Invited Feature Article

pubs.acs.org/Langmuir

Colloid and Materials Science for the Conservation of Cultural

Heritage: Cleaning, Consolidation, and Deacidification
Piero Baglioni,* David Chelazzi, Rodorico Giorgi, and Giovanna Poggi
Department of Chemistry and CSGI, University of Florence, via della Lastruccia 3 - Sesto Fiorentino, 50019 Florence, Italy

ABSTRACT: Serendipity and experiment have been a

frequent approach for the development of materials and
methodologies used for a long time for either cleaning or
consolidation of works of art. Recently, new perspectives have
been opened by the application of materials science, colloid
science, and interface science frameworks to conservation,
generating a breakthrough in the development of innovative
tools for the conservation and preservation of cultural heritage.
This Article is an overview of the most recent contributions of
colloid and materials science to the art conservation field,
mainly focusing on the use of amphiphile-based fluids, gels,
and alkaline earth metal hydroxide nanoparticles dispersions
for the cleaning of pictorial surfaces, the consolidation of artistic substrates, and the deacidification of paper, canvas, and wood.
Future possible directions for solving several conservation issues that still need to be faced are also highlighted.

■ INTRODUCTION
Conservation science is a complex discipline that deals with the
restoration and preservation of a large variety of materials
constituting our cultural heritage. At first sight, one might think
that science, art, and humanities are disconnected disciplines.
However, our way of thinking and behaving depends strongly on
the legacy of physical artifacts and intangible attributes of a
society, inherited from past generations, maintained in the
present, and possibly bestowed for the benefit of future
generations.
Because of the complexity of artistic and historical substrates,
conservation science has explored different routes, developing
several approaches for solving conservation issues. For instance,
new resins that are more stable than natural ones, while
exhibiting similar optical properties, have been developed and
applied as varnishes for retouching paintings.1 Furthermore, the
analysis of materials is often considered to be a preliminary step
for suggesting treatments for works of art: in the conservation of
matte paintings, the analysis of the physical and optical properties
of the painted layers is the key to choosing the best materials for
their consolidation.2 Electrochemistry and corrosion science
have proven useful in conserving bronze outdoor statuary,3 and
colloid science has been providing an increasingly important
contribution to the development of restoration tools. Among the
systems specifically tailored for conservation issues, nano-
particulate inorganic sols (nanosols),4 colloidal silica,5 and
alkoxysilane6 play an important role in stone and wood
conservation. In particular, because of their high surface-to-
volume ratio, nanosols are metastable and usually hydrolyze to
form 3D xerogel networks that improve the mechanical
properties and resistance to water, fire, and microbial or insect
attack of wood or stone objects.
Concepts and tools7−10 belonging to the realm of colloid and
materials science, which have acquired a leading role in the
development of advanced and functional tools constituting a
large portion of the commercial products that are consumed daily
by millions of people all over the world and used in a variety of
applications including cosmetics, food, and pharmaceutics,11−13
may lead to a dramatic enhancement of the effectiveness and
durability of restoration interventions.
Typically, works of art comprise both movable and immovable
objects. The first class includes all of the documentary and
historical manuscripts and books, usually made of paper or
parchment, easel paintings on wood or canvas, and a large variety
of objects such as statuettes, jewelry, and textiles. Immovable
works of art mainly consist of mural/wall paintings, architectonic
substrates, statues, and several kinds of stone-based artifacts.
Regardless of their nature, artifacts are irremediably exposed to
several degradation agents: physical erosion, chemical degrada-
tion, temperature, relative humidity, light, and microorganisms,
all accounting for the natural aging of art materials. Moreover,
anthropic activities increase the concentrations of SO2, NOx, and
VOC (volatile organic compound) gases in the atmosphere that
eventually lead to the corrosion of artistic substrates,
contributing to the degradation of works of art. Finally, it must
be outlined that in some cases conservation issues are due to past
extemporized restoration interventions that were based on trial-
and-error practice.
Depending on the type of artistic substrate, different tasks are
necessary for conservation purposes. A large fraction of
Received: November 8, 2012
Revised: February 19, 2013
Published: February 25, 2013

