DOI: 10.

1007/s00339-004-2530-4
Appl. Phys. A 79, 347351 (2004)
Materials Science & Processing
Applied Physics A
t. poli
1
l. toniolo
1,u
o. chiantore
2
The protection of different Italian marbles with
two partially ourinated acrylic copolymers
1
CNR ICVBC Sezione Milano Gino Bozza, Politecnico di Milano, P. za L.da Vinci 32,
20133 Milano, Italy
2
Dipartimento di Chimica IFM, Universit di Torino, via Giuria 7, 10125 Torino, Italy
Received: 23 July 2003/Accepted: 15 December 2003
Published online: 19 May 2004 Springer-Verlag 2004
ABSTRACT Committing stone protection to polymeric materi-
als started in the sixties but the study and knowledge of the
complex and multiple interactions between stone and poly-
mers has only been carried out recently. Its important to
note that, together with the factors related to the polymeric
system itself, intrinsic properties of the stone substrate, like
composition, porosity, and crystalline characteristics, play a rel-
evant role. In this paper the issues related to protection of
three different Italian marbles have been investigated: Can-
doglia marble, employed in the building of the Milan Cathe-
dral, Carrara marble, widely used in sculpture and historical
architecture, and S. Giuliano marble, used in the building
of the Pisa Cathedral and its famous leaning tower. Speci-
mens coming from blocks of the three quarried stones have
been characterized, treated with two new partially uorinated
acrylic copolymers, 2,2,2-triuoroethyl methacrylate/methyl
acrylate (TFEMA/MA), and triuoromethyl-2,2,2-triuorethyl
methacrylate/methyl acrylate (HFIMA/MA), and tested ac-
cording to UNI-Normal Italian protocol. All the measurements
including capillary water absorption, static contact angles,
colour variation, water vapour permeability, and SEM mor-
phological analysis have been carried out before and after the
polymeric treatment. The aim of this work is to evaluate the
protective efcacy of these two new partially uorinated acrylic
copolymers on the three different marbles, and to correlate the
different behaviours with the polymers properties and with the
stone substrates characteristics.
PACS 61.41.+e; 81.05.Lg; 68.08.de; 68.60.wm
1 Introduction
The chemical corrosion due to aggressive pollu-
tants, freezing and thawing cycles, and the crystallisation of
salt solutions absorbed from the environment are the main
causes of the deterioration of stone materials exposed to
outdoor conditions. The most appropriate way to avoid this
deterioration is to prevent or reduce, at least, water pene-
tration into the stone bulk, since condensed water is mainly
responsible for stone decay. The use of polymers as protective
u Fax: +390270602899, E-mail: lucia.toniolo@polimi.it
coatings for stone materials, started in the sixties as conse-
quence of the huge growth of macromolecular chemistry and
the successful diffusion of synthetic resins in many differ-
ent elds [1, 2]. The acrylic and silicone resins seemed to be
the denitive answer to the outdoor exposed stone materi-
als [3]. But the new products have been adopted and widely
employed by restorers without considering that these mate-
rials havent been studied and developed specically for the
preservation of cultural heritage. Moreover, often the appli-
cation has been carried out without a deep knowledge of the
polymers properties and of the interactions between stones
and hydrophobic lms. These facts, with the great heterogene-
ity of stone materials and with the different environmental
situations, are the main causes of unsatisfying performance
obtained by synthetic resins in the protection of outdoor ex-
posed stone monuments. A new class of protective polymers,
based on uoro-acrylic structures, has been prepared and
tested on natural stones during the last ve years [4, 5]. The
main characteristics of these products are the presence of u-
orine, the acrylic backbone and an easy and relatively lowcost
synthetic process [6]. Other interesting features are enhanced
water repellency [7, 8] and durability, overall transparency,
and high solubility [9, 10]. During this experimental work
many copolymers have been studied, prepared, and tested on
different stone substrates, mainly Noto calcarenite [5, 11, 12],
and Candoglia marble [1214], in order to identify the best
performing polymeric structure. In this work two copoly-
mers, the 2,2,2-triuoroethyl methacrylate/methyl acrylate
(TFEMA/MA), and the triuoromethyl-2,2,2-triuorethyl
methacrylate/methyl acrylate (HFIMA/MA), have been
tested on different white marbles, Carrara, and S. Giuliano, to
obtain information about the relationship between perform-
ance and substrates characteristics.
