Progress in Organic Coatings 114 (2018) 47–57

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Progress in Organic Coatings

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

Protective features, durability and biodegration study of acrylic and MARK

methacrylic fluorinated polymer coatings for marble protection
⁎
Valentina Sabatinia,b, , Cristina Cattòc, Giuseppe Cappellettia,b, Francesca Cappitellic,
Stefano Antenuccia,b, Hermes Farinaa,b, Marco Aldo Ortenzia,b, Stefano Camazzolaa,b,
Giuseppe Di Silvestroa,b
a
Department of Chemistry, Università degli Studi di Milano, Via Golgi 19, 20133 Milan, Italy
b
CRC Materials & Polymers Laboratory (LaMPo), Department of Chemistry, Università degli Studi di Milano, Via Golgi 19, 20133 Milan, Italy
c
Department of Food Environmental and Nutritional Sciences, Università degli Studi di Milano, Via Celoria 2, 20133 Milan, Italy

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

Keywords: In the present paper, a new fluorine based methacrylic monomer, 1H,1H,2H,2H-Perfluoro-octyl-methacrylate
Polymeric coating (POMA), was synthesized via esterification reaction from methacryloyl chloride and 1H,1H,2H,2H-Perfluoro-1-
Methacrylic monomer octanol. Furthermore, POMA was used to prepare with methyl methacrylate (MMA) via free radical poly-
Free radical polymerization merization a novel fluorinated methacrylic polymer (MMA_POMA), in order to overcome the well-known
Marble protection
technical problems related to the use of acrylic monomer-based commercial protectives, such as Paraloid B72®.
Polymer biodegradation
Indeed, in Paraloid B72® −obtainable from the copolymerization reaction of ethyl methacrylate (EMA) and
Fungal deterioration
methyl acrylate (MA)- the presence of an acrylic hydrogen atom in alpha to the carbonyl group can start photo-
chemical degradation reactions that are able to promote fungi attack and proliferation.
The properties of MMA_POMA and the two references synthesized, EMA_MA and EMA_MA_POMA −in terms
of macromolecular structure, molecular weights, thermal features and water repellency- were determined;
furthermore, the long-term behavior of these polymeric protective agents was estimated by means of accelerated
aging tests exploiting UV radiations. Their behavior over time was checked via Size Exclusion Chromatography
(SEC), Fourier Transform Infrared (FT-IR) spectroscopy and biodegradation assay. Lastly, MMA_POMA resin was
applied on two marble substrates −Calcite and Dolomite- and its wetting properties were successfully assessed
and compared to the same features displayed by the reference polymers.
This work demonstrates that a polymer protective prepared starting from methacrylic and fluorinated
monomers, i.e. MMA and POMA, is an efficient way to obtain resins with satisfactory water repellent properties
and enhanced durability than acrylic based polymers without the use of any photo stabilizer additive.

1. Introduction
The degradation of cultural heritages and buildings is a natural and
irreversible decay process; water permeation into the stone is con-
sidered the main responsible of its degradation, especially for porous
marbles, such as Calcite and Dolomite [1], largely used in ancient and
contemporary art. Once water penetrates the stone, chemical reactions
(i.e. carbonate dissolution [2]), physical processes (such as freezing/
thawing cycles [3] and/or crystallization/precipitation [4]) and biolo-
gical degradation [5] can occur, dramatically affecting the quality and
properties of marble based materials.
Thus, the application of hydrophobic coatings to stone materials is
an effective way to preserve stone artefacts and protect cultural
heritages and constructions from decay, limiting the water penetration
into the porous substrates.
Any protective coating for stone must be compatible with the sub-
strate, water repellent, capable to avoid the ingress of chemicals or
other harsh agents and concomitantly inhibit fungi and bacteria pro-
liferation. At the same time it must be permeable to water vapour,
transparent, easy to apply, durable and reversible or, at least, the sur-
face where it is applied must be re-treatable, i.e. the coating must be
easy to remove [6].
Many are the examples of the use of either organic polymers for the
protection of stone objects and structures, such as polysiloxanes [7,8]
and acrylic resins [9], or inorganic (TiO2 or SiO2)-based coatings for the
consolidation of stone made manufactures [10]. Limited durability,

⁎
Corresponding author at: Department of Chemistry, Università degli Studi di Milano, Via Golgi 19, 20133 Milan, Italy.
E-mail address: valentina.sabatini@unimi.it (V. Sabatini).