© 2013 American Chemical Society 5110 dx.doi.org/10.1021/la304456n | Langmuir 2013, 29, 5110−5122
Langmuir
Figure 1. Degradation of a wall painting. (A) Paint layer detachments (white spots). (B) Salt efflorescence. (C) Paint layer flaking and detachment due
to the presence of organic coatings. The polymer coating acts as a barrier preventing the natural “breathing” of the surface and consistently increasing the
mechanical stresses due to salt crystallization at the painting−polymer interface.
conservation interventions consists of cleaning surfaces,
consolidating surfaces and bulk layers, and deacidification.
Cleaning mainly consists of the selective removal of dirt, grime
(greasy material, dust, etc.), and natural or synthetic polymers
from the surface of coated movable and immovable works of art.
The application of natural varnishes has been largely performed
in the past and has been traditionally adopted by easel painting
artists that wanted to enhance the visual properties of their
works. In addition to improving the appearance through the
saturation of color, traditional conservation practice foresees the
use of such materials to provide a vast number of different artistic
substrates with hydrophobic properties and surface protection.
Starting from the second half of the 20th century, synthetic
polymers have been enthusiastically adopted, mainly because
they were thought to be highly resistant to aging and easily
removable. Unfortunately, synthetic polymers undergo degrada-
tion similarly to that of natural resins, resulting in the decrease of
their solubility in net solvents and in the significant alteration of
their visual aspect (mainly yellowing).14 Because of their
adhesive properties, synthetic polymers have been used to
readhere detached or damaged parts in the external layers of
works of art. For instance, acrylate, vinyl, silicone, and epoxy
polymers are widely used for the consolidation and protection of
stone and wall paintings. However, the use of synthetic adhesives
results in the strong alteration of physicochemical properties of
the original substrates, such as porosity, water capillarity, water
vapor permeability, and surface wettability,15,16 generating in the
long term enhanced degradation that can proceed even up to the
loss of the artifacts.
Another important class of works of art subjected to
degradation are cellulose-, parchment-, and leather-based
artifacts (mainly documentary and historical manuscripts and
books), which are threatened mainly by hydrolysis and oxidation
reactions (acidity plays a fundamental role in the catalysis of
these reactions) that lead to the loss of paper/parchment
mechanical resistance.17,18 Conservation practice usually in-
volves the use of alkaline aqueous solutions for paper
deacidification whereas polar solvents are discouraged on
collagen-based substrates. However, water causes the swelling
of cellulose fibers and the leaching of compounds associated with
paper (inks, sizing, etc.). This limitation has favored the
development of nonaqueous deacidification methods.
In the past 15 years, tools from nanoscience and in particular
from colloid and surface science were demonstrated to overcome
some of the limits of traditional restoration methodologies by
providing, in a new cultural framework, innovative method-
ologies and materials for the above-described conservation
issues. As a result, several reliable, easy to use, and inexpensive
5111
Invited Feature Article
tools have been conceived and offered to conservators,
constituting a new palette of treatments that exhibit high
compatibility with the original artistic substrates and therefore
grant long-term durability.
The aim of this Feature Article is to illustrate some of the main
achievements attained for the conservation of cultural heritage in
the framework of surface and colloid science, providing an up-to-
date overview focused on the research activity of the authors of
this Feature Article, including future directions and perspectives
in the field. In this regard, nanostructured fluids such as
microemulsions and micellar solutions, highly retentive chemical
gels, and nonaqueous dispersions of alkaline nanoparticles will be
described in the following sections.
■
PROTECTION AND RESTORATION OF CULTURAL
HERITAGE
In this section, we report three applications of colloid science that
address a large fraction of conservation issues: (i) cleaning with
nanostructured fluids, (ii) the use of gels to control/enhance the
cleaning action, and (iii) the application of nanoparticles for
consolidation and deacidification purposes.
Wall Painting Cleaning: Microemulsions and Micellar
Solutions. The main component of the majority of mural
paintings is calcium carbonate, which is obtained by the reaction
of calcium hydroxide (hydrate lime) with atmospheric CO2. In a
typical wall painting belonging to the classic tradition, three
layers can be individuated: the so-called arriccio constitutes the
inner layer that is in contact with the wall structure. Its
composition is rich in sand, which is used as a filler to improve the
mechanical properties of the plaster. The second layer, called the
intonaco, is obtained by mixing equal amounts of lime and sand.
The paint layer, consisting of a mixture of pigments and calcium
hydroxide, is located on the intonaco. Frescoes are paintings in
which the pigments are applied directly to the wet intonaco layer.
The application of coloring materials on dried surfaces is called
the secco technique. In this case, the paint layer may also contain
organic binders such as egg, milk, and animal glues.
Wall paintings are commonly subjected to two important
degradation pathways: (i) the formation of sulfates depleting and
weakening the carbonate layer and (ii) the solubilization and
recrystallization of sulfate salts during relative humidity cycles
(chloride and nitrate salts can also be present, even in large
amounts), leading to mechanical stress within the wall pores and
eventually to the pores’ collapse. As a result, the paint layer
exhibits flaking and detachment (Figure 1).
As stated above, the use of synthetic polymers as coating and
protective agents has been widely practiced by conservators to
dx.doi.org/10.1021/la304456n | Langmuir 2013, 29, 5110−5122
Langmuir Invited Feature Article

