow (PROA)
BR Teppisol Matte Fire Red (EGA) Red Génesis y Gnosis – Peri Helio (Vigo, 2015) n.s.
BG Green RAL 6024 (KROMO) Green Artemisa vulgaris – Doa Oa (Carballo, 2018) n.s.
BP Pink RAL 4010 (KROMO) Pink Artemisa vulgaris – Doa Oa (Carballo, 2018) n.s.
SY Light Yellow RV 1021 (MONTANA Yellow A Guarda escrita nas estrelas – Nuvi & Titanium (IV) oxide-rutile, monoazo yellow, disazo pyrazolone
COLORS) Éxfico (A Guarda, 2018) orange
SP Tutti Frutti RV 151 (MONTANA COLORS) Pink A Guarda escrita nas estrelas – Nuvi & Rutile, transparent yellow iron oxide, monoazo BONA
Éxfico (A Guarda, 2018) manganese blue, quinacridone red 122
SO Orange RV 2004 (MONTANA COLORS) Orange A Guarda escrita nas estrelas – Nuvi & Rutile, transparent yellow iron oxide, disazo pyrazolone orange
Éxfico (A Guarda, 2018)
SG Valley Green RV 6018 (MONTANA Green A Guarda escrita nas estrelas – Nuvi & Rutile, monoazo yellow, transparent yellow iron oxide,
COLORS) Éxfico (A Guarda, 2018) chlorinated copper phthalocyanine
SFO FLUOR Orange (MONTANA COLORS) Fluor Minero asturiano de padre gallego – Spok n.s.
Orange (Ordes, 2015)
SFG FLUOR Green (MONTANA COLORS) Fluor Minero asturiano de padre gallego – Spok n.s.
Green (Ordes, 2015)

2.2. Mockup preparation
Substrates were painted with the different paints following the
manufacturer’s recommendations regarding application. The 4 B-type
paints were applied by brush in as many layers as necessary to ensure
complete coverage: 1 application for red, pink and green (BR, BP and
BG, respectively) and 3 applications for yellow (BY) at intervals of 48 h.
The 4 S-type green, orange, pink and yellow paints (SY, SP, SO and SG,
respectively) and 2 SF-type green and orange paints (SFG and SFO,
respectively) were applied by spray – at a 45◦ angle at a distance of 30
cm from nozzle to substrate surface – for the time necessary to fully and
evenly cover the surface. Mockups were left to dry for 1 month in a dark
laboratory environment.
2.3. Artificial solar ageing test
The mockups were irradiated using 4 300 W OSRAM Ultra Vitalux
artificial daylight bulbs placed at a vertical distance of 50 cm from the
surfaces of the mockups and at a distance from each other of 30 cm to
ensure even and equal irradiation of all the specimens. Testing consisted
of 210 repeated cycles of 22 h of exposure to radiation followed by 2 h of
darkness (representing 4620 h of exposure in total). The maximum
temperature reached on the mockup surfaces was 40 ± 1 ◦ C.
2.4. Analyses
Changes in mockup appearance and colour were monitored as
follows:
(1) Stereoscopic microscope visualization of mockups before and
after the exposure test using a Nikon SMZ800.
(2) Colour characterization of mockups in the CIELab and CIELCH
spaces [23] before the exposure test, during the exposure test
(every 15 days, representing 330 h of irradiation), and after
testing (4620 h of irradiation). Measurements (6 per mockup)
were made using a Minolta CM-700d spectrophotometer with a
pulsed xenon lamp (with UV cut filter), in specular component
excluded (SCE) mode, spot diameter 3 mm, illuminant D65 and
observer angle 10◦ . Variables were measured as follows: lumi­
nosity L*, which takes values from 0 (black) to 100 (white); a*
(positive values for red and negative values for green); b* (posi­
tive values for yellow and negative values for blue); C* (chroma);
and h (hue). To evaluate colour changes, differences were
measured as ΔL*, Δa*, Δb*, ΔC*ab, ΔH*, while ΔE*ab reflected
overall change, with the original mockup colour taken as the
reference value.
To investigate mineralogical, chemical and physical changes that
could explain colour changes, mockups for which colour changes were
visible to researchers were analysed. It was unanimously found that
perceived colour changes corresponded to a threshold of ΔE*ab>5 CIE­
Lab units, corroborating previous researchers [24], according to whom a
colour change is visually perceptible to an inexperienced observer when
ΔE*ab>3.5 CIELab units, while two different colour changes can be
definitely distinguished when ΔE*ab>5 CIELab units.
Consequently, for the mockups for which ΔE*ab>5 CIELab units, the
following analyses were performed before and after the exposure test:
(1) Micromorphological and compositional analysis, via scanning
electron microscopy (SEM) with energy-dispersive x-ray (EDX)
using a QUANTA 200 in both secondary electron (SE) and back­
scattered electron (BSE) detection modes. Observation conditions
were a working distance of 9− 11 mm, accelerating potential of
20 kV and specimen current of ~60 mA. The specimens were
studied by observing the surface directly, and by studying the
paint layer in cross-sections to the mockup surface; for this,
specimens embedded in epoxy resin (EpoThin 2 Epoxy Resin and
EpoThin 2 Epoxy Hardener) then cut and polished to a mirror
shine.
(2) Analysis of water-solid contact angle of the paint surface, using a
Phoenix-300 Touch SEO contact angle analyser, with an outer
diameter of 0.012′′ (0.3048 mm) and an inner diameter needle of
0.005′′ (0.127 mm). Measured were 3 drops of 8 μL per mockup
following Spanish standards [25].
(3) Adherence to the substrate, evaluated by a peeling test –
following [26] – based on using double-sided Tesa Powerbond
adhesive tape, applied and removed 3 times consecutively to each
mockup. Peeled-off material was determined as the tape weight
differences for averages per mockup before and after application.
(4) Mineralogical analysis by XRD, using the equipment and method
described above. Analysed for each mockup was the powder
obtained by scraping the paint surface, taking care not to remove
material from the substrate.
(5) ATR-FTIR analysis, using the equipment and method described
above, to analyse the powder obtained from scraping the paint
surface.
3. Results
3.1. Pre-test characterization of paints, substrates and mockups
Table 2 shows the mineralogical composition of the concrete and
brick substrates. The concrete was composed of quartz, potassium
feldspar, sodium plagioclase and micas (the aggregate) and calcium