http://dx.doi.org/10.1016/j.porgcoat.2017.10.003
Received 6 March 2017; Received in revised form 29 September 2017; Accepted 5 October 2017
Available online 13 October 2017
0300-9440/ © 2017 Elsevier B.V. All rights reserved.
V. Sabatini et al.
modification of structural properties, fungi and bacteria proliferation
and poor physical and chemical compatibility with stone substrates are
often observed when organic treatments are used [11]. Inorganic resins,
conversely, seem to have some advantages in terms of good durability
and a higher compatibility with the stone substrate, but they usually are
not able to penetrate sufficiently inside the stone resulting, thus, in a
poor consolidating effect [12].
Referring to organic products, polymer coatings prepared starting
from acrylic monomers are typically employed as protective agents of
stones. During the last decades, the most satisfactory commercial ac-
rylic resin, obtainable via free radical polymerization between a mix-
ture of acrylic and methacrylic monomers, i.e. ethyl methacrylate
(EMA) and methyl acrylate (MA), was Paraloid B72® due to its good
water repellence and optically clear appearance [13]. Despite the
common use of photo stabilizing agents with Paraloid B72® [13], the
presence in the acrylic monomer of a hydrogen atom in alpha position
to carbonyl group that is capable to start photo-chemical degradation
reactions leads to severe durability issues.
In particular, Paraloid B72® photo-chemical degradation process
proceeds through the formation of radicals that determine the polymer
reticulation via cross-linking reactions promoting fertile conditions for
fungi proliferation and attack, scarce adhesion to porous substrates and
insufficient water drainage from the coated surface [14].
In order to overcome the above-mentioned limits of Paraloid B72®,
the aim of the present work was to synthesize a new polymer coating as
stone protective with satisfactory water repellent properties and im-
proved durability, combining the use of fluorinated and methacrylic
monomers and without the adding of any photo stabilizer agent.
A new kind of a fluorinated methacrylic monomer, 1H,1H,2H,2H-
Perfluoro-octyl-methacrylate (POMA), was synthesized via esterifica-
tion reaction between methacryloyl chloride and 1H,1H,2H,2H-
Perfluoro-1-octanol.
A new type of polymer protective was prepared via free radical
polymerization between POMA and methyl methacrylate
(MMA_POMA), thus overcoming the poor durability of acrylic protec-
tives. As references, EMA_MA and fluorinated EMA_MA
(EMA_MA_POMA) resins (obtained with the introduction of POMA
monomer in EMA_MA polymeric chain) were synthesized.
In order to determine the long-term properties of MMA_POMA resin,
accelerated exposure tests under UV radiations were performed. The
macromolecular structure, molecular weights, thermal features and
water repellence behavior of MMA_POMA resin, compared to those of
both EMA_MA and EMA_MA_POMA, were investigated before and after
the UV exposure simulation test via 1H NMR and Fourier Transform-
Infrared (FT-IR) spectroscopies, Size Exclusion Chromatography (SEC),
Differential Scanning Calorimetry (DSC) and Water Contact Angle
(WCA) measurements.
Moreover, the ASTM G 21-96 “Standard Practice for Determining
Resistance of Synthetic Polymeric Materials to Fungi” [15] was em-
ployed to test the MMA_POMA resistance to fungal degradation with
respect the references EMA_MA and EMA_MA_POMA.
Lastly, all the synthesized resins were applied on two porous marble
substrates −Calcite and Dolomite- largely used in historical cultural
heritages and modern buildings [16,17].
2. Experimental
2.1. Materials
Ethyl methacrylate (EMA, 99%), methyl acrylate (MA, 99%), me-
thyl methacrylate (MMA, 99%), methacryloyl chloride (97%),
1H,1H,2H,2H-Perfluoro-1-octanol (97%), α,α’-Azoisobutyronitrile
(AIBN, 99%), triethyl amine (TEA, ≥99.9%), sodium bicarbonate
(≥99.7%), sodium sulfate (≥99.99%), cyclohexane (99.5% anhy-
drous), methanol (99.8% anhydrous), ethyl acetate (≥99.8% anhy-
drous), distilled water Chromasolv® (≥99.9%), hydrochloric acid (HCl,
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Progress in Organic Coatings 114 (2018) 47–57
37%), tetrahydrofuran (THF, ≥99.8% anhydrous), chloroform-d
(CDCl3, 99.96 atom% D), fluorescent brightener 28 and sterile phos-
phate buffered saline (PBS) were supplied by Sigma Aldrich and used
without purification. Calcite and Dolomite marbles were purchased
from Marmi Orobici Graniti S.p.A.
2.2. Synthesis of POMA
A 100 cm3 three-necked round bottom flask was equipped with a
nitrogen inlet adapter, an internal thermometer adapter, an overhead
magnetic stirrer and a reflux condenser. The flask was flushed with
nitrogen, charged with 20 cm3 of methylene chloride, methacryloyl
chloride (2.8 g), 1H,1H,2H,2H-Perfluoro-1-octanol (9.8 g) and TEA
(2.9 g), the latter used to neutralize hydrochloric acid formed during
the esterification reaction. The solution was carefully cooled at 0 °C and
then left under stirring for 16 h: afterwards it was gradually brought
back to room temperature. TEA was removed from the resulting solu-
tion through several washings with an aqueous solution of hydrochloric
acid at 5% w/w. The remaining traces of hydrochloric acid were re-
moved through several washings with an aqueous solution of sodium
bicarbonate at 5% w/w and then the solution was dehydrated with
sodium sulfate. The salt was removed via filtration and the resulting
solution was dried under vacuum (about 4 mbar) at 40 °C for 1 h (96%
yield).
2.3. Synthesis of EMA_MA, EMA_MA_POMA and MMA_POMA copolymers
Three polymers with acrylic/methacrylic functionalities
−EMA_MA, EMA_MA_POMA and MMA_POMA- were synthesized. The
exact amount of the monomers used for the syntheses are reported in
Table 1.
In a representative polymerization procedure, a 100 cm3 two-
necked round bottom flask was equipped with a nitrogen inlet adapter,
a reflux condenser and an overhead magnetic stirrer. The flask was
flushed with nitrogen, charged with 40 cm3 of cyclohexane and:
- EMA_MA copolymer: EMA, MA and AIBN, the latter used as free
radical initiator;
- EMA_MA_POMA copolymer: EMA, MA, POMA at 1% w/w respect to
not fluorinated acrylic monomers and AIBN;
- MMA_POMA copolymer: MMA, POMA at 1% w/w respect to MMA
and AIBN.
The solution was put in an oil bath, heated for 24 h at 70 °C and
then gradually cooled to room temperature. The solution obtained was
precipitated into a large excess of methanol under stirring and a white
solid precipitate was obtained. The solid was recovered via filtration
and given the difficulties in completely removing unreacted acrylic and
methacrylic monomers from EMA_MA, EMA_MA_POMA and
MMA_POMA samples, the polymers were washed with methanol for
several days under stirring. After washing, they were dried in a vacuum
oven (about 4 mbar) at 40 °C for 48 h and then the absence of residual
