Appl Phys A (2014) 114:723–732

DOI 10.1007/s00339-013-7942-6

Commercial Ca(OH)2 nanoparticles for the consolidation

of immovable works of art
P. Baglioni · D. Chelazzi · R. Giorgi · E. Carretti ·
N. Toccafondi · Y. Jaidar

Received: 7 June 2013 / Accepted: 19 August 2013 / Published online: 31 August 2013
© Springer-Verlag Berlin Heidelberg 2013

Abstract Calcium hydroxide nanoparticles are effective 1 Introduction

components for the consolidation treatment of immovable
works of art, such as carbonate stone and wall paintings The use of compatible restoration materials is a key concept
that exhibit both surface and structural degradation. Several that has acquired growing importance in the consolidation
formulations have been recently developed, with different of immovable cultural heritage such as wall paintings and
characteristics (dispersing solvent, particle size distribution stone. The basic idea is to consolidate objects and master-
and particle structure), which are expected to result in differ- pieces using materials whose physico-chemical nature is as
ent long-term consolidating properties. In this contribution, close as possible to the original work of art’s materials, so to
the carbonation of a commercial Ca(OH)2 nanoparticle for- grant the durability of the treatment and the long-term sta-
bility of the consolidated substrates.
mulation (Nanorestore® ) was characterized through Fourier
Calcium carbonate is the main component of the major-
transform infrared (FTIR) analysis. Nanoparticle films were
ity of wall paintings and carbonate stone (limestone, mar-
laid on KBr pellets and stored at room temperature under
ble etc.). Typically, classic wall paintings such as frescoes
controlled relative humidity and CO2 pressure. FTIR anal-
include an inner layer (arriccio) in contact with the wall
ysis was used to quantitatively detect the formation of cal-
structure, the intonaco layer (usually obtained by a 1:1 mix-
cium carbonate. Fitting of the experimental data allowed
ture of lime and sand) and the paint layer, which comprises
the description of the mechanism of carbonate nucleation
a mixture of pigments and calcium carbonate, formed by
and growth. The compatibility of the Nanorestore® formu-
the reaction of calcium hydroxide with atmospheric CO2 .
lation for wall painting consolidation was assessed through In the secco painting technique, pigments are applied on
optical and electron microscopy, colorimetry and water ab- the dried intonaco using organic binders (egg or milk) or
sorption capillarity measurements. The formulation’s effec- vegetal extractives. Both stone and wall paintings can un-
tiveness in consolidating powdering painted layers was as- dergo different kinds of degradation, including corrosion by
sessed through application on site and on detached sam- acid rain, freeze–thaw cycles, physical erosion, crystalliza-
ples of Mesoamerican wall paintings belonging to the pre- tion/solubilization cycles of salts (such as sulfates, nitrates
Columbian archaeological sites of Ixcaquixtla and Calakmul and chlorides) [1–3] and biodegradation due to bacteria,
(Mexico). fungi, molds and lichens [4, 5].
Starting from the 1960s, synthetic organic materials such
as acrylate and vinyl copolymers have been continuously
used both as protective hydrophobic coatings and to con-
solidate wall paintings and stone, and they are still widely
diffused in restoration practice. The main problem related
P. Baglioni (B) · D. Chelazzi · R. Giorgi · E. Carretti · to the use of these materials lies in the lack of compatibil-
N. Toccafondi · Y. Jaidar ity with the carbonate-based works of art, which eventually
Department of Chemistry and CSGI, University of Florence, results in the degradation of the treated objects due to the
via della Lastruccia 3, 50019 Sesto Fiorentino, Florence, Italy
e-mail: baglioni@csgi.unifi.it
strong alteration of the substrate porosity, capillarity, per-
Fax: +39-055-4573032 meability to water vapor and wettability [6, 7]. Moreover,
724 P. Baglioni et al.