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E.M. Alonso-Villar et al. Progress in Organic Coatings 154 (2021) 106180

Table 2
Mineralogical composition (presence) of paints and substrates (by XRD) and organic composition (by FTIR) (main group). Q: quartz, M: micas; KF: potassium feldspar;
P: plagioclase (albite); T: talc; C: calcite; B: barite; K: kaolinite; Cl: chlorite; TiO2: titanium dioxide; G: goethite (n.a.: not applicable; PVA: polyvinyl acetate).
ID Q M KF P T C B K Cl TiO2 G OTHER ORGANIC PHASE

Concrete x x x x x n.a.
Brick x x x x n.a.
BY x x x x PVA
BR x x x PVA
BG x x PVA
BP x x PVA
SY x x x K2Cr2O7 Alkyd
SP x Alkyd
SO x x Alkyd
SG x x Alkyd
SFO x x Acrylic
SFG x x Acrylic

carbonate. No C-S-H phases or non-hydrated cement phases were
detected. The brick was composed of quartz, microcline, biotite and
albite.
Table 2 also shows the mineral phases detected in the 10 paints as
applied to aluminium foil and confirms a remarkably different compo­
sition. B-type paints all contained calcite and SY, SO and SG paints had
traces of goethite, an inorganic pigment typical of reds and yellows
colours. TiO2 and talc were also identified in 8 and 5 of the 10 paints,
respectively. Barite was occasionally detected in BY, while phyllosili­
cates (chlorite and kaolinite), also commonly used as fillers, were
evident in BR and BY paints. Potassium chromate was detected in SY
paint (calcium, potassium and zinc chromates are frequently used as an
organic pigment in some yellowish paints, e.g., PY36).
Table 2 also shows the generic polymer of the organic phase for each
paint, while Table 3 shows the FTIR fingerprint bands used to identify
the different paint components (polymer base, chromophores, fillers
and, occasionally, inorganic pigments).
B-type paints typically have a polyvinyl acetate (PVA) base, S-type
paints are alkyd-based and SF-type paints are acrylic-based. Identifica­
tion was carried out taking into account the typical fingerprint bands of
each large group of organic polymers (Table 3). The bands are also
depicted in Fig. 1, which shows spectra for a representative paint for
each group (PVA-based BR, alkyd-based SP and acrylic-based SFG).
The position of the band corresponding to C– – O (carbonyl) stretch­
ing was used to differentiate PVA from alkyd and acrylic paints: in PVA
paints, this band occurred at a slightly higher wavenumber (1728− 1735
cm− 1) [27], as was also observed for the BY, BR, BG and BP paints.
Likewise, the band corresponding to C(=O)-O ester at around 1231
cm− 1 also made it possible to discriminate between the different paint
types: this band appears at a slightly higher wavenumber for alkyd
paints [27]. Thus, for the SY, SP, SO and SG paints this band lays be­
tween 1250 cm-1 and 1255 cm-1, and between 1227 cm-1 and 1231 cm-1
for the remaining paints. Another typical fingerprint for alkyd paints is
the existence of characteristic doublets at 1602− 1584 cm− 1 – assigned
to C–– C aromatic stretching [6,28] – and at 1114− 1066 cm− 1 – assigned
to C-H in plane bending [27]. Doublets were clearly identified only in
the SY, SO, SP, SG paints (Table 3).
The SO, SP, SG and SY paints differed from the B-type paints in the
shape of the bands assigned to the stretching vibration of the C–H group
in the region between 2850 cm− 1 and 2960 cm− 1. In the S-type paints,
this vibration manifested in 2 intense bands, differentiated at 2854 cm− 1
and 2925 cm− 1, typical of aliphatic C–H stretching due to alkyd poly­
mer oil content. In the B-type paints, 2 bands were observed at higher
frequencies (2878 cm− 1 and 2927 cm− 1), with the small shoulder at
2954 cm− 1 typical of vinyl paints [6,27].
Another band that discriminated between the different paint types

Table 3
FTIR fingerprint bands used to identify organic phase compounds in the paints. FTIR bands assigned to inorganic fillers and consulted references are also indicated.
BOND TYPE WAVENUMBER (cm− 1) ASSIGNED TO REFERENCE PAINT/ID

O-H stretching – intramolecular bonded 3615− 3670 OH of phyllosilicates and/or FeOOH [30,31] BY, BR, SY, SO, SG, SFO, SFG
O-H stretching vibration 3430− 3300 Acryl, PVA, alkyd [15,16,30] SFO, SFG, SN,
N-H stretching Doublet 3295− 3380 Amide [30] Chromophore
2925
C-H stretching Acryl, PVA, alkyd [27,30] BY, BR, BG, BP, SY, SP, SO, SG, SFO, SFG
2885
1721− 1723 Alkyd and acrylic resins SY, SP, SO, SG, SFG, SFO
C=O carbonyl stretching [27]
1728− 1735 PVA BY, BR, BG, BP
N-H def. primary amide 1645− 1556 Azo group [30] SY, SG, SFO, SFG
C=C aromatic group doublet 1602− 1584 Alkyd [27,28] SY, SP, SO, SG
N=N 1505− 1555 Azo compounds [29] SY, SG, SFO, SFG
C-H bending; C=C aromatic stretching 1485 – [30] SFO, SFG
C-O asymmetric stretching 1420 Calcite BY BR, BG, BP
1434
C-H bending PVA [27] BY, BR, BG, BP
1374
1227− 1235 Acryl and PVA BY, BR, BG, BP, SFO, SFG
C(=O)-O ester [27]
1250− 1252 Alkyd SY, SP, SO, SG,
C-H/C-C/C-O/C-C(=O)-O stretching 1150 Acryl [27] SFO, SFG
C-H/C-C/C-O/C-C(=O)-O stretching doublet 1114− 1066 Alkyd [27] SY, SP, SO, SG
C-H/C-C/C-O/C-C(=O)-O stretching 1026− 1020 PVA [27] BP, BV
Si-O 1018 Talc [30] BY, BR, SY, SFO, SFG
OH out-of-plane deformational mode 905 FeOOH [34,35] SY, SP, SG, SO
C=O carbonate 875 Calcite [30] BY, BR, BG, BP
C-H bending of aromatic units 750− 728 Acryl, alkyd [15,30] BY, BR, SP, SO, SP, SG, SFO, SFG
C-O out-of-plane 714 Calcite [30] BY, BR, BG, BP
Ti-O 690− 614 TiO2 [33] BG, BP, SY, SP, SO, SG
Si-O 670 Talc [30] BY, BR, SY, SFO, SFG
Fe-O stretching 460 FeOOH [30,34] SY, SO, SP, SG