solvents was checked via isothermal thermogravimetric analysis (TGA),
performed for 2 h at 70 °C under nitrogen flow. Fig. 1 shows the re-
presentative procedure for the synthesis of EMA_MA, EMA_MA_POMA
and MMA_POMA.
Table 1
Loadings of the reagents for EMA_MA, EMA_MA_POMA and MMA_POMA.
Sample EMA (g) MA (g) MMA (g) POMA (g) AIBN (g)
EMA_MA 14.0 6.0 – – 2.0 × 10−2
EMA_MA_POMA 14.0 6.0 – 0.2 2.0 × 10−2
MMA_POMA – – 10.0 0.1 1.0 × 10−2
V. Sabatini et al.
Fig. 1. Synthetic route for EMA_MA, EMA_MA_POMA and MMA_POMA copolymers.
2.4. Characterization of polymers
2.4.1. Nuclear magnetic resonance: 1H NMR
1
H NMR spectra were collected at 25 °C with a BRUKER 400 MHz
spectrometer. Samples for the analyses were prepared dissolving
10–15 mg of POMA, EMA_MA, EMA_MA_POMA and MMA_POMA in
1 cm3 of CDCl3.
2.5. Preparation of EMA_MA, EMA_MA_POMA and MMA_POMA foils
Polymeric foils were obtained via solution casting: polymers were
dissolved in ethyl acetate using 21% w/w concentration and the cor-
responding solutions were cast onto a PTFE substrate. The solvent was
evaporated for 24 h in vacuum oven (about 4 mbar) at 40 °C. Foils
thickness was in the range 120–125 μm; thickness was evaluated by
Nikon eclipse ME600 optical microscope with Nikon digital camera
light DS_Fi1, software Nis-Elementi BR, magnification 50X.
2.6. UV exposure simulation test
To evaluate the stability of the polymers under UV radiations, an
accelerated aging test was performed in according to UNI 10925:2001
standard method [18]. The test was conducted for 100 h (T = 25 °C and
p = 1 atm), with Ultra Vitalux lamp characterized by a wavelength of
315–400 nm for UVA rays and 280–315 nm for UVB ones.
2.7. Characterization of the films
2.7.1. Differential scanning calorimetry (DSC)
DSC analyses were conducted using a Mettler Toledo DSC1; the
samples were prepared weighting from 5 to 10 mg each in a standard
40 μl aluminium pan, heating from 25 °C to 125 °C at 10 °C/min and
using an empty 40 μl aluminium pan as reference. The thermal beha-
viour of the samples obtained after the UV exposure simulation test was
studied with the same thermal program.
2.7.2. Water contact angle (WCA) analyses
Surface wetting properties of the polymeric foils (4 × 4 cm, at-
tached on a glass slide) were assessed by contact angle measurement
using a Krüss Easydrop Instrument. The contact angle values were ob-
tained by depositing a drop (1 μl) of double distilled water on both the
air and the PTFE sides of the foils. At least, ten measurements were
taken on each sample to get reliable values, averaging the results ob-
tained. The wetting properties of the films obtained after the UV ex-
posure test were also determined.
2.7.3. Size exclusion chromatography (SEC)
The effect of UV exposure on the molecular weight of the polymeric
samples was evaluated using a SEC system having Waters 1515 Isocratic
HPLC pump and a four Phenomenex Phenogel (5 × 10−3Å-5 × 10−4Å-
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Progress in Organic Coatings 114 (2018) 47–57
5 × 10−5Å-5 × 500 Å) columns set with a RI detector Waters 2487
using a flow rate of 1 cm3/min and 40 μl as injection volume. Samples
were prepared dissolving 40 mg of polymer in 1 cm3 of anhydrous THF;
before the analysis, the solution was filtered with 0.45 μm filters.
Molecular weight data were expressed in polystyrene (PS) equivalents.
The calibration was built using monodispersed PS standards having the
following nominal peak molecular weight (Mp) and molecular weight
distribution (D): Mp = 1600000 Da (D ≤ 1.13), Mp = 1150000 Da
(D ≤ 1.09), Mp = 900000 Da (D ≤ 1.06), Mp = 400000 Da
(D ≤ 1.06), Mp = 200000 Da (D ≤ 1.05), Mp = 90000 Da (D ≤ 1.04),
Mp = 50400 Da (D = 1.03), Mp = 30000 Da (D = 1.06),
Mp = 17800 Da (D = 1.03), Mp = 9730 Da (D = 1.03),
Mp = 5460 Da (D = 1.03), Mp = 2032 Da (D = 1.06), Mp = 1241 Da
(D = 1.07), Mp = 906 Da (D = 1.12), Mp = 478 Da (D = 1.22); Ethyl
benzene (molecular weight = 106 g/mol). For all analyses, 1,2-di-
chlorobenzene was used as internal reference. The molecular weights of
the samples obtained after the UV exposure test were also determined.
2.7.4. Fourier transform- infrared (FT-IR)
FT-IR spectra of the unaged and aged polymer films were obtained
on a Spectrum 100 spectrophotometer (Perkin Elmer) in attenuated
total reflection (ATR) mode using a resolution of 4.0 and 256 scans, in a
range of wavenumber between 4000 and 400 cm−1. A single-bounce
diamond crystal was used with an incidence angle of 45°.
2.7.5. Scanning electron microscopy (SEM)
SEM studies were carried out by a Leica Electron Optics 435 VP
microscope. The investigations were performed with an acceleration
voltage of 15 kV and 50 pA of current probe. The samples were
mounted on aluminium specimen stubs with double-sided adhesive
tape and sputter-coated with a 20 nm thick gold layer in rarefied argon,
using an Emitech K550 Sputter Coater, with a current of 20 mA for
180 s.
2.8. Biological degradation
2.8.1. Preparation of EMA_MA, EMA_MA_POMA and MMA_POMA films
Polymeric films were obtained via brushing: polymers were dis-
solved in ethyl acetate using 21% w/w concentration and the corre-
sponding solutions were brushed on plain glass slides (7.6 × 2.6 cm) to
obtain a thin layer, using a paint brush with bristles made with
Polyamide 6. The solvent was evaporated for 24 h in vacuum oven
(about 4 mbar) at 40 °C. For each sample, two films were prepared: one
film was used unaged, the other one was artificially aged in an aging
chamber, as described in 2.6 paragraph.
2.8.2. Biodegradation assay (ASTM method)
The ASTM G21-96 (2002) [15] method was used to evaluate the
ability of fungi to grow on the synthetic polymers as previously re-
ported by Cappitelli and co-workers [19]. Preliminary experiments
were performed with Aspergillus niger (ATCC 9642) and Penicillium pi-
nophilum (ATCC 11797). Briefly, a spore suspension of the two fungi
was obtained and washed three times in order to avoid any residue from
the cultural medium. Spore suspensions were diluted to
(1 ± 0.2) × 106 spore/cm3 with sterile mineral solution and an equal
volume of the five spore preparations was pooled. Polymer samples
were placed, in triplicate, into Petri dishes filled with minimal salts agar
and a small volume of the pooled spore preparation is sprayed directly
onto the test samples. The inoculation was carried out 5 days after the
polymers synthesis and, when relevant, ageing. As no residue from the
cultural medium was present, the polymer samples were the only
source of carbon available for the fungal strains. The procedure was
also applied to a positive control made of pure cellulose (Supporting
information, Fig. S1). Negative controls were performed by spraying
sterilized mineral medium without spores on the polymer samples
(CNN1) as well as just putting the test samples on the Petri dishes filled
V. Sabatini et al.
with minimal salts agar without any kind of further treatments (CNN2).