Figure 2. Details of wall paintings by Masaccio and Masolino in the Brancacci Chapel, Florence. The right upper panel shows wax spots under UV light
before cleaning. The right lower panel shows the same area after cleaning with a microemulsion under visible light. On the left, the entire scene after
restoration is shown (courtesy of Piero Baglioni).

Table 1. Composition of Some Amphiphilic Cleaning Systems That Have Been Used for the Conservation of Cultural Heritagea
Xyl21,22 Xyl-ND8,22 EAPC23,24 APG25
component % component % component % component %
water 85.40 water 86.20 water 73.30 water 99.00
SDS 4.10 SDS 3.90 SDS 3.70 AGE 0.52
1-PeOH 7.90 1-PeOH 6.50 1-PeOH 7.00 AGESS 0.12
p-xyl 2.60 p-xyl 1.80 PC 8.00 p-xyl 0.36
ND 1.60 EA 8.00
a
SDS, sodium dodecyl sulfate; 1-PeOH, 1-pentanol; p-xyl, p-xylene; ND, nitro diluent, a commercial mixture of 62% toluene, 15% butyl acetate, 15%
ethyl acetate, 6% n-butyl alcohol, and 2% cellosolve acetate; PC, propylene carbonate; EA, ethyl acetate; AGE, alkyl polyglycoside ester; AGESS,
sodium alkyl polyglycoside sulfosuccinate.