4
E.M. Alonso-Villar et al.
Fig. 1. FTIR spectra (absorbance) of SP, SFG and BR paints scraped from the aluminum foil, BR applied to brick (BR-B) and to concrete (BR-C).
was located in the fingerprint band of C–O stretching vibration between
1200 cm− 1 and 900 cm-1. Distinctive was absorption at around 1026 cm-
1
and around 1150− 1170 cm-1 for the PVA-based and acrylic-based
paints, respectively [27,28]. Observed in the BP and BG paints was ab­
sorption at around 1020 cm-1 that was not evident for the remaining
paints (in BY and BR this effect overlapped with that for talc), while in
the SFO and SFG paints, a peak was observed at 1150 cm-1 that was not
evident for the remaining paints.
For the SY, SG, SFO and SFG paints, a band was clearly detected
between 1505 cm− 1 and 1556 cm-1 that could be assigned to the
stretching vibration of the N–– N azo group (Table 3) [29]; these same
paints had a band between 1644 cm− 1 and 1556 cm− 1 that was assigned
to the N–H bending of primary amide [30]. The SFO and SFG paints also
showed a doublet at 3295 cm− 1 and 3380 cm− 1 that corresponded to the
N–H stretching vibration of the amides. All these bands could be
attributed to azo-type chromophore compounds, as, according to the
manufacturers, SY, SP, SG and SO paints have mono- and diazo-type
chromophores. We were unable to obtain information from the
5
Progress in Organic Coatings 154 (2021) 106180
manufacturer about the nature of the SFG and SFO paints, but the FTIR
information confirmed them as having azo-type chromophores.
Regarding paint fillers and inorganic pigments, talc was identified by
FTIR (confirming XRD results) in the 5 paints (BY, BR, SY, SFO and SFG)
from the bands at 3670 cm− 1 (O-H stretching), 1018 cm− 1 (asymmetric
Si-O-Si stretching) and 670 cm− 1 (O-H stretching) [30–32]. The pres­
ence of TiO2 was corroborated by FTIR only for 6 paints (BG, BP, SY, SP,
SO and SG), from the wide band lying between 614 cm− 1 and 690 cm− 1
[33]. The presence of calcite was confirmed by FTIR in the 4 paints for
which it was also detected by XRD (BG, BP, BY and BR), from the bands
at 1420 cm− 1 but especially at 875 cm− 1, which does not overlap with
any organic component bands. Oxyhydroxylated forms of iron
(FeOOH-goethite type) added as an inorganic pigment were verified by
FTIR for 3 paints (SY, SG and SO). In the SP mockups, where this
pigment was not identified by XRD, there appeared to be FTIR evidence
of its presence in that the characteristic 905 cm-1 band was detected [34,
35].
Fig. 2 shows images of mockup surfaces, where the appearance after
E.M. Alonso-Villar et al. Progress in Organic Coatings 154 (2021) 106180

Fig. 2. A-F: Stereoscopic micrographs of the surfaces of BR on concrete (A) and on brick (B), SY on concrete (C), SP on brick (D), SFO on concrete (E) and SFG on
brick (F). G-J: SEM micrographs of the surfaces of SO on concrete (G) and on brick (H) and SFO on concrete (I) and SFG on brick (J).

6
E.M. Alonso-Villar et al.
applying the paints were found to differ depending on the paint and the
substrate. In the BR concrete and brick mockups, small bubbles were
observed (Fig. 2-A and 2-B). Bubbles were also observed in SY and SP
mockups, but differing depending on the substrate: in the concrete
mockups (Fig. 2-C), the bubbles were large (up to 2 mm in diameter) and
a few had burst, whereas in the brick mockups (Fig. 2-D) the bubbles
were much smaller and more numerous and most had burst, leaving
many holes on the surface. In the SFO and SFG mockups, an apparently
denser craquelure developed in the concrete mockup (more fissures per
unit area) compared to the brick mockup (Fig. 2-E and 2-F). The same
figures show the influence of surface roughness on the final finish:
concrete surfaces were rougher than brick surfaces (e.g., Fig. 2-A versus
2-B).
SEM observations of mockup surfaces corroborate the above obser­
vations, confirming the differences in roughness (Fig. 2-G and 2-H).
Likewise, the formation of bubbles was also evident, with larger bub­
bles on concrete (Fig. 2-G) than on brick (Fig. 2-H). For example, in the
BR mockups, bubbles left holes measuring 40 μm in diameter on con­
crete, but measuring less than 15 μm on brick. For the SO concrete
Fig. 3. A-B: Stereoscopic micrographs of cross-sections of BR on concrete (A) and SO on brick (B). C-F: SEM micrographs of BR on concrete (C) and on brick (D), SO
on concrete (E) and SFO on brick (F).
7
Progress in Organic Coatings 154 (2021) 106180
mockups there were numerous bubbles measuring 70 μm in diameter
(Fig. 2-G), while in the SO brick mockups, few bubbles there were
(Fig. 2-H) measured around 15 μm in diameter.
SEM also confirmed the formation of craquelure in the SF paints
(Fig. 2-I and 2-J), less dense (but with deeper and more open cracks) in
concrete (Fig. 2-E and 2-I), and denser (but with finer cracks) in brick
(Fig. 2-F and 2-J).
Visualization of mockup cross-sections also confirmed differences
between the 3 paint types (Fig. 3):
(1) Thickness. The 3 types of paints were thicker when applied to
concrete, especially B-type paints (150 μm on concrete and 30 μm
on brick; Fig. 3-A) and SF-type paints (125 μm on concrete and 40
μm on brick; Fig. 3-B) and less so for S-type paints (very similar
for both substrates at 50− 70 μm).
(2) Texture. BR (PVA-based) was made up of an organic phase (low
contrast according to the BSE detector, indicating great richness
in C) that agglutinated a large quantity of Ca-rich and Si, Mg and
O-rich particles (corresponding to calcium carbonate and talc
E.M. Alonso-Villar et al. Progress in Organic Coatings 154 (2021) 106180