All Petri dishes were incubated for 28 days at 30 °C and 85% humidity
and, every 7 days, fungal growth was verified by epifluorescence mi-
croscopic analysis.
2.8.3. Epifluorescence microscopy and image analysis
Fungi grown on synthetic polymers were stained using 0.1 mg/cm3
Fluorescent Brightener 28 at room temperature in the dark for 25 min
and then rinsed with sterile PBS. Samples were visualized using a Leica
DM 4000 B (Leica Microsystems, Milan, Italy) microscope with excita-
tion at 335 nm and emission at 433 nm. Images were captured with a
20x objective and acquired by a Cool_SNAP CF camera (Photometrics
Roper Scientific, Rochester, NY, USA). Percent area covered by fungi
was calculated via Image J software (ImageJ 1.49 v, National Institute
of Health, Bethesda, MD, USA) by analysing at least ten random images
for each sample. Average of obtained data is reported. According to the
ASTM G21-96 (2002) [15] method, on the basis of percentage area, a
growth ratings were assigned as follows: 0, no growth; 1, traces of
growth (less than 10%); 2, light growth (10–30%); 3, medium growth
(30–60%); 4, heavy growth (60% to complete coverage).
2.8.4. Colonization curves
Colonization curves were constructed according to Cattò and co-
workers [20,21] with some modifications. Briefly, percentage area
covered by fungi was plotted against the time and the polynomial
Gompertz model [22] was used to calculate the lag phase length (days)
and the maximum specific colonization rate (% area/day), using
GraphPad Prism software (version 5.0, San Diego, CA, USA). The lag
phase length corresponds to the time of fungal adaptation prior starting
the active colonization, while the maximum specific colonization rate
represents the maximum increase of the percentage area covered by
fungi during the experimental time.
2.8.5. Statistical analysis
Two-tailed ANOVA and Student’s t-test analysis, via a software run
in MATLAB environment (Version 7.0, The MathWorks Inc, Natick,
USA), were applied to statistically evaluate any significant differences
among the samples and concentrations according to Motulsky [23]. The
ANOVA and Student’s t-test analysis were carried out after verifying
data independence (Pearson’s Chi-square test), normal distribution
(D’Agostino-Pearson normality test) and homogeneity of variances
(Bartlett’s test). Tukey’s honestly significant different test (HSD) was
used for pairwise comparison to determine the significance of the data.
Statistically significant results were depicted by p-values ≤ 0.05.
2.9. Application of polymer coatings on marbles surfaces and WCA analyses
Polymers were dissolved in ethyl acetate using 21% w/w con-
centration. The application of coatings on marbles surfaces (Calcite and
Dolomite slabs of 10 × 10 cm, Supporting information Fig. S2) was
carried out using a brush with bristles made with Polyamide 6 in order
to obtain on marble surface a homogeneous and thin polymer layer of
around 120–130 μm; coatings thickness was evaluated as described in
2.5 paragraph. The same experimental procedure reported previously in
2.7.2 paragraph was adopted to determine wetting properties of bare
and coated marbles. The surface morphology of the uncoated marbles
was also characterized by profilometry, using a Bruker DektakXT con-
tact profilometer that it is equipped with a diamond cursor running on
the object surface and following local surface irregularities. The cursor
is linked with an optical transductor. The vertical displacements are
recorded by a photoelectric cell and amplified. The signal appears di-
rectly on the monitor of the analyser. The diamond point was 2.5 mm in
thickness. Each measurement was 10 mm in length and a 50 mm in-
terval separated two parallel measurements. For a given test line, the
roughness was defined in μm as the arithmetical mean of peaks above
and under the baseline. The mean roughness (Ra) was defined as the
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Progress in Organic Coatings 114 (2018) 47–57
Fig. 2. 1H NMR spectrum of POMA.
average of ten successive measurements; the quadratic mean (Rq) was
expressed as the quadratic average of the profile points deviations from
the mid-line.
3. Results and discussion
3.1. Synthesis and wetting characterization of EMA_MA, EMA_MA_POMA
and MMA_POMA copolymers
A new fluorinated methacrylic monomer, POMA, was synthesized
via esterification reaction between methacryloyl chloride and
1H,1H,2H,2H-Perfluoro-1-octanol. The structure of the product ob-
tained was determined via 1H NMR spectroscopy (Fig. 2).
A new type of polymer protective was prepared via free radical
polymerization between POMA and methyl methacrylate
(MMA_POMA). As references, EMA_MA and fluorinated EMA_MA
(EMA_MA_POMA) resins were synthesized. The structure of the pro-
ducts obtained was determined via 1H NMR spectroscopy, respectively
Fig. 3 for EMA_MA, Fig. 4 for EMA_MA_POMA and Fig. 5 for MMA_-
POMA.
Protective properties and durability both to weather variation and
biological attack are mandatory requirements for a cultural heritage
coating. Regards to the hydrophobicity, the wetting features of the
synthesized acrylic and methacrylic coatings were investigated by WCA
measurements (Table 2, second column). The samples were prepared
via solvent casting deposition and cast onto a PTFE mold: contact angle
measurements were acquired at both the air and PTFE sides of the
polymer foils.
The water contact angle of EMA_MA, both in the case of the air and
PTFE sides, is around 82°; this value increases up to 90° for
EMA_MA_POMA and MMA_POMA, owing to the addition of the fluori-
nated monomer, but only for the PTFE side.
The wetting difference between the air and PTFE sides can be as-
cribable to the re-organization of the fluorinated groups of the poly-
meric chains during the evaporation of the solvent and to the high af-
finity with the hydrophobic PTFE mold surface. As described by
Sabatini et al. [24], during the evaporation of the solvent, the apolar
groups in contact with a hydrophobic surface −the PTFE mold- are
orientated towards the hydrophobic surface, caused by the scarce affi-
nity towards the solvent. The mold side of EMA_MA and EMA_MA_-
POMA foils is characterized by higher WCAs than the ones measured at
the air side of the membranes themselves due to the selective orienta-
tion of the fluorinated chains on the PTFE side surface.
SEM analyses for EMA_MA, EMA_MA_POMA and MMA_POMA
samples were performed in order to clarify the influence of POMA
fluorinated pendant chains on the surface properties of the polymeric
foils prepared. Fig. 6 presents the morphology from both air-side and
PTFE-side of EMA_MA, EMA_MA_POMA and MMA_POMA foils.
In the case of EMA_MA, no surface difference is detectable between
the air-side (6a) and the mold-side of the polymeric foil (6b). When
V. Sabatini et al. Progress in Organic Coatings 114 (2018) 47–57