2 Experimental
2.1 The copolymers
The two copolymers, the 2,2,2-triuoroethyl
methacrylate/methyl acrylate (TFEMA/MA) and the tri-
uoromethyl-2,2,2-triuorethyl methacrylate/methyl acry-
late (HFIMA/MA), were prepared by radical polymerisation
(60

C, 70 h) in freeze-thaw-pump degassed dioxane solu-

tions (about 1.5 mol L
1
total monomer concentration) using
AIBN(1.5 mol %) as the initiator [6].
348 Applied Physics A Materials Science & Processing
Copolymer molar ratio % F Tg (

C) M
n
M
w
HFIMA/MA 2:1 40.7 48
TFEMA/MA 2:1 27 43 21000 36000
TABLE 1 Characteristics of the tested polymers
In Table 1 compositional characteristics and glass transi-
tion temperatures are reported. The application of the poly-
mers was carried out by capillary absorption from a lter
paper pad saturated with a 5 wt % solution of the copolymer
in ethyl acetate (Fluka, for HPLC 99.8%). The treatment was
prolonged over 8 h; the treated specimens were dried at room
temperature on glass beads for 24 h and then at 40

Cfor 24 h.
Finally they were dried at 50 Pa for 24 h at room temperature
and stored in silica gel desiccators.
2.2 The stone materials
The natural stone materials selected for the test-
ing are: Carrara marble, a white veined metamorphic stone
with a uniform saccaroid crystalline structure and an open
porosity of around 2%. S. Giuliano marble, a white-grey, not
completely metamorphic material, with a very ne crystalline
structure. In Table 2 the main physical properties of the con-
sidered stones (Candoglia marble included) are summarized.
The stone specimens were cut into squared blocks of 5
52 and 551 cm sizes. The surface of each specimen
was smoothed with abrasive carborundum paper (Nr. 180).
The specimens were then carefully washed with deionised
water and dried for 24 h at 40

C followed by 24 h under
vacuum (50 Pa) at room temperature; they were then nally
weighed and stored in silica gel dessicator before treatment.
2.3 The testing methodologies
Water repellency, water capillary absorption, water
vapour permeability, and colorimetric tests were performed
on the stone specimens, according to uni cultural heritage pro-
tocol, before and after application of the polymer coating [15].
To give a prompt evaluation of the amount of water
absorbed by capillarity action, the results are reported as
a relative capillary index (ICr), a parameter suggested in
the protocol [15]. ICr comes from the ratio of the areas de-
scribed by the capillary absorption curves before and after
treatment [16].
Color changes were measured with a CR-200 Minolta col-
orimeter, based on the L*a*b* coordinates of the CIELAB
space. Static contact angle measurements were performed
with a Lorentzen &Wettre instrument.
Density Total open Open Open Maximum Capillary
porosity microporosity macroporosity capillary absorption
(mercury) absorption coefcient
(g/cm
3
) (%) (%) (%) (mg/cm
2
) [15]
Candoglia 2.72 0.64 0.23 0.45 4.0 0.0243
Carrara 2.60 1.90 1.30 0.70 8.0 0.1533
S. Giuliano 2.61 0.57 0.10 0.50 2.0 0.0044
TABLE 2 Characteristics of the considered stones
FIGURE 1 ICr (Relative Capillary Index) values obtained by the two
copolymers on the selected substrates
3 Results and discussion
The two copolymers, HFIMA/MA and TFEMA/
MA, have been already tested on Noto stone and Candoglia
marble [5, 1114].
The great open porosity of the calcarenite (30%), allows
penetration of a large amount of protective polymer, and em-
phasizes the efcacy of both copolymers (Fig. 1).
The protection of stone with low porosity ( 2%), like
Candoglia marble, is more critical; most of the polymer
remains on the surface of the stone and is exposed to the
ageingprocess [1214]. On these substrates, the results ob-
tained for the copolymers are similar; in order to highlight
the different performances of the polymers it has been neces-
sary to enlarge the experimentation to two new critical stone
substrates, and with an enlarged number of specimens too.
4 The penetration of the polymers
The ability of the polymer solution to penetrate into
the stone substrate is one of the most important factors for
a successful protective treatment. The amount of product that
can penetrate the porous matrix of the stone is a key param-
eter, especially in the case of low porosity materials, where
the treatment tends to accumulate on the surface of the speci-
mens [17].