improve both the mechanical properties of flaking frescoes and a
painting’s appearance. In particular, acrylic polymers constitute
the majority of synthetic products used in the restoration and
conservation of inorganic substrates. However, flaking and
detachment phenomena are enhanced by the presence of these
hydrophobic coatings over the surface (Figure 1). Therefore, the
degradation of the polymers and the severe alteration caused by
these materials to artistic substrates require their removal.
The first application of amphiphile-based systems for the
cleaning of works of art dates back to the end of the 1980s, when
a water-based microemulsion was specifically designed and used
for the removal of hydrophobic wax spots from the surface of
Renaissance wall paintings in the Brancacci Chapel in Florence
(Figure 2).
The inspiration for applying a microemulsion for cleaning
came to one of the authors of this Article (P.B.) from a study by
De Gennes and Taupin.19 The four-component microemulsion
cleaning system used on the Brancacci Chapel paintings was a
modification of the so-called French microemulsion and
consisted of dodecane droplets stabilized in water by a sodium
dodecyl sulfate ionic surfactant and a 1-pentanol cosurfactant.
With respect to traditional cleaning with pure solvents, the main
advantage in the use of microemulsions relies on an enhance-
5112
ment of grime/soil removal and on the confinement of the
hydrophobic material (wax) inside the oil (in the present case,
dodecane) microemulsion droplets. This avoids the spreading of
the dissolved wax into the wall pores, as would have occurred
with pure solvents.20
Another important general feature is that aqueous amphiphilic
systems allow a significant decrease in the amount of organic
solvents involved in a typical cleaning procedure, therefore
depressing the system’s toxicity and environmental impact.
Usually, the concentration of the dispersed organic phase is
below 10−15% and varies according to the different cleaning
systems, as reported in Table 1.
In addition to that, regardless of the type of microemulsion or
micellar solution applied, the use of a confining system to trap a
micellar solution or microemulsion is always encouraged in order
to have fine control of the cleaning action. In the case of cleaning
mural paintings, the confining system usually consists of a
poultice of cellulose pulp loaded with the selected complex fluid.
Whenever direct solubilization of the coatings takes place, the
poultice acts as a spongelike tool, further limiting the diffusion of
any solubilized material within the porous matrix of the substrate.
This, together with the hydrophilic barrier provided by the
continuous aqueous medium of the microemulsion, strongly
dx.doi.org/10.1021/la304456n | Langmuir 2013, 29, 5110−5122
Langmuir
hinders the redeposition of solubilized hydrophobic material in
the wall’s pores, as would occur with neat solvents (Figure 3).
Figure 3. Organic coatings on a porous substrate (A). On the left (B),
the use of neat organic solvents causes the solubilization of the coating
within the pores (B1 brown) and the redeposition of the dissolved
coating within the substrate’s pores upon solvent evaporation (B2). On
the right (C), the continuous aqueous phase acts as a hydrophilic (C1
blue) barrier, preventing the penetration of the removed hydrophobic
material within the porous substrate. The poultice acts as a spongelike
tool, further limiting the spreading of the removed polymer (C2).
When the cleaning fluids produce only the swelling of the
coatings, as occurs with silicon polymers, gentle mechanical
action is required to complete the removal process. Interestingly,
the latter case indeed represents an ideal condition for selective
cleaning because the coating is peeled off without being
solubilized and no residues are left on the substrate.
At the end of the 1990s, two oil-in-water microemulsion
systems were developed, differing from each other in the ionic
(sodium dodecyl sulfate, SDS) or nonionic (polyoxyethylene
sorbitan monoleate, TWEEN 80)21 surfactant. The oil phase
consisted of xylene26,27 because of its high affinity for aged acrylic
polymers. In particular, the system containing SDS and 1-
pentanol as cosurfactants (Xyl, see Table 1) has proven to be
effective in many practical case studies. The interaction
mechanism between the cleaning system and acrylic polymeric
coatings has been investigated in order to achieve a thorough
comprehension of the different steps involved in the cleaning
process.24 Upon interaction with the polymer, a fraction of the