Fig. 3. 1H NMR spectrum of EMA_MA.

Fig. 4. 1H NMR spectrum of EMA_MA_POMA. Fig. 5. 1H NMR spectrum of MMA_POMA.

POMA is added, it is possible to observe that the surface at the air-side Table 2
remains similar to the one of EMA_MA-air side (6c, EMA_MA_POMA and Static contact angles (θ) determined before and after the aging test.

6e, MMA_POMA), while the surface at the mold-side of the foils changes Sample θ (°) unaged θ (°) aged
from smooth to rough (6d, EMA_MA_POMA and 6f, MMA_POMA). In
according with WCA data reported in Table 2, this is a further evidence EMA_MA-air side 83 ± 2 61 ± 4
that POMA monomer, in contact with the hydrophobic PTFE mold, EMA_MA-PTFE side 82 ± 1 58 ± 3
EMA_MA_POMA-air side 79 ± 2 73 ± 4
orients the apolar fluorinated chains, less affine to the solvent, to the EMA_MA_POMA-PTFE side 88 ± 1 71 ± 2
mold surface, changing the foil surface in correspondence of the PTFE- MMA_POMA-air side 65 ± 1 66 ± 1
side from smooth to rough, thus promoting the formation of a more MMA_POMA-PTFE side 90 ± 1 88 ± 1
hydrophobic surface than EMA_MA-mold side.