synthetic polymers can undergo yellowing and alteration of can be obtained using templates such as a water-in-oil mi-
their molecular weight resulting in decreased solubility in croemulsions [21] or hydrosoluble polymers [22], or using
net solvents [8]. calcium alkoxides as intermediates through a high-pressure
An alternative to synthetic polymers for consolidation alcohol–thermal reaction [13]. By using the aforementioned
purposes is the use of inorganic consolidants and, among processes, several different formulations can be obtained,
these, calcium hydroxide must be considered as a particu- exhibiting different particle sizes (from a few nanometers
larly indicated material. In fact, Ca(OH)2 can be delivered up to 200–400 nm), structure (e.g. hexagonal platelets) and
onto the surface layers and through the porous matrix of using dispersing solvents such as ethanol, 1-propanol and
artistic objects, where it reacts with CO2 (carbonation pro- 2-propanol.
cess) recreating a network of calcium carbonate that bridges In top-down processes the starting materials are reduced
microdetachments and flaking or powdering parts, provid- from bulk size to the nanoscale using different forms of en-
ing consolidation and long-term stability since the physico- ergy such as mechanical, chemical, thermal etc.
chemical properties of the treated substrates are left unal- For instance, typical top-down approaches use either
tered. However, the use of both aqueous solutions and dis- grinding of bulk materials (e.g. in a mill [23]) or thermal de-
persions of Ca(OH)2 is not advisable. composition. Another common example is nanolithography,
For what concerns saturated Ca(OH)2 aqueous solutions where an etching process is carried out to obtain nanometer-
(i.e. limewater), it must be considered that due to the low scale structures either using UV light or X-rays, or chemi-
solubility of calcium hydroxide, limewater is too weak as a cally.
consolidating material. In fact, a large amount of solution Presently, a practical top-down method for obtaining
must be used in order to achieve some consolidating effect, Ca(OH)2 nanoparticles is based on the thermo-mechanical
and the application of large amounts of water is detrimen- treatment of slaked lime, where the complete slaking of
tal to wall paintings’ porous matrices, since it can favor the lime is obtained through high temperature and pressure [12].
pore collapse through freeze–thaw cycles, the transport of In this way, the unreacted calcium oxide core of lime parti-
soluble salts and the presence of microorganisms [9]. More- cles is hydrated, leading to volume expansion that fragments
over, aqueous dispersions of Ca(OH)2 are not stable and fast the particles down to the nanoscale. The process leads to the
clustering and sedimentation of the hydroxide particles oc- production of large quantities of highly crystalline hexag-
cur, with undesired practical consequences (scarce penetra- onal portlandite nanoparticles whose average size is 150–
tion and veiling of the treated surface). 300 nm, which can be stably dispersed in 2-propanol with-
For these reasons, the use of both limewater and aqueous out any need of purification or additional treatments, and
dispersions of calcium hydroxide has been deemed disad- the particle size distribution and polydispersity can be tuned
vantageous and alcohol, rather than water, has been chosen by adjusting both temperature and pressure [13]. These as-
as a carrier for hydroxide particles since early research work pects and the feasibility of the process make this production
on innovative materials for wall painting consolidation [10]. method particularly advantageous in the framework of ap-
As a matter of fact, dispersions of Ca(OH)2 nanoparticles plications to cultural heritage consolidation, granting an up-
in short-chain alcohols have been proven to be effective for scaled production to meet the needs of end users and con-
consolidation treatments [9–13]. The small dimensions of servators.
particles grant the dispersions stability, ease the penetration In the last decade, calcium hydroxide nanoparticles ob-
through porous substrates and increase the reactivity of the tained from bottom-up processes have been used with high
particles to CO2 . efficiency for the restoration of lime-based wall paintings
The preparation of nanoparticles can be carried out and stone [11, 24]. Recently, dispersions of calcium hydrox-
through either bottom-up or top-down processes. The main ide nanoparticles obtained from the aforementioned top-
difference between the two approaches concerns the starting down method and mixed with barium hydroxide nanopar-
material from which particles are obtained. In bottom-up ticles have been effectively used for the consolidation of
processes nanoparticles are built atom by atom or molecule Mesoamerican wall paintings [12], and the Nanorestore®
by molecule, using several techniques such as crystal growth product has been positively assessed for the consolidation
from liquid or vapor phase, deposition or solid-state sinter- of dolostone [25]. The positive results reported by these
ing. For instance, a reliable method is to precipitate particles tests and the continuous demands by end users are being
from liquid phase through the homogeneous phase reaction paralleled by research work aimed to investigate the mech-
between solutions that are mixed together. Following this anism of carbonation and to characterize the calcium car-
approach, the synthesis of calcium hydroxide nanoparticles bonate phases produced through the process. The latter as-
can be performed through a homogeneous phase reaction ei- pect has been the subject of a work by Lòpez-Arce et al.
ther in water [11, 14–17] or in organic solvents to reduce the [26], where the Nanorestore® product was exposed to differ-
particle size [18–20]. Alternatively, Ca(OH)2 nanoparticles ent relative humidity values (RH = 33 %, 54 %, 75 % and
Commercial Ca(OH)2 nanoparticles for the consolidation of immovable works of art 725