Table 4
L*, C*ab and H* variations after artificial solar ageing testing and global colour change (ΔE*ab) in paints applied to concrete and brick. In brackets, change behaviour: l,
linear; q, quick initial change; -, undefined. In grey colour, samples with ΔE*ab>5 CIELab units.

fillers, respectively) measuring 1− 30 μm (Fig. 3-C and 3-D). In
contrast, the alkyd-based SO paint (Fig. 3-E) looked very
different, with an organic phase (very low contrast under BSE
detector, so very rich in C) of granular texture; these granules
appeared surrounded by very small titanium particles (high
contrast under BSE, sizes less than 1 μm). Similarly, the SFO and
SFG paints (Fig. 3-F) also had a different texture than the other
paints, as they were formed of very low contrast C- and S-rich
grains with well-defined edges, embedded in a matrix composed
of small titanium fragments (less than 1 μm) and, occasionally, Si-
, O- and Mg-rich grains (corresponding to talc). Another impor­
tant difference between the 3 types of paints was the amount of
inorganic fillers. B-type (PVA-based) paints (Fig. 3-C and 3-D)
had more filler than S-type (alkyd-based) paints (Fig. 3-E),
while the SF-type (acrylic-based) paints (Fig. 3-F) had the least
amount of inorganic fillers.
and were assigned to talc, appeared wider in the paints on both sub­
strates (Fig. 1). This could be attributed to 2 kinds of contributions:
(1) Silicates in both substrates (quartz, feldspars and micas in con­
crete, and feldspars and micas in brick). The Si-O bond vibration
mode in the different structural configurations of those minerals
ranges between 1100 cm− 1 and 1066 cm− 1 [31,36].
(2) Hydrated C-S-H gel, with absorption at around 976 cm− 1 [37].
Note, however, that, on comparing the intensity ratios of the
bands of the organic phase and of the peaks corresponding to the
silicates, the intensity of the bands assigned to silicates was
observed to be higher in paints applied to concrete than to brick;
this could be due to the dragging of substrate particles during the
scraping of the paint. This possibility is remote in the case of
brick, much smoother and more resistant to scraping than
concrete.

The FTIR spectra of the paints applied to brick and concrete differed
3.2. Paint durability during and after artificial daylight ageing
from the spectra of the paints themselves. The band at around 1018
cm− 1, which corresponded to the asymmetric Si-O-Si stretching mode
Table 4 shows colour parameter variations, after 210 days of

Fig. 4. Variations in ΔE*ab and ΔC*ab for SO and SFG on concrete during exposure.