polymer, i.e. MMA_POMA resin, prepared without the adding to

3.2. Aging study polymer formulation of any photo stabilizer additive, a UV accelerated
exposure test was performed.
In order to determine the long-term behavior of the new tailored

51
V. Sabatini et al.
Fig. 6. SEM images of a) EMA_MA-air side, b) EMA_MA-PTFE side, c) EMA_MA_POMA-air side, d) EMA_MA_POMA-PTFE side, e) MMA_POMA-air side and f) MMA_POMA-PTFE side.
Figs. 7–9 show respectively a comparison between FT-IR spectra,
collected before and after the aging test, of i) EMA_MA, ii) EMA_MA_-
POMA and iii) MMA_POMA resins. The peaks (a) in the
∼3100 − 2800 cm−1 range are related to the bending of CeH ali-
phatic bonds [25]; the stretching of carbonyl ester groups (C]O) (b) is
between ∼1750 cm−1 and ∼1600 cm−1 [25] and the characteristic
absorption band for the symmetric stretching vibration of CeO con-
jugated to carbonyl ester groups (c) appears between ∼1350 cm−1 and
∼1100 cm−1 [25].
In the case of EMA_MA and EMA_MA_POMA samples, it is possible
to observe that the shape of (a) and (b) absorption peaks changes after
the UV exposure test, showing a significant variation of the character-
istic bands related to CeH aliphatic bonds and the same carbonyl
groups, in according with the occurred degradation phenomena of
polymeric bonds, i.e. the breaking of macromolecular chains them-
selves in corresponding of aliphatic and carbonylic groups [26–28].
This behavior is probably due to the presence in EMA_MA and EMA_-
MA_POMA macromolecular structures of hydrogen atoms, deriving
from acrylic monomer MA, in alpha position to carbonyl groups that are
able to start the photo-chemical degradation of the polymers, with both
the splitting of aliphatic chains and the breaking of the chemical bonds
52
Progress in Organic Coatings 114 (2018) 47–57
between the carbonyl groups and the fluorinated aliphatic pendant
chains, as it is possible to observe at around 1710 cm−1 with the pre-
sence of a sharp peak related to the formation of carbonylic degradation
products [29].
In the case of MMA_POMA samples, no significant differences are
detectable between FT-IR spectra collected before and after the aging
test.
Furthermore, the effect of UV exposure can be highlighted by the
evaluation of the number average molecular weight (Mn ), the weight
average molecular weight (Mw ), the peak molecular weight (Mp) and
the molecular weight distribution (D) by SEC (Table 3).
In the case of aged resins, EMA_MA and EMA_MA_POMA samples
become insoluble: only MMA_POMA based polymer remains soluble
after sunlight exposure test. Such behavior is due to the formation of
radicals that make the polymers reticulated via cross-linking reactions
[13,14] confirming the photo-chemical degradation process of acrylic
resins.
For MMA_POMA polymer the variation of the molecular weights
and the relative distribution (Table 3) before and after the aging test are
negligible, clearly evidencing the photo stability of the methacrylic
polymer
V. Sabatini et al.
MMA_POMA thermal properties were also assessed and compared
with the one obtained by EMA_MA and EMA_MA_POMA (Table 3). As
reported, EMA_MA and EMA_MA_POMA samples have gelled after UV
exposure test and the comparison of their thermal properties measured
before and after the aging test and also with MMA_POMA resin was not
possible.
The glass transition temperatures (Tg) of EMA_MA, EMA_MA_POMA
and MMA_POMA unaged are respectively 40, 38 and 89 °C. After the
aging test, MMA_POMA Tg remains almost the same.
To verify the influence of the ageing procedure on the wetting
properties of the three resins, WCA values were re-measured (Table 2,
third column). A significant decrease of θ was observed for both sides of
EMA_MA and EMA_MA_POMA polymer foils: this is further evidence
that the photo-chemical degradation of the polymer has occurred;
worth of note is the unchanged wetting behavior observed for MMA_-
POMA sample, that shows the same difference of wettability between
53
Progress in Organic Coatings 114 (2018) 47–57
Fig. 7. FT-IR spectra of EMA_MA i) collected before and after the
aging test, and magnification of a) bending CeH area and b)
stretching C]O area.
Fig. 8. FT-IR spectra of EMA_MA_POMA i) collected before and after
the aging test, and magnification of a) bending CeH area and b)
stretching C]O area.
the two sides of the polymer foil measured before the aging test.
3.3. Biodegradation study
The potential susceptibility of MMA_POMA to fungal degradation in
comparison to the reference EMA_MA and EMA_MA_POMA polymers
has been investigated by the standard ASTM G 21–96 procedure [15],
before and after their aging. The ASTM G 21–96 method has been
chosen in this study as it is a well-known and wide spread method, for
instance used by the industry to evaluate the resistance of materials to
fungal attack prior to their trading. In order to well distinguish fungal
growth on the synthetic polymers and avoid false positive results, fungi
were stained with a probe specific for fungi and observed by epi-
fluorescence microscope in a non-invasive way. Means of percentage
areas covered by fungi for each time step were calculated and values
obtained are reported in the Supplementary Material (Table S1 and Fig.
V. Sabatini et al. Progress in Organic Coatings 114 (2018) 47–57

Fig. 9. FT-IR spectra of MMA_POMA i) collected before and after the

aging test, and magnification of a) bending CeH area and b)
stretching C]O area.