90 %) and monitored at large time intervals (7, 14, 21 and 28 wall paintings belonging to the archaeological site of Ix-
days) using several analytical techniques. Results indicated caquixtla (Puebla, Mexico). In all cases the dispersion was
a strong influence of RH on the precipitation and transfor- applied by gentle brushing on the painted layer, using a sheet
mation of calcium carbonate polymorphs. In particular, it of Japanese paper to protect the sample surface. The dis-
has been shown that higher RH (75–90 %) results in the for- persion was applied until it was ‘rejected’ by the surface,
mation of amorphous calcium carbonate, monohydrocalcite, then a humid cellulose poultice was placed upon a sheet of
calcite, aragonite and vaterite, with faster carbonation lead- Japanese paper over the treated surface and allowed to dry,
ing to larger particle size and higher crystallinity. Lower RH in order to favor carbonation. After treatment, the detached
values (33–54 %), on the other hand, lead to the production Calakmul samples were then stored at room temperature and
of vaterite, with a slower carbonation resulting in the forma- RH = 60 % for five months, before characterization was car-
tion of smaller particles with lower crystallinity. ried out.
The aim of the present contribution is to report a study Colorimetry analysis was carried out using a PrimeTM
on the carbonation mechanism of the Nanorestore® formu- X BTC621E spectrometer based on the CIE-Lab∗ system.
lation, so to correlate it to the consolidation effectiveness The color difference E ∗ between two samples is calcu-
that has been observed through on-site applications to im- lated as
movable artistic and historical objects.  2  2  2 1/2
E ∗ = L∗ + a ∗ + b∗ ,
The effects of the product application onto wall paintings
belonging to the Mesoamerican cultural heritage will also where L∗ is the difference in the luminosities, a ∗ is the
be discussed, in particular focusing on the effective consoli- difference in the green–red scale and b∗ is the difference
dation of the painted layers and the high compatibility with in the blue–yellow scale. The selected wave range was 400–
the original substrates, which results in the minimization (or 800 nm. Five measurements were averaged to obtain one
full avoidance) of any physico-chemical and aesthetical al- data point.
teration of the treated surfaces. Optical investigation was carried out with a Reichert op-
tical microscope.
The scanning electron microscopy (SEM) investiga-
2 Experimental details tion of Ca(OH)2 nanoparticles and of archaeological sam-
ples (Calakmul samples, before and after treatment with
The Nanorestore® commercial product (dispersion of Nanorestore® ) was carried out using a field emission gun
Ca(OH)2 nanoparticles in 2-propanol, 5 g/L, nanoparticle FEG-SEM (Sigma, Carl-Zeiss) working at 3 kV accelera-
size around 250 nm) was produced at CSGI and used for tion potential (working distance: 4.4 mm; using a secondary
both the carbonation characterization and application on ar- electron detector).
chaeological samples. Water absorption tests by capillarity were performed on
For the carbonation characterization, Fourier transform the Calakmul detached samples, according to the UNI 10859
infrared (FTIR) transmission was selected to perform a standard. Water was absorbed through the painted layer from
quantitative analysis of calcium hydroxide nanoparticle Whatman filter paper soaked in water, and the quantity of
transformation into carbonate. For this purpose, 30 µL of water absorbed was plotted as a function of time.
the commercial product Nanorestore® was deposited onto
a KBr pellet (200 mg) containing 0.0125 wt% of Prus-
sian Blue (PB) as an internal standard [27]. PB has an 3 Results and discussion
intense absorption band at 2094 cm−1 . The carbonation
of calcium hydroxide was investigated by monitoring the The Nanorestore® product is a dispersion (in 2-propanol) of
ratio between the area of the CaCO3 peak at 712 cm−1 hexagonal portlandite platelets whose average size is around
(OCO bending in-plane mode [28]) and the area of the PB 250 nm (see Fig. 1). Typically, for consolidation purposes
2094 cm−1 peak. The pellet was kept at room temperature the particles are applied by brushing onto degraded sub-
in a box where the concentration of CO2 was maintained strates, penetrate within the object pores and form layers of
at 1000 ± 100 ppm, and RH was 75 % (using a saturated hexagonal platelets [20, 29]. The particles then react with
atmospheric CO2 , turning into a network of calcium car-
NaCl solution). The spectra were recorded using a BioRad
bonate that embeds and fixes flaking grains and pigments.
FTS-40 spectrometer with 4 cm−1 resolution and 64 scans.
Therefore, the formed CaCO3 is not merely a filler, but acts
The spectral range was 4000–400 cm−1 .
as a consolidant.
The application of Nanorestore® was carried out on de-
The simple chemical equation of the carbonation process
tached wall painting samples coming from the archaeo-
is
logical Maya site of Calakmul (Campeche, Mexico) and
stored at the CSGI laboratories, and, directly on site, on Ca(OH)2 + CO2 → CaCO3 + H2 O.
726 P. Baglioni et al.