8
E.M. Alonso-Villar et al.
artificial daylight ageing. ΔL*, ΔC*ab, ΔH* and ΔE*ab all underwent
modifications reflecting colour changes. The mockups were divided into
2 groups according to the ΔE*ab reached at the end of the test: the group
that showed ΔE*ab<5 CIELab units and the group that showed ΔE*ab>5
CIELab units. As mentioned, ΔE*ab = 5 CIELab units was established as
the threshold value at which colour changes become visible to the
human eye.
The mockups that showed ΔE*ab<5 CIELab units were BP, BG, BY,
SG, SY and SP applied to concrete and brick. The colour change in the
green and pink paints (BG, BP, SG and SP) was greater for the concrete
mockups than for the brick mockups, while the reverse occurred for the
yellow paints (BY and SY). For all the paints with the exception of SY,
the greatest contribution to ΔE*ab was chroma C*ab (which suffered a
reduction, causing a colour shift towards grey that was independent of
the substrate), while for SY, the greatest contribution to ΔE*ab was hue
H* (which increased).
The mockups that suffered ΔE*ab>5 CIELab units were BR, SO, SFO
and SFG applied to concrete and brick. In these paints, colour changes
were greater for brick than for concrete mockups, except for SO, where
the reverse was the case. The changes in SFO and SFG were notably
greater and occurred much faster than in BR and SO. For SFG and SFO,
ΔE*ab reached 5 CIELab units a mere 15 days after starting the test,
compared to 90 days for the SO concrete mockup, 105 days for the SO
brick mockup, 150 days for the BR concrete mockup and 135 days for
the BR brick mockup. The parameter that most contributed to change
was again C*ab, which suffered a reduction, indicating colour fading.
Within the group of mockups in which ΔE*ab>5 CIELab, paint colour
parameters evolved differently over time, as follows:
(1) Linear behaviour (Fig. 4-A and 4-C; (l) in Table 4). The increase or
decrease was progressive and constant for almost all BR and SO
colour parameters for concrete and brick.
(2) A quick initial change (increase or decrease), during the first 45
days, which then slowed down ([q] in Table 4). This occurred in
the ΔE*ab evolution of SF paints and in the H* evolution of SO
paint. In the case of SF paints, the evolution of ΔE*ab over time
was determined by the behaviour of chroma (C*ab) (Fig. 4-B and
4-D).
(3) Undefined behaviour ((-) in Table 4). No clear trend was detected
in colour parameter change evolution, as exemplified by the
evolution in the L* coordinate for BR. This behaviour occurred in
those samples that suffer the lowest ΔE*ab.
Fig. 5 shows visible colour changes in the surfaces of some of the
painted mockups before and after the exposure test. Colour changes
were intense in SF-type paints (SFO and SFG, Fig. 5-A to 5-D) applied to
both concrete and brick. Furthermore, in the mockups initially affected
by craquelure, some loss of the paint layer – greater for brick mockups
than for concrete mockups – left a partially exposed surface along with
apparently unaltered paint (compare Fig. 5-A, 5-B, 5-C and 5-D). Colour
changes in BR and SO (Fig. 5-E and 5-F) were less intense, despite these
paints having ΔE*ab>5 CIELab units. Outside of colour changes, the
mockups showed no physical deterioration.
Cross-sections viewed under a stereoscopic microscope confirmed
that, in the B-type (PVA) and S-type (alkyd) paints, colour changes
occurred evenly throughout the paint layer, whereas in the SF-type
(acrylic) paints, colour changes occurred in the microns closer to the
paint surface (compare Fig. 5-G and 5-H).
BR, SO, SFG and SFO, as mockups for which ΔE*ab>5 CIELab units,
were further analysed to explore possible reasons for the deterioration in
colour. SEM study of the surfaces of these mockups confirmed the sig­
nificant colour loss in SFO and SFG. In concrete mockups (Fig. 6-A), the
craquelure widened after exposure. while in the brick mockups (Fig. 6-
B), circular segregations rich in titanium (Ti) were clearly observed
(Fig. 6-C). SEM study of the mockups of B- and S-type paints did not
evidence any noticeable differences.
9
Progress in Organic Coatings 154 (2021) 106180
Cross-section visualization under SEM confirmed a physical separa­
tion between the paint layer and the substrate for brick mockups of all
the paints in this group; this separation measured as much as 25 μm for
SO (Fig. 6-D). In cross-sections of the SFO and SFG mockups, SEM evi­
denced no textural or compositional differences in paint layers in depth
from the exposed surface that would explain the loss of colour observed
under the stereoscopic microscope (Fig. 5-G and 5-H).
The physical separation of the paint layer may partly account for the
results of the peeling test before and after exposure to artificial daylight
exposition (Fig. 7-A). Several observations can be made in relation to
Fig. 7-A:
(1) The amount material extracted for SFG, SFO and, most especially,
for BR was greater for concrete than for brick, both before and
after exposure; no differences between substrates were detected
for SO. The greater amount of material extracted may be related
to the fact that the adhesive tape dragged away grains of aggre­
gate from the concrete; for brick specimens (smoother and more
compact), only paint, which weighs less, would has been
removed.
(2) The amount of material extracted for SFG and SFO on either
substrate and for BR only on concrete was greater after exposure
to artificial daylight. This is striking because, observed in the
brick mockups but not in the concrete mockups, was a clear post-
test separation between paint and substrate that would facilitate
material removal by the adhesive tape.
(3) Greater amounts of material were removed for SFO and SFG,
whose pre-test craquelure intensified after exposure to daylight.
(4) Although material losses were greater after the exposure test, the
pre- and post-test differences were only statistically significant
for the BR concrete mockups, while, for the remaining cases,
standard deviation values for the 3 removals of material were
very high both before and after the exposure test.
Paint deterioration was also evident from data on variations in the
surface contact angle (Fig. 7-B). Before artificial daylight exposure,
contact angles were greater than 90◦ (corresponding to hydrophobic
surfaces) for the SFO and SFG mockups (and greater for brick than for
concrete), but barely reached 80◦ for BR and SO. After artificial daylight
exposure, contact angles were reduced for all paints, with only SFO on
concrete having a contact angle close to the theoretical hydrophobicity
value (89.20◦ ±1.11◦ ). In the concrete mockups, the contact angle was
most reduced in SFG and least reduction in SFO; in the brick mockups,
the greatest reduction in contact angle occurred in SFO and the least
reduction occurred in BR.
Colour, texture and surface property changes were observed not to be
due to mineralogical changes. On comparing pre- and post-test miner­
alogical composition of the paints, there was no evidence of the disap­
pearance of mineral phases present in the non-exposed paints or the
appearance of new mineral phases.
From the molecular point of view, FTIR confirmed changes, although
only in the organic phase. All specimens experienced a reduction in
bands at 3400− 3300 cm− 1 (O-H stretching), 2925 cm− 1 (C-H stretch­
ing), 1721− 1735 cm− 1 (C=O carbonyl stretching) and 1227-1252 cm− 1
(C(=O)-O ester). To rule out substrate influence and to quantify and
relate band reductions to paint deterioration, the ratios between the
intensity of FTIR bands of the organic phase of the paints and a FTIR
band of the filler present in the paints (which remained unaltered after
test) were calculated from spectra obtained before and after the test,
obtaining the percentage variations of these ratio after the test. If this
percentage is positive, it would mean that the organic polymer FTIR
band suffered an increase (relative to the unalterable reference band,
that of the filler). If it is negative, it would mean that the polymer band
suffered a decrease, always relative to the filler. Bands corresponding to
the stretching vibration modes of O-H (3394 cm-1), C-H (2925 cm-1) and
C(=O)-O (1732 cm-1) were selected as organic phase FTIR bands; the
E.M. Alonso-Villar et al. Progress in Organic Coatings 154 (2021) 106180

Fig. 5. Stereoscopic micrographs of mockups before (A, C, E and G) and after (B, D, F and H) testing. A-B: SFO surface on brick; C-D: SFG surface on concrete; E-F:
cross-section of SO on brick; G-H: cross-section of SFO on brick.