Theoretically, if a product penetrates uniformly in the
stone matrix we should nd half the amount of it in the half
volume specimens.
As is evident from data reported in Table 3, this nearly
happens in the case of TFEMA/MA applied to Carrara mar-
POLI et al. The protection of different Italian marbles with two partially ourinated acrylic copolymers 349
HFIMA/MA TFEMA/MA
sample mg/cm
2
mg/cm
3
sample mg/cm
2
mg/cm
2
552 CR1 0.72 0.35 552 MR1 0.92 0.47
552 CR2 1.05 0.51 552 MR2 1.23 0.62
552 CR3 0.93 0.47 552 MR3 1.16 0.56
552 CR4 0.77 0.39 552 MR4 0.86 0.44
average 0.87 0.43 average 1.04 0.52
551 CR5 0.83 0.90 551 MR5 0.70 0.86
551 CR6 0.78 0.74 551 MR6 0.69 0.74
TABLE 3 Amount of product absorbed by Carrara
marble samples
Average amount Static contact angle ICr
of product [16]
(mg/cm
3
)
552 (

)
HFIMA/MA 0.83 108 3 0.70
TFEMA/MA 0.70 94 4 0.67
TABLE 4 Average amount of product, static contact angles and relative
Capillary Index obtained on Candoglia marble treated with the two consid-
ered copolymers
ble (about 30% of polymer in the 551 cm specimens),
while it is not veried in the case of HFIMA/MA, the 5
52 cmand 551 cmspecimens contain a similar amount
of the latter. Its possible to suppose that TFEMA/MA hav-
ing a shorter and simpler side chain, could penetrate deeper,
even in a low porosity substrate like Carrara marble, while
HFIMA/MA tend to accumulate on the surface. On average,
on the 552 cm specimens the content of TFEMA/MAis
20%larger than HFIMA/MA(Table 3).
On Candoglia marble (Table 4) HFIMA/MA shows the
same behaviour observed on the Carrara one, absorbing simi-
lar amounts of copolymer in all specimens (0.83 mg/cm
2
).
TFEMA/MA, on the contrary, shows a lower polymer content
(0.70 mg/cm
2
), probably because it is unable to penetrate into
Candoglias porous matrix as it partially does into Carraras.
S. Giuliano marble has an irregular structure due to the
incomplete metamorphization and to the presence of quartz
and calcite re-crystallization veins. The very low porous ma-
trix often presents deep microfractures between the different
crystalline systems. Therefore the penetration of products in
the specimens cant be uniform. In both series, the one treated
with HFIMA/MA and the one treated with TFEMA/MA,
there are two specimens that absorb twice the amount of poly-
mer than the two others (Table 5), having the same thickness.
The presence of such important differences between the
specimens doesnt allow to evaluate the ability of the poly-
HFIMA/MA TFEMA/MA
sample mg/cm
2
mg/cm
3
sample mg/cm
2
mg/cm
2
552 CS1 0.40 0.20 552 MS1 0.72 0.36
552 CS2 0.42 0.21 552 MS2 0.87 0.43
552 CS3 0.90 0.44 552 MS3 0.42 0.21
552 CS4 0.87 0.43 552 MS4 0.44 0.22
average 0.65 0.32 average 0.61 0.30
551 CS5 0.44 0.49 551 MS5 0.57 0.62
551 CS6 0.35 0.38 551 MS6 0.45 0.43
TABLE 5 Amount of product absorbed by S. Giuliano
marble samples
mer solutions to penetrate into the stone bulk. On average, S.
Giuliano marble absorbs less product than Carrara.
5 Colour variations and supercial water repellency
The two copolymers show a similar behaviour on
both substrates, Carrara marble and S. Giuliano marble, as
highlighted by the E obtained values (Tables 6 and 7).
E variations are around two, a value that is near to the
lower limit of the human eye perception. The L*a*b* coordi-
nate that gives the higher contribution to the colour changing
is for both substrates, L* (brightness): all the treatments in-
duce a little darkening of the surface. Therefore, it can be
concluded that uorinated copolymers behave, in terms of the
variations induced on the appearance of marble surfaces, at
least as well as conventional acrylic protectives, whose posi-
tive optical properties are well known.