Fig. 2 α (alpha, degree of carbonation) as a function of time for a

deposit of nanoparticles of Ca(OH)2 (Nanorestore® ) onto a KBr pellet

tra of the Nanorestore® product deposited on the KBr pellet

(see Experimental details).
Fig. 1 FEG-SEM image of Ca(OH)2 nanoparticles (Nanorestore® ).
Bar is 100 nm Complete carbonation (α = 1) was achieved after about
230 h (roughly 9.5 days). The profile of the α plot shows a
short induction time (0–13 h), an acceleration period (13–
According to the literature, the gas–solid reaction is gen- 130 h) and a final stage (130–230 h) during which α slowly
erally incomplete (< 80 %) due to the formation of a car- increases up to 1.
bonate layer around the hydroxide particles, and at low CO2 In order to deduce the carbonation mechanism, we tested
pressure (< 1 bar) the carbonation efficiency depends, be- several models for solid-state reactions, and the one that best
sides temperature and relative humidity (RH), on the parti- fitted the experimental data was found to be the Avrami–
cle size, sorbent chemical structure and fluid dynamics [30– Erofeev model [40–42], according to which the formation of
37]. Moreover, the catalytic role of high RH values has been CaCO3 takes place through a nucleation and growth mecha-
demonstrated, resulting in an increase of carbonation up to nism.
85 % at T ≈ 20 ◦ C and PCO2 ≈ 6.5 mbar [38]. Beruto and According to this model, the basic expression of α is
Botter have also claimed that the CO2 pressure (< 1 bar) has  
no significant effect on the carbonation reaction at any RH α = 1 − exp −(kt)M (2)
(< 90 %) [38]. Dheilly et al. showed that at RH = 100 %, where k is the reaction rate constant and the exponent M
T = 10 ◦ C and low level of CO2 , a carbonation reaction is related to the reaction mechanism. In fact, M can be ex-
occurred up to about 93 % in 10 days [39]. It is worth men- pressed as a function of three parameters, P , S and Q:
tioning that wall paintings in closed environments such as
European churches and castles frequently experience high M = (P /S) + Q (3)
values of RH and low temperatures, while several archae- where P = 1, 2 or 3 corresponds to fiber, sheet or polygonal
ological sites include underground chambers, belonging to form growth; S = 1 corresponds to phase-boundary growth,
partially excavated buildings, where very high RH values while S = 2 to diffusion of the component through a liquid
are typically recorded. phase; Q = 0 corresponds to no nucleation, while Q = 1
Based on these assumptions, we investigated the carbon- indicates constant nucleation.
ation of commercial Ca(OH)2 nanoparticles (Nanorestore® ) The linear form of Eq. (2) is
at RH = 75 % and room temperature, monitoring through  
FTIR the development of calcium carbonate at controlled M ln t + M ln k = ln ln(1 − α)−1 (4)
CO2 concentration (≈ 1000 ppm). Figure 2 reports the plot The parameters M and k can be obtained by plotting
of the degree of carbonation α as a function of time, α being ln[ln(1 − α)−1 ] as a function of ln t. In the case of the
defined as Nanorestore® system, the fitting of the experimental data
( AA712 )t (see Fig. 3) allowed us to obtain k = 1.09 × 10−2 and
α= PB
(1) M = 2.42. The M value (close to 2) has been interpreted
( AA712 )t
PB f by considering P = 2 (sheet growth), S = 2 (diffusion of
where A712 and APB are, respectively, the areas of the CO2 within a film of water molecules formed on the surface
CaCO3 peak at 712 cm−1 and of the PB internal standard of the Ca(OH)2 particles) and Q = 1 (constant nucleation).
peak at 2094 cm−1 , t is a generic carbonation time and The carbonation mechanism of Nanorestore® accounts
tf indicates the end of the carbonation reaction, when the for the consolidation effectiveness that has been reported
3643 cm−1 Ca(OH)2 peak is no longer detected in the spec- through practical applications on both wall paintings and
Commercial Ca(OH)2 nanoparticles for the consolidation of immovable works of art 727