10
E.M. Alonso-Villar et al.
Fig. 6. A and B: SEM micrographs (BSE detector) of SFO on concrete (A) and on brick (B); C: spectrum obtained by EDS of SFO on brick before (left) and after (right)
testing. D: Cross-section of SO on brick.
FTIR band used as reference was the band at 1018 cm-1 (asymmetric Si-
O-Si stretching mode) assigned to talc, whose intensity should remain
the same after the test, given that talc is inert to solar radiation. Since
talc was also absent in the 2 substrates, any influence of brick or con­
crete composition could be ruled out in calculating FTIR intensities
ratio. In the case of BR mockups, the band at 670 cm-1 (O–H stretching)
of talc was selected because the band assigned to C(=O)-O stretching
vibration for PVA (1020 cm-1) overlaps the band at 1018 cm-1 of the
Si–O group of talc. For SO paint, changes could not be quantified
because titanium (614 cm-1 and 690 cm-1) – the only inert inorganic
compound that could be used as reference – overlaps with the C–H
stretching and bending vibrations of the aromatic ring of the alkyd base
of the paint.
Table 5 shows percentage variations of the calculated FTIR in­
tensities ratio. In all the cases, the calculated ratios were reduced. The
percentage variation varied depending on the substrate: for BR on
concrete, the band that changed most – it almost disappeared – was
O–H stretching (3400− 3300 cm− 1), while for BR on brick, the band
that changed most was the C– – O carbonyl stretching (1721− 1735
− 1
cm ). SFO and SFG also behaved differently depending on the sub­
strate: in concrete mockups, the most changed band was that of C– –O
carbonyl stretching (1721− 1735 cm− 1), while in brick mockups this
band was reduced by 81.1 % for SFO but only 13.4 % for SFG. The
reduction on the intensity of organic phase FTIR bands after the test may
indicate volatilization of small molecules resulting from radiation-
induced polymer degradation [10]. More specifically, the reduction of
the intensity of C–H stretching band at 2925 cm− 1 suggests hydrogen
abstraction processes. Some authors associate the change in this band
with destruction of the backbone structure of the polymer [10,11].
Regarding the band at 1721 cm− 1, the reduction would suggest partial
11
Progress in Organic Coatings 154 (2021) 106180
loss of carbonyl groups in the polymer. However, no widening of the
carbonyl peak towards lower wavenumbers (at around 1700− 1680
cm− 1) was detected, and, according to the literature, this loss leads to
the formation of ketone groups [10,11,21].
Notable was the reduced intensity in the band at 3400− 3300 cm− 1
(O-H stretching). In most published studies, organic polymer deterio­
ration has usually been associated with increased intensity of that band
reflecting oxidation processes (formation of alcohols, carbonyls, perox­
ides, etc). The disappearance of this band may indicate a rapid reaction
of radicals with free OH groups - formed from scission reactions - to form
ester and ketones. The non-increase or widening of the carbonyl group
band, indicating a subsequent ketone-formation reaction, would sug­
gest, as a more likely hypothesis, the reduction of the O–H stretching
band at 3400− 3300 cm− 1, and a loss of low-molecular weight molecules
through volatilization.
4. Discussion
Characterization of the 10 different paints applied to brick and
concrete revealed compositional differences: brush-applied paints were
PVA-based, spray paints were alkyd-based and fluorescent paints were
acrylic-based. FTIR confirmed that the paints for which the factory
composition was known had azo-type chromophores, while FTIR points
to possibly azo for several paints for which no manufacturer information
was available (SFG and SFO). Mineralogically, the usual minerals were
used as fillers and extenders. All the B-type paints had calcite as a filler,
while some also included talc (BY and BR) and others included TiO2 (BP
and BG). S-types paints all contained TiO2 which can act as both a white
pigment and an opacifier, and SG, SO and SY included goethite as a
possible inorganic pigment. Fluorescent paints (SFO and SFG)
E.M. Alonso-Villar et al. Progress in Organic Coatings 154 (2021) 106180

Fig. 7. Results of peeling test (A) and contact angle measurements (B) for BR, SO, SFG and SFO on concrete and on brick before and after testing.