solvents (1-pentanol and xylene) migrates from the micro-
emulsion droplets to the coating; because of the loss of the
organic fraction, the micelle size decreases and the swollen
polymer detaches from the surface, resulting in surface cleaning.
The structure of the microemulsion has been characterized down
to the nanoscale by small angle X-ray scattering (SAXS), small-
angle neutron scattering (SANS), and photocorrelation spec-
troscopy (QELS).28
To enhance the removal effectiveness, the Xyl microemulsion
can be modified by adding to the oil phase variable amounts of
nitro diluent (ND), a commercial blend of solvents (mainly
toluene, butyl acetate, and ethyl acetate). QELS analyses showed
5113
Invited Feature Article
that the microemulsion consists of droplets with a hydrodynamic
diameter of about 17 to 18 nm.22 The efficacy of this system (Xyl-
ND, see Table 1) was positively assessed during the cleaning of a
late 14th century wall painting (Cappella Guasconi) in Arezzo,
Italy,22 and in several other restoration interventions where aged
Paraloid was removed.
Besides acrylic polymers, vinyl-based coatings have been
largely used for the consolidation and protection of works of art.
Xylene is not a good solvent for this class of polymers because of
its low polarity; therefore, different amphiphilic systems
containing polar organic phases were developed, characterized,
and assessed in recent applications. Propylene carbonate (PC)
was successfully included in a four-component system consisting
of SDS, 1-pentanol, water, and 22%PC.22 This system has been
fully characterized by self-diffusion NMR and SAXS in order to
clarify the nature of its nanostructure.29 It was reported that
propylene carbonate is mainly solubilized in the continuous
phase (water), but a significant amount (40% w/w) is contained
in the micelles, acting mainly as a cosurfactant for the SDS
micelles, decreasing their size and aggregation number by
increasing the mean headgroup area of SDS. This system has
been successfully tested in Siena (paintings of Lorenzo di Pietro
called “il Vecchietta” in the Old Sacristy of Santa Maria della
Scala (15th century)) and in Conegliano (mural paintings of
Pozzoserrato from the external walls of the Santa Maria dei
Battuti Cathedral (16th century)), where it efficiently removed
polyvinyl acetate and acrylic polymers not removable with
conventional cleaning systems such as neat solvents.22,30
The four-component system (water/SDS/PC/1-pentanol)
was later modified by adding ethyl acetate (EA), which is a good
solvent for both vinyl and acrylic copolymers. The composition
of this system, named EAPC, is indicated in Table 1. EAPC is one
of the most effective tools recently developed for the removal of
polymeric coatings from artistic substrates. The structure of
EAPC has been recently investigated by SANS contrast
variation,28 deuterating in a selective fashion the EAPC
components to determine the structure and constituent location
of this complex fluid. The presence of two solvents (EA and PC)
that are soluble in both the dispersed and the continuous phase
points to the definition of the system as composed of swollen
micelles even if its structure is definitely more complicated. The
interaction of EAPC and the polymeric coating is affected by the
presence of a water-soluble blend of organic solvents that
dynamically exchange between micelles and the continuous
phase, leading to a faster and more efficient interaction with the
polymer layer.23 Interesting case studies concerned the removal
of acrylic−vinyl copolymers (Mowilith products) that were
widely applied to mural paintings belonging to the Mesoamer-
ican cultural heritage (Mayapan − Yucatan, Mexico; Cholula −
Puebla, Mexico)24 (Figure 4).
This system was also found to be efficient in the removal of
acrylic−vinyl copolymers and siliconic resins that are usually
impossible to remove with conventional cleaning systems. Figure
5 shows the cleaning of a wall painting in the Annunciation
Church in Nazareth, Israel, where a mixture of different
polymers, including siliconic resins, were successfully removed
with the EAPC system.28
The formulations containing xylene and propylene carbonate
solvents require the presence of significant amounts of SDS.
Nonionic surfactants exhibit the advantage, over ionic
surfactants, of lowering the CMC, thus allowing the use of
smaller amounts of nonvolatile components that might remain as
residues on the painting after the cleaning. An interesting
dx.doi.org/10.1021/la304456n | Langmuir 2013, 29, 5110−5122
Langmuir Invited Feature Article