As predictable, examining the static contact angles results,
the polymer with the highest uorine content (HFIMA/MA)
shows the highest static contact angle on both substrates
(about 10 degrees higher) (Tables 8 and 9).
On S. Giuliano marble the measured angles are little
higher thanks to the higher heterogeneity of the surface [7, 8].
In any case, the obtained angle values are rather high (> 95),
considering the degree of smoothness of the marble surfaces.
The static contact angles measurement will become a criti-
cal parameter to analyze, after the planned thermal and UV
ageing steps.
6 Water absorption by capillarity
The uniform crystalline matrix of Carrara marble
permits a great reproducibility of the capillary absorption
curves. Although, both copolymers give rather good results on
a critical substrate like Carrara marble, HFIMA/MA shows
a better efcacy, even with a lower polymer penetration. Rela-
tive Capillary Index (ICr) values ranging between 0 (max
protection effect) and 1 (lowprotection effect) obtained with
350 Applied Physics A Materials Science & Processing
HFIMA/MA TFEMA/MA
sample E L a b sample E L a b
CR1 0.83 0.83 0.02 0.01 MR1 1.53 1.50 0.31 0.05
CR2 0.68 0.67 0.00 0.12 MR2 1.04 0.94 0.34 0.28
CR3 0.82 0.80 0.04 0.18 MR3 1.89 1.80 0.28 0.53
CR4 0.78 0.78 0.01 0.03 MR4 1.68 1.67 0.23 0.05
CR5 0.78 0.76 0.01 0.17 MR5 0.91 0.87 0.06 0.26
CR6 0.48 0.48 0.01 0.02 MR6 0.79 0.77 0.02 0.18
average 0.73 0.72 0.01 0.08 1.31 1.26 0.20 0.12
TABLE 6 Colour variation observed on Carrara
marble samples after the treatments
HFIMA/MA TFEMA/MA
sample E L a b sample E L a b
CS1 2.12 1.68 0.1 1.29 MS1 0.9 0.82 0.21 0.29
CS2 2.14 1.79 0.05 1.17 MS2 1.11 0.88 0.27 0.62
CS3 0.86 0.73 0.03 0.45 MS3 1.63 1.35 0.21 0.89
CS4 1.04 0.71 0.14 0.75 MS4 2 1.6 0.38 1.13
CS5 0.94 0.67 0.07 0.65 MS5 1.26 0.97 0.02 0.8
CS6 1.96 1.56 0 1.18 MS6 2.08 1.63 0.04 1.29
average 1.51 1.19 0.02 0.92 1.50 1.21 0.19 0.84
TABLE 7 Colour variation observed on S. Giu-
liano marble samples after the treatments
HFIMA/MA TFEMA/MA
sample ICr sample ICr
CR1 109 5 0,51 MR1 96 4 0,68
CR2 107 5 0,55 MR2 100 3 0,67
CR3 104 5 0,47 MR3 90 4 0,81
CR4 104 4 0,73 MR4 97 2 0,69
CR5 106 4 MR5 94 4
CR6 106 3 MR6 97 2
average 106 0,57 average 95,7 0,71
TABLE 8 Static contact angles and ICr values observed on Car-
rara marble samples after the treatments
HFIMA/MA TFEMA/MA
sample ICr sample ICr
CS1 112 4 1,48 MS1 105 3 0,55
CS2 110 3 0,88 MS2 105 2 0,50
CS3 108 3 0,33 MS3 107 6 0,75
CS4 115 9 0,42 MS4 105 2 0,93
CS5 113 5 MS5 107 3
CS6 114 5 MS6 105 2
average 112 0,78 average 105,7 0,68
TABLE 9 Static contact angles and ICr values observed on
S. Giuliano marble samples after the treatments
HFIMA/MA are about 20% lower than those obtained with
TFEMA/MA(Table 8) (Fig. 1).
On the S. Giuliano marble the situation is more complex.
The intrinsic unhomogeneity of the stone and the very low
porosity determine a widely spread collection of data con-
cerning water absorption. This condition doesnt allow a co-
herent evaluation of the protective efcacy of the copolymers.
In any case, for both copolymers, the lower the amount of
protective uptake (Table 7) the lower the ICr values (Table 9).