Table 3 polymers, unaged and artificially aged, did not show statistically dif-
SEC data and glass transition temperatures of EMA_MA, EMA_MA_POMA and ferences among them, with the exception of MMA_POMA aged which
MMA_POMA samples before and after the aging test.
maximum specific colonization rate resulted higher than those of the
Sample Mn (Da) Mw (Da) Mp (Da) D Tg (°C) other polymers. Moreover, MMA_POMA aged results the only polymer
with a colonization rate statistically higher than the corresponding
EMA_MA unaged 31800 63400 49100 2.0 40 unaged one.
EMA_MA aged n.d. n.d. n.d. n.d. n.d. To summarize, it is clearly seen from the data reported that the
EMA_MA_POMA unaged 29500 61900 45600 2.1 38
susceptibility to fungal colonization of the different samples after UV
EMA_MA_POMA aged n.d. n.d. n.d. n.d. n.d.
MMA_POMA unaged 27000 57000 42400 2.1 89 aging test is significantly affected by the chemical structure of the
MMA_POMA aged 25000 56000 42000 2.2 87 monomers adopted during the polymerization reaction.
EMA_MA sample, both unaged and aged, shows the lowest percen-
tage area of fungal coverage respect to EMA_MA_POMA and
S3). MMA_POMA, but among artificially aged samples EMA_MA aged is
At the end of the experiments (28 days), both unaged and artificially characterized by a shorter lag phase in comparison to the corresponding
aged polymers showed a percentage area covered by fungi statistically unaged sample.
different to the respective negative control, with percentage values less Correlating this behavior with the data previously obtained after the
than 10%, corresponding to the rate 1 of the ASTM methodology aging test, i.e. the high instability of acrylic polymers over UV radia-
(Fig. 10). Unaged polymers did not show statistically differences among tions, this is further evidence that the photo-chemical degradation of
them, while artificially aged polymers resulted in a different amount of the polymer affects the durability of polymeric resin itself, favoring the
fungal colonization: EMA_MA_POMA aged showed the highest percen- fungal grown and colonization, i.e. promoting a short lag phase.
tage area of fungal coverage, followed by MMA_POMA aged and For EMA_MA and MMA_POMA unaged samples the percentages of
EMA_MA aged that showed values statistically comparable with those fungal coverage area are statistically comparable, but after aging
of unaged polymers. MMA_POMA resin is more prone than EMA_MA to fungal colonization;
Furthermore, the comparison between unaged and the corre- both in the case of unaged polymers and aged ones, MMA_POMA lag-
sponding artificially aged samples revealed that EMA_MA_POMA aged phase length remains almost the same before and after the aging test.
was more prone to be colonized by fungi with respect to the corre- Furthermore, the combined use of an acrylic monomer, i.e. MA,
sponding unaged one, followed by MMA_POMA and EMA_MA samples. with a fluorine based monomer (POMA) favours the fungal degradation
Fungal colonization against the time was also analysed for each of polymeric coating: in fact, EMA_MA_POMA aged shows the highest
unaged and aged polymers. Colonization curves versus the time were percentage area of fungal coverage and among aged samples, it is more
obtained and the colonization parameter of lag phase length (days) and prone to be colonized by fungi with respect to the corresponding un-
the maximum specific colonization rate (% area/day) were calculated aged one.
(Supplementary Material, Table S2). To the authors’ best knowledge the present data, i.e. of a suscept-
In Fig. 11A, the lag phase length values are reported. Among unaged ibility to a fungal grown and colonization promoted by the combined
samples, EMA_MA showed the longest lag phase, followed by EMA_- use of acrylic and fluorinated monomers, have never been reported in
MA_POMA and MMA_POMA. Among artificially aged samples, EMA_- previous scientific literature.
MA_POMA showed a longer lag phase in comparison to EMA_MA and
MMA_POMA. The comparison between the unaged and the corre-
sponding artificially aged samples revealed that only EMA_MA aged 3.4. Application of EMA_MA, EMA_MA_POMA and MMA_POMA resins on
presented a lag phase significantly shorter than the corresponding un- marbles surfaces
aged polymers.
As regarding the maximum specific colonization rate (Fig. 11B), all The comparison of both chemical and biological data measured

54
V. Sabatini et al. Progress in Organic Coatings 114 (2018) 47–57

Fig. 10. Fungal growth on the synthetic polymers

after 28 days of incubation. A: Mean of the percentage
area covered by fungi ± standard deviation calcu-
lated by analysing at least ten random microscope
images of three independent replicates. Different su-
perscript letters indicate significant differences
(Tukey’s HSD, p ≤ 0.05) between the means of syn-
thetic polymers. A star (*) indicates statistically sig-
nificant difference at the 95% confidence level be-
tween the unaged and the respective artificially aged
samples polymers. B, C: Representative epi-
fluorescence microscope images of fungi stained with
fluorescent brightener 28 (blu fluorescence) and
grown on negative controls (B) and unaged and aged
polymers (C); λex at 335 nm and λem at 433 nm,
20 × ; Scale bar = 50 μm.

before and after the aging test demonstrates that a polymer resin pre- well as the resistance to fungal attack than acrylic polymers.
pared starting from methacrylic and fluorinated monomers, i.e. MMA Within this context, the use of MMA_POMA based resin can be a way
and POMA, is an efficient way to obtain a protective with satisfactory to obtain a satisfactory protective for stone substrates.
water repellent properties and enhanced photo chemical durability as The pure and fluorine modified resins were applied on two marble