Figure 4. Removal of organic coatings from a Mesoamerican mural painting in Cholula (upper panel). On the bottom left (A), the presence of the
organic coating significantly alters the readability of the painting. On the right (B), the same area partially cleaned after the application of a
microemulsion (courtesy of Piero Baglioni).

Figure 5. Wall paintings in the Conon Apse (Annunciation Church in Nazareth, Israel). On the left, the effect of the polymer coating on the pictorial
surface. On the right, the same area after complete removal achieved by using the EAPC system.28

application of nonionic surfactants concerned the use of alkyl
polyglycoside (APGs) for the formulation of cleaning systems
(Table 1); in particular, an oil-in-water microemulsion, formed
from less than 1% of a mixture of polyglucoside surfactants and
about 0.5−1% oil, was successfully applied for the removal of
Paraloid B72 (70:30 ethyl methacrylate/methyl acrylate
copolymer) from the wall paintings in Santa Maria della Scala,
Siena, Italy.25
Research efforts are currently devoted to the development of
novel formulations involving the use of biodegradable nonionic
5114
surfactants with the aim of producing more environmentally
friendly, but still effective, systems.
Easel Painting Cleaning: Gels. A stratigraphy of a typical
easel painting is depicted in Figure 6. Starting from the bottom,
the supporting material consists of linen (or another natural
cellulosic fiber); a preparation layer (ground layer) made of
gypsum (or lead carbonate) mixed with animal glue is laid on the
support in order to create a homogeneous substrate upon which
the artist paints by using pigments, in most cases, dispersed in oil
(paint layer). Finally, a varnish layer is laid over the paint layer for
both aesthetic and protective purposes.
dx.doi.org/10.1021/la304456n | Langmuir 2013, 29, 5110−5122
Langmuir Invited Feature Article

Figure 6. (Left) Stratigraphy of a typical easel painting. (Right) Stratigraphy of an easel painting restored using a traditional approach. Usually, during
the restoration, a second canvas is glued to the back side of the painting (relining adhesive and canvas), and after the thinning of the aged varnished using
neat solvents or solvent gels, fresh varnish is often applied to the front of the canvas.

Figure 7. (Left) SEM image of the relining glue covering the linen sample. (Right) Linen sample after the removal of the acrylic vinyl copolymer glue by
the application of an acrylamide/bisacrylamide hydrogel loaded with the EAPC system.44

