Universit degli Studi di Parma

Hybrid inorganic-organic coatings based on PMMA for the

protection of sandstones
Silvia Alinovi (1), Andrea Lorenzi (1), Ilaria Alfieri (1), Federica Bondioli (2),
Giovanni Predieri (1), Laura Bergamonti (1,2), Danilo Bersani (3), Pier Paolo Lottici (3)
(1) Chemistry Department, University of Parma, Parco Area delle Scienze 17/A, 40124 Parma (Italy) giovanni.predieri@unipr.it
(2) Industrial Engineering Department, University of Parma, Parco Area delle Scienze 181/A, 40124 Parma (Italy)
(3) Physics and Earth Sciences Department, University of Parma, Parco Area delle Scienze 7/A, 40124 Parma (Italy)
Inorganic-organic hybrid coatings made of polymethylmethacrylate (PMMA) additioned by an inorganic filler based on SiO2 and ZrO2, for the protection of sandstones of
interest for cultural heritage have been studied. The selected test materials are two sandstones, named Pietra Serena and Pietra Dorata, outcropping in Tuscany (Italy)
and widely used as building stones. XRD, FT-IR and Raman investigations were carried out to characterize the synthesized hybrid materials and coatings. To evaluate the
efficacy of the treatment, water absorption test by capillarity (UNI EN 15801:2010), contact angle (UNI 11207:2007) and colorimetric measurements (UNI EN
15886:2010) were performed.

A simple procedure to synthesize inorganic-organic hybrid coatings made of

polymethylmethacrylate (PMMA) additioned by an inorganic filler based on
SiO2 and ZrO2 using the sol-gel technique, is here presented.
PMMA was dissolved in AUGEO SL191 and MEK then TEOS and
ZrOCl2*8H2O in ethanol were added as precursors for the oxides.
The solution was kept at RT for three hours. Two composites were prepared
with PMMA/SiO2/ZrO2 at 90/5/5 and 80/10/10 weight proportion.
The powders obtained by drying the sols were analyzed by FT-IR, Raman
spectroscopy and X-ray diffraction (XRD). The sols were applied on Pietra
Serena and Pietra Dorata.
PMMA-TEOS-ZrOCl 2*8H 2O

PMMA/SiO2/ZrO2 80/10/10

Intensity

XRD of the powdered hybrid

PMMA/SiO2/ZrO2 (80/10/10).
No crystalline features are
present.

10

20

30

40

50

60

70

FTIR spectra of the powdered hybrid

PMMA/SiO2/ZrO2 (80/10/10) (up) and 90/5/5
(down)). The main functional groups of the
composite are evident.

Raman spectrum of the powdered hybrid PMMA/SiO2/ZrO2

(80/10/10). Only PMMA features are clearly visible.

80

Stereomicroscope images of pietra dorata (left) and pietra serena (right).

Raman spectra of pietra dorata: points with

different proportions of calcite (C) and quartz (Q)
are shown.

Raman spectra of pietra serena in two different points.

Several minerals are evidenced: quartz (Q), anatase
(A), calcite (C), K-feldspar (likely sanidine S) and
carbon, (arrows) .

The Pietra Dorata sandstones can be classified as terrigenous arenites with plane-parallel stratification showing
yellowish colour. The siliciclastic component is mainly made up of quartz, K-feldspar, plagioclase, often chloritized
biotite, muscovite. The cement is made up of spatitic and micritic calcite and looks pigmented by iron oxides.
The Pietra Serena sandstone shows fine medium grain size and grey-bluish colour, with white mica lamellae
(muscovite). It is mainly made up of quartz, feldspar and phyllosilicate grains with minor amounts of siliciclastic rock
fragments. Both stones are found in Tosco-Emilian Appennine.
To evaluate the efficacy of the treatments, colorimetric tests, water absorption by capillarity and
conctact angle measurements were performed, according to UNI-EN Normal for natural stones.

a
CAPILLARITY ABSORPTION

- UNI EN 15801:2010
Water absorption
(Kg/m2).

by

capillarity

ESEM images of the Pietra Dorata (a) and Pietra Serena (b)
with the hybrid PMMA/SiO2/ZrO2 coating.

The absorption coefficient AC is

determined from the slope of the
linear fit to the curves up to 2 hrs
(insert).

Absorption Coefficient (AC)

Pietra serena
Pietra dorata

Untreated
0.01
0.025

Treated
0.003
0.015

COLORIMETRIC MEASUREMENTS - UNI EN 15866:2010

3
2.5
2
E*

Qi (Kg/m2)

Qi (Kg/m2)

1.5

Pietra Serena 90-5-5

Pietra Serena 80-10-10

1
Pietra Dorata 90-5-5
0.5
Pietra Dorata 80-10-10
0

CONTACT ANGLE MEASUREMENTS - UNI EN 11207:2007

80
70

90

Pietra
Serena

80
70

60

Angle

40

Untreated

10
0

50

Untreated
Untreated

40

30
20

60
Angle

Untreated

50

Pietra
Dorata

30
Treated 90-10

Treated 90-10

20
10

Treated 80-20

Treated 90-10

Treated 80-10

Treated 90-10

The results on the water absorption and on the contact

angle indicate, for Pietra Serena and Pietra Dorata
coated
with
hybrid
PMMA/SiO2/ZrO2,
an
improvement of the water repellency. The total color
difference introduced by the coatings is acceptable,
without evident modifications of the aesthetic
appearance.