stone [12, 25]. As a matter of fact, the formation of a calcium ground tomb in which RH varies approximately between 70
carbonate network within the pores of artistic/architectonic and 98 %. The tomb decorations comprise mural paintings
substrates, as described above, produces the consolidation executed on a carbonate substrate with a lime-based tech-
of weakened surfaces. nique, where polysaccharide additives were added to lime.
Recently, SEM analysis showed the formation of sheets The paintings presently exhibit severe degradation, due to
of CaCO3 nanocrystals upon carbonation of calcium hy- biodegradation (growth of microorganisms), to the effect of
droxide nanoparticles onto a mortar specimen that exhibited salt crystallization and to the swelling of the polysaccharide
surface powdering [43]. additives caused by high RH values, all resulting in the flak-
As an example of on-site consolidation intervention us- ing and powdering of the pictorial layer. As discussed in the
ing nanoparticles synthesized through the top-down method, introduction, the use of aqueous methods for consolidation
it has been chosen to report here the preservation of the ar- is strongly discouraged, and alcohol dispersions of calcium
chaeological site of Ixcaquixtla, located south of the city of hydroxide were preferred.
Puebla, Mixtec area, Mexico. The site includes an under- In fact, the on-site application of Ca(OH)2 nanoparticles
(in 2-propanol) resulted in the strengthening of the weak-
ened pictorial surface, which allowed the safe removal of
salts. In this way, it was possible to recover and reveal larger
portions of the paint layer (see Fig. 4).
As mentioned above, the consolidation treatment must be
compatible, i.e. with little or no alteration of the original
substrate properties, while granting the strengthening of the
weakened substrate. In order to further evaluate this aspect,
several wall painting fragments, coming from the archaeo-
logical site of Calakmul (Campeche, Mexico), were treated
with Nanorestore® and characterized afterwards.
Figures 5, 6 and 7 show the optical microscope images
of the painted layer of Calakmul samples, before and after
Fig. 3 Fit of the experimental data relative to the carbonation kinetic
of the Nanorestore® product through the Avrami–Erofeev model (R 2 the consolidation treatment. The samples comprise a yellow,
is 0.9648) green (formed by mixing a blue and a yellow pigment) and

Fig. 4 The three-chamber tomb of the underground site of Ixcaquixtla of the painted layer. (Bottom) Detail of the treatment with Ca(OH)2
(Puebla, Mexico). (Top left) Painted layer before the application of nanoparticles (application of humid poultices after treatment with the
Ca(OH)2 nanoparticles. (Top right) The consolidation treatment al- Ca(OH)2 particle dispersion)
lowed the removal of salts, recovering and revealing larger portions
728 P. Baglioni et al.

Fig. 5 Optical microscope

images (40×) of the painted
layer (yellow pigment) of wall
painting samples belonging to
the Calakmul (Mexico) Maya
archaeological site. (Left)
Before treatment. (Right) After
treatment with Nanorestore® .
Bar is 100 µm

Fig. 6 Optical microscope

images (40×) of the painted
layer (green pigment) of wall
painting samples belonging to
the Calakmul (Mexico) Maya
archaeological site. (Left)
Before treatment. (Right) After
treatment with Nanorestore® .
Bar is 100 µm

Fig. 7 Optical microscope

images (40×) of the painted
layer (red pigment) of wall
painting samples belonging to
the Calakmul (Mexico) Maya
archaeological site. (Left)
Before treatment. (Right) After
treatment with Nanorestore® .
Bar is 100 µm

red painted layer. The pictures have been taken after five powdering is observed and the cotton swab does not remove
months of carbonation of the nanoparticles. From the opti- pigments from the surface (see Figs. 8, 9 and 10).
cal microscope investigation it is evident that the applica- Figures 11 and 12 show the FEG-SEM images of the
tion of Nanorestore® caused almost no aesthetical alteration painted layer (yellow and red pigments) of wall painting
of the painted layer. Both the color hue and the pigment samples, before and after the consolidation treatment. For all
grain texture appear practically unaltered after the treatment. the pigments it is evident that the treatment results in the
These observations match the result obtained by colorime- formation, upon full carbonation of the Ca(OH)2 nanoparti-
try. In fact, a color difference (E ∗ = 4.2) was detected be- cles, of a smoother and more homogeneous painted surface,
tween untreated and treated red painted layers, for which the with decreased roughness that macroscopically corresponds
color alteration was indeed expected to be the biggest. to reduced color powdering and an increased mechanical re-
As a matter of fact, all the treated samples exhibited a sistance to abrasion.
higher resistance to a simple mechanical test, carried out by The measurements of water absorption by capillarity rise
rolling a cotton swab on the painted layer before and af- (see Fig. 13) indicate that, despite the consolidation effect
ter consolidation treatment. Before treatment, the powdering and the reduced microroughness, the treatment does not af-
painted layer sticks to the swab, while after carbonation of fect the kinetics of capillary suction by the substrates. Both
the nanoparticles the painted layer is consolidated so that no the asymptotic value of absorption (M), which quantifies the
Commercial Ca(OH)2 nanoparticles for the consolidation of immovable works of art 729