Because of photooxidation and thermal oxidation,31 the
varnish layer naturally ages, undergoing both discoloration and
cracking, altering the readability and visual appearance of the
work of art. In addition to that, oil and varnish may release acid
products that catalyze the hydrolysis of the cellulose constituting
the canvas, resulting in the loss of the mechanical properties of
the canvas support.32 The traditional conservation approach
foresees the thinning of the aged varnish using neat solvents or
solvent gels, even though the varnish solubility strongly decreases
upon aging; after this operation, fresh varnish, natural or
synthetic, is often applied. The reinforcement of the degraded
canvas is carried out by gluing a new canvas on the back of the
easel painting. (This operation is called relining.) Figure 6 shows
the stratigraphy of the easel painting after restoration with
traditional materials.
Nowadays synthetic polymers, including glues and varnishes,
are frequently used for canvas relining. Synthetic polymers, in
particular, poly(vinyl acetate) (PVAc) adhesives, favor further
degradation of the support because of the products formed
during their own degradation, making their removal compul-
sory.33,34
Varnishes and glues can be directly removed using neat
solvents. As for wall paintings, the use of neat solvent has two
main contraindications: (i) the solubilized materials diffuse
within the work of art layers; (ii) several solvents are harmful to
both the operator and the environment. To avoid these issues,
amphiphilic aqueous systems could be used. However, aqueous
systems cannot be directly used on water-sensitive works of art
(such as easel paintings) because of the possible swelling and
mechanical stress of the canvas, the ground, and the paint layers.
The confinement of these cleaning fluids in highly retentive gels
allows the thinning of natural and synthetic polymeric layers and
their controlled removal.
In recent years, several authors have largely investigated the
synthesis of new classes of gels, exploring their potential as
cleaning tools for cultural heritage objects.9,35−39 The application
5115
of gels for the removal of dirt and coatings from artistic substrates
underwent a major advancement in the late 1980s when Richard
Wolbers proposed the use of polymers (e.g., poly(acrylic acid))
as gellants.40 These systems (called solvent gels) enabled the
control of components such as cosolvents, enzymes, and
detergents, limiting the evaporation of solvents and their
penetration into the artifact to be cleaned. However, the network
of these physical gels is based on weak interactions (dipole−
dipole interactions and/or hydrogen bonding), leading to the
presence of residues left on the artifact after gel application.41
The removal of these residues would require the use of solvents,
reproducing the problems connected to the application of neat
solvents.41
An elegant solution to the residue issue is the use of chemical
gels whose network is formed by covalent bonds. Such materials
can be loaded with micelles or microemulsions or with polar neat
solvents while exhibiting high retention capability. For instance,
it has been shown that acrylamide-based chemical gels can be
obtained through the radical polymerization of acrylamide
monomer and N,N′-methylene bisacrylamide (cross-linker).42,43
The resulting tridimensional network of covalent bonds
produces systems that can be loaded with water or micellar
solutions/microemulsions, exhibiting good retention properties.
In recent work, acrylamide gels have been synthesized and loaded
with the EAPC amphiphile-based fluid for the selective removal
of adhesives used for canvas relining.44
Model samples simulating the back side of canvases treated
with adhesives have been relined using an acrylic vinyl copolymer
such as Mowilith DMC5 (a commercial copolymer consisting of
65% vinyl acetate and 35% n-butyl acrylate).44 The removal of
the adhesive from the surface was achieved by using two different
acrylamide/bisacrylamide hydrogels loaded with EAPC. In
particular, the two gels have a constant cross-linker/monomer
ratio but differ for the polymer network concentration and were
characterized by means of differential scanning calorimetry
(DSC), scanning electron microscopy (SEM), and small-angle
dx.doi.org/10.1021/la304456n | Langmuir 2013, 29, 5110−5122
Langmuir
Figure 8. pHEMA/PVP thin gel film application over a model sample simulating the Tibetan painting technique of Thang-Ka (tempera magra), which is
very sensitive to water. The panel on the left is the artificially soiled Thang-Ka. Soil is removed without damaging the pictorial layer, using the gel loaded
with water.46
X-ray scattering (SAXS). A higher concentration of polymer
resulted in a more compact structure that allowed the
confinement of aqueous systems in smaller pores and thicker
pore walls, resulting in different mechanical properties and water
retention capability. The hydrogel with the more compact
structure swelled the coating layer that was then removed by
gentle mechanical action. The absence of any detectable gel
residues, determined via FT-IR ATR measurements, is also
clearly shown by SEM images of the samples (Figure 7), where
the excellent cleaning and removal of the adhesive are evident.44
The same acrylamide-based polymeric network has been
considered to formulate a magnetically responsive gel tailored to
clean marble, mural, and easel paintings. This gel consists of a
network functionalized with CoFe2O4 nanoparticles, which can
be loaded with an oil-in-water microemulsion for the selective
removal of Paraloid B72 coatings. Besides the control of the
cleaning action, these responsive systems allow the minimization
of the mechanical action needed to remove them from the
treated substrate, as required in the cleaning of very precious