paint and the substrate, as concrete and brick are both porous and also
Table 5
have an absorption capacity that could favours bubble formation during
Percentage variations after the test of the ratio between the intensity of the
application. The size of the bubbles may also be related to the size of the
organic phase bands (3394 cm− 1, 2925 cm− 1 and 1732 cm− 1) and the intensity
pores in the substrate: SEM observations of the cross-sections showed
of the reference band considered (talc; 670 cm− 1 for BR and 1081 cm-1 for SO,
SFG and SFO). Values for concrete and brick mockups are shown. that porosity in concrete was more heterometric than in brick, which,
compared to concrete, has pores that are much smaller in diameter.
CONCRETE BRICK
RATIO There could also be a relationship with the paint formula, specifically
BR SFG SFO BR SFG SFO with surface active agents with emulsifying properties [4], as these
OH str. (3394) /Si-O − 94.5 − 81.1 − 25.9 − 0.5 − 10.1 − 13.4 compounds favour the formation of foam bubbles that remain intact
(talc) during drying, so their absence should facilitate foam bubble breakage
CH str. (2925) / Si-O − 76.9 − 38.9 − 27.8 − 35.2 − 35.5 − 42.0 during drying. However, this did not seem to happen in our study, as the
(talc)
C=O carbonyl str. − 43.9 − 77.3 − 60.6 − 68.9 − 13.2 − 80.3
same paint formed broken bubbles in brick and whole bubbles in con­
(1732) / Si-O (talc) crete, representing, therefore, a significant influence on the substrate.
Craquelure is related to shrinkage during polymer drying processes
[6] – in this study, during oxidation – or to an excess of paint. Inter­
additionally included talc. estingly, however, in our case, this only occurred with the 2 fluorescent
The paint finishes were different once applied to the concrete or paints (SFO and SFG). Since craquelure did not occur in S-type paints,
brick. PVA-based B-type paints (the only paints that had calcite as a we can rule out any link to the application method, because both (SF and
filler) obtained a smooth even finish, with no defects. The finish for S type) are applied as a spray. Furthermore, since craquelure occurs a
alkyd-based S-type and acrylic-based SF-type paints (with TiO2 as a few seconds after application (with the paint still fresh), so retraction
filler) had defects: bubbles in the yellow and pink alkyd paints (SY and and contraction phenomena associated with oxidation due to drying can
SP) and craquelure in the fluorescent paints (SFO and SFG). The be ruled out. It seems more likely, considering the speed of crack for­
different failure morphologies could be related to the different nature of mation just after application, that the craquelure formation is related to
the paint organic phases (craquelure- acrylic paints; bubbles-alkyd rapid solvent evaporation.
paints) although the paint formulation seems to be more decisive The presence of bubbles in the SY and SP paints did not seem to
since bubbles form in only two (SY and SP) of the 4 alkyd S-type paints. compromise their resistance to deterioration, since none of the corre­
The influence of the substrate on defect intensity was clear: 1) craque­ sponding mockups underwent colour change of ΔE*ab>5 CIELab units.
lure affecting SF-type was denser in brick than in concrete, although Colour resistance seems to have been due to the alteration of the organic
cracks were wider and deeper in concrete samples; 2) bubbles were phase of the paints. There were no mineralogical changes and, from the
larger on concrete and smaller on brick. chemical point of view, FTIR confirmed a reduction in the typical bands
Bubble formation could be related to the interaction between the