Fig. 8 Mechanical abrasion test with a cotton swab, performed on the painted layer (yellow pigment) of wall painting samples (≈ 10 cm long)
belonging to the Calakmul (Mexico) Maya archaeological site, before (left) and after (right) treatment with Nanorestore®

Fig. 9 Mechanical abrasion test with a cotton swab, performed on the painted layer (green pigment) of wall painting samples (≈ 10 cm long)
belonging to the Calakmul (Mexico) Maya archaeological site, before (left) and after (right) treatment with Nanorestore®

Fig. 10 Mechanical abrasion test with a cotton swab, performed on the painted layer (red pigment) of wall painting samples (≈ 10 cm long)
belonging to the alakmul (Mexico) Maya archaeological site, before (left) and after (right) treatment with Nanorestore®

maximum water absorption of the sample, and the coeffi- unaltered for the three samples. It is worth noticing that the
cient of average absorption (CA, i.e. the slope of the linear degradation of these samples mainly consists in the powder-
part of the curve, expressed as mg cm−2 s−1/2 ), which in- ing of the painted layer, while the underlying carbonate sub-
dicates the rate of absorption per unit area, are practically strate is still in a good state. Therefore, in this case a com-
730 P. Baglioni et al.

Fig. 11 SEM images (15 K×) of the painted layer (yellow pigment) of wall painting samples belonging to the Calakmul (Mexico) Maya archae-
ological site. (Left) Before treatment. Bar is 2 µm. (Right) After treatment with Nanorestore® . Bar is 1 µm

Fig. 12 SEM images (15 K×) of the painted layer (red pigment) of wall painting samples belonging to the Calakmul (Mexico) Maya archaeolog-
ical site. (Left) Before treatment. Bar is 2 µm. (Right) After treatment with Nanorestore® . Bar is 1 µm

patible consolidation treatment is expected to strengthen the Another important aspect concerns the application me-
painted layer without altering the substrate porosity (in the thod: as a general rule several applications at lower particle
case of severe substrate degradation, e.g. by salt crystalliza- concentration allow a more and effective gradual consolida-
tion, consolidation should also result in the partial reduc- tion with respect to one application at higher concentration.
tion of porosity, recovering the original pore size distribu- In this case, in fact, the particles tend to cluster and form
tion). To summarize, for the powdering wall painted samples aggregates that lie only in the surface of the substrate, with
considered in this study, water absorption measurements in- scarce penetration. As a result there is a lack of consolida-
dicate that consolidation of the pictorial layer takes place tion and the occlusion of surface pores, and the possible for-
mation of white glazes.
while avoiding the occlusion of pores, so to maintain the
For the consolidation of Calakmul samples, the size of
natural permeability of the substrates to water vapor.
the selected nanoparticles (around 250 nm) exhibited a good
Control of the treatment can be achieved mainly by
match with the substrate porosity, and a lower concentration
matching both substrate and nanoparticle size distribution.
of particles (2.5 g/L) with respect to the standard product
As mentioned above, the literature reports several methods (5 g/L) was used.
for the production of nanoparticles with different size and
polydispersity. For instance, heavily degraded porous matri-
ces may exhibit a porosity gradient, so that mono-disperse 4 Conclusions
nanoparticles would only prove partially effective for con-
solidation, while particles with multi-modal size distribution The carbonation mechanism of Ca(OH)2 nanoparticles
would exhibit an increased effectiveness. (Nanorestore® ) was investigated. The experimental data
Commercial Ca(OH)2 nanoparticles for the consolidation of immovable works of art 731

Fig. 13 Comparison of the capillary rise profiles for the yellow, green and red painted layer of wall painting samples belonging to the Calakmul
(Mexico) Maya archaeological site, before and after treatment with Nanorestore®

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