55
V. Sabatini et al.
Fig. 11. Fungal colonization parameter related to the synthetic polymers. Panel A shows
the lag phase length (days), while panel B depicts the maximum specific colonization rate
(% area/day). Parameters were calculated from fungal colonization curves obtained by
fitting the percentage area covered by fungi against the time with the polynomial
Gompertz model. Data represent the mean ± standard deviation calculated by analysing
at least ten random microscope images of three independent replicates. Different super-
script letters indicate significant differences (Tukey’s HSD, p ≤ 0.05) between the means
of synthetic polymers. A star (*) indicates statistically significant difference at the 95%
confidence level between the unaged and the respective artificially aged samples poly-
mers.
Table 4
Static contact angles (θ) measured on coated marbles.
Sample θ (°) Calcite θ (°) Dolomite
EMA_MA 72 ± 2 71 ± 2
EMA_MA_POMA 80 ± 1 83 ± 2
MMA_POMA 93 ± 2 98 ± 2
substrates −Calcite and Dolomite- and their wetting properties were
assessed (Table 4). The morphology of the two marble samples was
preventively characterized by profilometry (Supporting Information,
Fig. S4 for Calcite slab and Fig. S5 for Dolomite slab) in order to in-
vestigate the possible influence of the marbles surface roughness on
coatings wetting properties. Calcite mean roughness (Ra) and quadratic
mean (Rq) are 0.02 μm and 0.03 μm respectively; in the case of Dolo-
mite slab Ra and Rq data increase up to 0.05 μm and 0.09 μm, probably
due to Dolomite porous surface [30]. In according with previously data
reported in literature [31], the surfaces of the two commercial marbles
are smooth and are not able to significantly affect the morphology of
the coated resins.
At first the wetting of bare Calcite and Dolomite marbles was de-
termined; both two marbles surfaces show a contact angle of around 50°
that increases up to an average value of 70° with EMA_MA coating
deposition. Further, contact angles of around 80° are observed in the
case of EMA_MA_POMA, whereas high hydrophobicity is achieved by
MMA_POMA-clad surfaces. The increase of θ observed on Dolomite
marble with respect to Calcite one could be ascribed probably to the
former porous surface [30].
As previously reported in the case of EMA_MA, EMA_MA_POMA and
MMA_POMA polymer foils, a re-organization of the fluorinated groups
of the polymeric chains is occurred during the evaporation of the sol-
vent and to the interaction with the polar surface of marbles. In this
case, the apolar groups in contact with a marble hydrophilic surface are
orientated towards the air side surface. Indeed, the air side of marble
bars coated is characterized by higher WCAs than the ones measured at
the air side of the polymer membranes themselves due to the selective
orientation of POMA fluorinated chains.
Correlating MMA_POMA macromolecular and biological data ob-
tained before and after the aging test, i.e. the high UV stability and the
low fungal colonization susceptibility, with the WCAs values measured
on both Calcite and Dolomite surfaces, the new polymer coating
56
Progress in Organic Coatings 114 (2018) 47–57
prepared in this work could be, in a future, used as innovative water
repellent and durable protective for a very large number of stones.
4. Conclusions
The use of polymeric protectives is very advantageous in fields
when the hydrophobic properties and high chemical and biological
stability are requested. Within this context, the use of polymer resins
bearing methacrylic and fluorinated monomers along the polymeric
chain can be a way to create tailor-made water repellent materials with
enhanced durability, without the addition of any stabilizing agent.
A new kind of a fluorinated methacrylic monomer, 1H,1H,2H,2H-
Perfluoro-octyl-methacrylate (POMA) was synthesized, and a new type
of polymer protective was prepared via free radical polymerization
between POMA and methyl methacrylate (MMA_POMA).
In order to determine the long-term properties of MMA_POMA resin,
an accelerated UV exposure test was performed. The macromolecular
structure, molecular weights, thermal features, water repellence beha-
vior and biodegradation of MMA_POMA, compared to those of the two
reference polymers synthesized −ethyl methacrylate (EMA)_methyl
acrylate (MA) and EMA_MA_POMA resins-, were investigated before
and after the UV test via 1H NMR and Fourier Transform-Infrared (FT-
IR) spectroscopies, Size Exclusion Chromatography (SEC), Differential
Scanning Calorimetry (DSC), Water Contact Angle (WCA) measure-
ments and biodegradation studies.
Combining the chemical and biological data measured before and
after the aging test, it was possible to conclude that a polymer pro-
tective prepared starting from methacrylic and fluorinated monomers is
an efficient way to obtain a resin with satisfactory water repellent
properties and enhanced durability than acrylic polymers. Furthermore,
the combined use of acrylic and fluorinated monomers promotes the
fungal degradation of polymeric coating.
To the authors’ best knowledge the present observation, i.e. of a
susceptibility to a fungal grown and colonization promoted by acrylic
and fluorinated monomers, have never been reported in previous sci-
entific works.
Lastly, MMA_POMA resin was successfully applied on two porous
marble substrates −Calcite and Dolomite-, showing satisfactory hy-
drophobic features.
The work is continuing with an emphasis placed on the study of the
influence of different processing conditions, such as the loading of
fluorinated monomer, on the properties of MMA_POMA resin. Water
repellent behavior, chemical and biological durability will be described
in subsequent publications.
Acknowledgments
The authors wish to express their gratitude to Dr. Ombretta Locci,
Dr. Marco Sciuccati and Dr. Martina Spagnoli for their experimental
contributes.
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.porgcoat.2017.10.003.
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