12
E.M. Alonso-Villar et al.
of C–H, O-H and C=O functional groups, suggesting the destruction of
the backbone structure of the polymer and the loss of compounds of low
molecular weight through volatilization. The loss of an organic phase
was very evident in one of the most degraded paints, SFO (Fig. 6-B), with
SEM detecting on the corresponding surface a relative enrichment of Ti.
The reduction of the contact angle in all the paints after the exposition,
specifically in those of water-repellent character (SF- type), was clear
evidence of the deterioration of the organic (non-polar) phase.
Colour fastness during testing appeared to depend on 3 factors:
(1) Type of organic base. The 2 acrylic-based paints (SFG and SFO)
experienced the greatest colour change (ΔE*ab>40 CIELab units),
very different from change in the PVA (B-type) and alkyd (S-type)
paints (no more than ΔE*ab>10 CIELab units). However,
considering that acrylic resins are highly resistant to solar radi­
ation [7,10], the greater colour deterioration of acrylic-based
paints (SFO, SFG) may be related to the stability of the fluores­
cent pigments. Initial colour variations in these paints were
substantial (already at 15 days, ΔE*ab>5 CIELab units, and after
testing, ΔE*ab>41 CIELab units), so it is reasonable to assume
exponential behaviour and colour stabilization at some point.
The great colour change in the SF-type paints may also be related to
the surface failure (craquelure) evident before the exposure test and
its intensification after exposure to artificial daylight.
Also, another possible reason for the greater degradation of SF-type
paints may be the presence of TiO2. It is known that, in polymers
with low photooxidative stability, the scattering effect of UV radia­
tion caused by TiO2 particles improves the ultimate response of the
polymer; but, in contrast, for polymer systems with good photooxi­
dative stability (like acrylic resins), the addition of TiO2 often leads
to a reduction in resistance to photooxidation through its photo­
catalytic effects [38]. For the SF-type paints, SEM confirmed a rela­
tive Ti enrichment of the surface (Fig. 6-B) that could point to a loss
of the organic phase. However, there are several reasons that would
indicate the low probability that TiO2, in SF-type paints, is the factor
that contributes the most to colour degradation. First of all, the TiO2
polymorph with the highest photocatalytic effect is anatase. The
other polymorphs rutile and brookite, due to their lighter effective
mass, smaller particle size and longer lifetime of photoexcited elec­
trons and holes [39] have a lesser catalytic effect. The TiO2 identified
by XRD in these samples is rutile so, without ruling out a possible
contribution, it is unlikely that the intense degradation of SF paints is
due exclusively to a photocatalytic effect of TiO2. On the other hand,
S-type paints, of an alkyd composition (and therefore, according to
the literature, less resistant to UV radiation than acrylic resins [7,
10]) and also containing TiO2-rutile, suffer a much less intense
degradation than SF paints. For all these reasons, the most likely
causes of colour degradation of SF paints would be related to 1) a
possible greater susceptibility to photodegradation of their specific
fluorescent pigments and 2) the contribution to the colour change of
the increase, after the exposure, of craquelure that initially appeared
after the drying of the paints.
(2) Colour (chromophore type). In the PVA-based (B-type) and alkyd-
based (S-type) paints, pink, yellow and green colours resisted
best, as indicated by their small ΔE*ab values, while orange and
red paints resisted worst (ΔE*ab = 8 to 11 CIELab units). It cannot
be ruled out that, in addition to the deterioration of the organic
base, the durability of the paints is influenced by the resistance to
sunlight of the chromophore itself. Unfortunately, we did not
have information on the type of pigment in each paint, nor was
FTIR able to shed any light on the issue
(3) Substrate type. In the specimens that experienced less colour
change (ΔE*ab<5 CIELab units), no relationship was observed
between the magnitude of the colour change and the substrate. In
the specimens that experienced more colour change (ΔE*ab>5
CIELAB units), change was greater in paints applied to brick,
13
Progress in Organic Coatings 154 (2021) 106180
except for SO (in this case, greater for concrete). While there was
no evidence that the paints photodegraded more when applied to
brick, 2 arguments would support that brick can favour the colour
change to be more intense:
(a) The paint layer on brick was less thick than on concrete. For
the same irradiation and exposure time conditions, paint
applied less thickly deteriorates more intensely and to a
greater degree.
(b) SEM confirms a clear separation between the paint layer and
the brick in all the brick mockups. Polymers adhere less well
to smooth surfaces than to rough surfaces [6] and brick is
much smoother than concrete. Mechanical forces (a third
mechanism to add to primary chemical bonding and sec­
ondary -polar- bonding) that contribute to polymer adhesion
to substrates are stronger on surfaces with numerically more
chemically active locations (a consequence of surface
roughness and a greater specific surface). In this sense, the
least favourable substrate is brick, which is much smoother
than concrete, also having a lower roughness and specific
surface. Therefore, it is not unreasonable to think that paint
adhesion on brick was already initially weak; also, brick has a
lower absorption capacity than concrete. During irradiation
testing, polymer degradation together with thermal oscilla­
tions (due to slight increases in temperature) may have led to
paint separation from the substrate. What is unquestionable
is that colour was influenced by the existence of a gap be­
tween the paint layer and the substrate.
The peeling test results did not reflect the SEM finding that BR, SFG
and SFO adhesion to brick decreased with artificial daylight exposure.
This reduced adhesion would imply that the amount of material
removed after the test were greater for brick than for concrete, yet the
opposite happened, both before and after the exposure test. This may be
partially due to the tape removing small grains of aggregate from the
concrete: the cohesion of the substrate (lower for concrete than for
brick) consequently affected test performance, revealing itself as a
limitation of the method. The fact that, after the test, the amount of paint
removed by the tape increased in concrete mockups (and not only in
brick mockups) indicates that exposure to artificial daylight likely also
affected paint adhesion to the concrete – although this could not be
verified by stereomicroscopy or SEM. Peeling test demonstrated the
lesser durability of SF paints, as the amount of removed material was
especially high for SF-painted specimens, especially after artificial
daylight exposure; this lesser durability may be due to the craquelure
observed in the SF mockups that increased after testing, especially in
concrete (in which cracks widened and deepened).
5. Conclusions
We tested the durability to artificial daylight of 10 different colour
(including fluorescent) paints, as used in urban art, applied by brush or
spray to concrete and brick. Prior characterization of the paints and
mockups (paint plus substrate) confirmed differing compositions
regarding the organic base: spray paints (S-type) were alkyd-based,
brush-applied paints (B-type) were PVA-based and fluorescent paints
(SF-type) were acrylic-based. There were also differences in the nature
and quantity of fillers: SF-type paints were much poorer in fillers than S-
type and B-type paints, and S-type and SF-type paints were richer in TiO2
than B-type paints.
Coating failures observed after the application of the paints were
related to paint composition (bubbles in S-type paints and craquelure in
SF-type paints) and to the substrate type: craquelure in SF-type paints
was denser in brick mockups than that in concrete mockups; the cracks
were finer and more superficial in brick samples whereas they were
wider and deeper in concrete. No coating failures were evident for B-
type paints.
E.M. Alonso-Villar et al.
The artificial daylight caused a colour degradation of the paints that
was related to organic phase degradation: FTIR confirmed a decrease in
the C-H, O-H, C(=O)-O stretching vibrations bands, suggesting chain
scissions and the formation of low molecular weight volatilizing com­
pounds. The relative enrichment of Ti on the SF-type paint surface
confirmed a loss of the organic phase.
Colour degradation varied depending paint composition (type of
base and filler), paint colour and substrate type. The loss of colour was
much more intense in SF-type (acrylic) paints (ΔE*ab>41 CIELab units)
than in either S-type (alkyd) or B-type (PVA) paints (ΔE*ab = 7 to 11
CIELab units). The formulation regarding pigment seems to influence
photostability: of the B-type colours, only red (BR) degraded, and of the
S-type colours, only orange (SO) degraded. The intense colour degra­
dation of the SF paints seems to be related to lower pigment photo­
stability, while coating failure in the form of craquelure undoubtedly
contributed to their lesser durability. Brick substrate adhesion of the
paints experiencing the greatest colour change was null after the expo­
sure test, and this loss of adhesion may contribute to intensifying the
colour change.
In selecting materials for urban artworks that are intended to last,
administrations and artists need to consider the impact of exposure to
daylight. Since SF paints show zero photoresistance, their use is strongly
discouraged. Of the spray (alkyd-based S-type) and brush-applied (PVA-
based B-type) paints, colour (and therefore pigment type) seems to be a
determining factor in durability/resistance, with reddish-orange colours
seeming to be the least durable/resistant. It is also important to take into
account the substrate and to properly condition artwork substrates
before applying paint, to ensure good adhesion (if brick) and reduce loss
of surface material (if concrete).
CRediT authorship contribution statement
E.M. Alonso-Villar: Conceptualization, Methodology, Data cura­
tion, Writing - original draft, Visualization, Investigation, Writing - re­
view & editing. T. Rivas: Conceptualization, Methodology, Data
curation, Writing - original draft, Visualization, Investigation, Supervi­
sion, Writing - review & editing. J.S. Pozo-Antonio: Conceptualization,
Methodology, Data curation, Writing - original draft, Visualization,
Investigation, Supervision, Writing - review & editing.
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgements
This work was supported by CONSERVATION OF ART IN PUBLIC
SPACES - CAPuS. Erasmus + Knowledge Alliance KA2: Cooperation for
innovation and the exchange of good practices, 2017-2021. Grant
Agreement Number 2017-3674/001-001. E. M. Alonso-Villar’s research
was partially financed by the same project. J.S. Pozo-Antonio’s research
was supported by the Spanish Ministry of the Economy and Competi­
tiveness through grant IJCI-2017-32771. FTIR, XRD and SEM analyses
were performed at the University of Vigo’s Research Support Centre for
Science and Technology (CACTI). Ailish Maher translated the manu­
script and revised the English in a near-final version of the manuscript.
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