This is not strictly connected to the polymer efcacy but to the
micro-structural characteristics of the stone substrate.
7 Conclusions
The introduction of uorine in the esteric side
chains of acrylic polymers dramatically increases the water-
repellency of the stone surface and in most cases allows a re-
duction of the water absorbed by capillarity. On low porosity
substrates this reduction is rather critical and the protection ef-
cacy varies with the specic type of stone structure. In the
case of Carrara marble, the protection efcacy is improved
by the increasing amount of uorine (HFIMA/MA 41%
TFEMA/MA 26%). In the case of Candoglia [12], a very
coarse crystal methamorphic stone, the considered copoly-
mers, remain on the surface and show a quite similar pro-
tective behaviour (Table 4). Regarding the third marble, S.
Giuliano, the protection effectiveness of the two copolymers
seriously depends on the microstructural quality of the stone
which dramatically changes fromone specimen to another.
Each marble, and moreover, each stone, has its own spe-
cic surface and bulk properties that affects the shielding
efcacy of a product. For a newand correct approach to a con-
servation problem, its decisive to study the stone/polymer
system and not to only consider the polymer characteristics.
POLI et al. The protection of different Italian marbles with two partially ourinated acrylic copolymers 351
The nal results of a correct laboratory testing, should be to
select the conservation product protective or consolidating
polymer-specically tuned for that substrate.
As for the efcacy of the polymers considered here, the
results have to be completed and integrated with the data com-
ing fromthe planned thermal and UVageing for a reliable and
denitive evaluation of the polymers performance.
REFERENCES
1 J. Delgado, E. Charola: Sci. Tech. Cultural Heritage 5 1, 93 (1996)
2 C.V. Horie: Materials for conservation (Butterworth & Co, London
1987)
3 R.P.J. van Hees, J.A.G. Koek, H. De Clercq, E. De Witte, L. Binda,
E.D. Ferrieri, E. Carraro: Proc. of 4th Int. Symp. on Conservation of
Monuments in the Mediterranean, Rhodes 611 May 1997, 3, p. 395
4 G. Alessandrini, L. Toniolo, C. Colombo: Proc. of 18th IIC Intern.
Congress, Melbourne 2000 p.1
5 G. Alessandrini, M. Aglietto, V. Castelvetro, F. Ciardelli, R. Peruzzi,
L. Toniolo: Appl. Polym. Sci. 76, 962 (2000)
6 F. Ciardelli, M. Aglietto, V. Castelvetro, O. Chiantore, L. Toniolo: Proc.
of New Millennium Int. Forum on Conservation of Cultural Property,
December 58th, Seoul, 2000 166181
7 C.D. Volpe, A. Penati, R. Peruzzi, S. Siboni, L. Toniolo, C. Colombo:
J. Adhesion Sci. Technol. 14, 273 (2000)
8 T. Poli, L. Toniolo, R. Peruzzi, M. Brugnara, C.D. Volpe: MRS Proceed-
ings Volume 712 Symp. II Materials Issues in Art and Archaeology VI
P.B. Vandiver, M. Goodway, J.L. Mass (Boston 2002)
9 O. Chiantore, M. Lazzari, V. Castelvetro, M. Aglietto: Proc. of Fluorine
in Coatings IV (Brussels 2001)
10 O. Chiantore, M. Lazzari: Polymer 42, 17 (2001)
11 O. Chiantore, M. Lazzari, T. Poli, C. Colombo, R. Peruzzi, L. Toniolo:
Proc. 5th Int. Symp. on Conservation of Monuments in the Mediter-
ranean Basin 2002, (Swets & Zeitlinger, Lisse 411 2002)
12 T. Poli: PhD thesis, Uni. of Turin, Italy 2002
13 T. Poli, L. Toniolo, O. Chiantore, M. Lazzari, V. Castelvetro, A. Man-
ariti: J. Cultural Heritage 3, 309 (2002)
14 O. Chiantore, C. Colombo, R. Peruzzi, T. Poli, L. Toniolo: Annali di
Chimica 91, 741 (2001)
15 UNI10921 Protocol Water repellents (2000)
16 R. Peruzzi, T. Poli, L. Toniolo: J. Cultural Heritage 4, 3, 93 (2003)
17 F. Casadio, L. Toniolo: J. Am. Inst. Conservation, in press (2004)