artifacts. In fact, these gels can be easily removed in the presence
of a magnetic field such as that of a simple permanent
magnet.43,45
Gels having a higher solvent retention capability are required
when water-based cleaning fluids are used for the cleaning of
hydrophilic and highly water-sensitive works of art (manuscripts
and watercolor paintings). For these artifacts, properly designed
gels were recently synthesized to prevent solvents from spreading
over the artifact surface and to release fluids at a slow rate so as to
perform gradual, nonaggressive cleaning at the interface. A
system with high control of water confinement can be obtained
with a semi-interpenetrating poly(2-hydroxyethyl-methacrylate)
(pHEMA) and poly(N-vinyl-1-pyrrolidone) (PVP) structure.
The rationale behind the choice of these components relies on
the balance between the mechanical strength, provided by
pHEMA, and the hydrophilic properties, granted by PVP, to
obtain a system that gradually releases the cleaning fluids while
avoiding gel residues on the treated surface. Moreover, these gels
are transparent, allowing the visual control of their cleaning
action, and can be realized as thin films (1 to 2 mm) and shaped
as wished (Figure 8).46
Another important class of materials for the selective cleaning
of synthetic coatings consists of high-viscosity polymeric
dispersions (HVPDs). These systems are not truly physical
gels according to their rheological behavior. It is well known that
poly(vinyl alcohol) (PVA) forms HVPDs in the presence of
borate ions, which act as cross-linkers between polymer chains.
The resulting 3D network is thermally reversible. PVA is
5116
Invited Feature Article
produced by the hydrolysis of poly(vinyl acetate), and depending
on its degree of hydrolysis, several HVPDs can be produced and
loaded with polar solvents, enzymes, and amphiphilic
systems.37−39 The main feature of these systems relies on the
possibility of their removal by peeling without the use of neat
solvents, as would occur with solvent gels.
In conclusion, by coupling highly retentive supporting gels
with nanostructured amphiphilic systems, a new palette of
cleaning tools has been offered to the conservator community.
These new cleaning systems have tremendous advantages when
easy, selective, and controlled removal of undesired layers (dirt,
grime, polymers, etc.) is required.
Consolidation and Deacidification: Alkaline Earth
Metal Hydroxide Nanoparticles. Alkaline earth metal
hydroxides can be used for a twofold task in the field of cultural
heritage conservation. As reported in the previous sections, wall
paintings and carbonatic stones can degrade for several reasons.
A valid alternative to the use of polymers for consolidation is
constituted by the use of inorganic consolidants. Among these,
nanoparticles of alkaline earth metal hydroxides can be
considered to be the most reliable and durable systems. In wall
painting consolidation, nanoparticles replace the original pig-
ment’s binder lost during the degradation process, reconsolidat-
ing the painting in a fully compatible way. In addition to that,
calcium and magnesium hydroxides have proven to be excellent
compounds for the deacidification of cellulosic works of art.
A wide range of different synthesis pathways have been
developed for the preparation of calcium, magnesium, strontium,
and barium hydroxide nanoparticles dispersed in short-chain
alcohols.47−55 The main rationale behind the research efforts
concerning the synthesis of nanostructured materials for both
consolidation and deacidification purposes is the control of the
size and shape of the particles that eases the penetration into the
substrate (i.e., wall painting or paper) and leads to enhanced
reactivity associated with the high surface area of the nano-
particles.
The use of hydroxide particle dispersions in short-chain
alcohols presents some advantages over the application of
saturated aqueous solutions such as limewater (a saturated
Ca(OH)2 solution), a widely used inorganic method for
consolidation. Calcium hydroxide has a low solubility in water,
and a large amount of limewater is usually necessary for the
treatment; however, a large amount of water in the wall painting
for porous matrices can favor the collapse of the pores related to
freeze−thaw cycles, the transport of salts, and the growth of
microorganisms. On the contrary, nanoparticles dispersed in
short-chain alcohols exhibit good penetration within the
dx.doi.org/10.1021/la304456n | Langmuir 2013, 29, 5110−5122
Langmuir
Figure 9. (Left) TEM image of calcium hydroxide nanoparticles as obtained via an alcohol thermal synthesis. (Right) SEM image of nanoparticles
adhering to cellulose fibers; the panel in the right upper corner is an enlargement (2-fold).
painting’s porous matrix at concentrations sufficient for a
complete consolidation process, making hydroxide nanoparticles
an optimal system for wall painting consolidation.
The second use of nanoparticles in conservation is related to
deacidification. Cellulose-based artifacts are usually threatened
by the concomitant action of hydrolysis and oxidation that leads
to the loss of the mechanical resistance of the fibers and to
discoloration phenomena of the substrate. As in the case of
consolidation of classical wall paintings, traditional deacidifica-
tion methodologies involve the use of highly alkaline aqueous
solutions. The ideal deacidifying agents are alkaline earth metal
hydroxides and carbonates, which are very compatible with the
substrate and its components and at the same time readily
neutralize acidity. However, the application of alkaline aqueous
solutions implies two significant drawbacks: (i) several paper
components, such as inks and sizing, are water-sensitive and (ii)
the high alkalinity of aqueous solutions may favor the alkaline
depolymerization of cellulose, which takes place at room
temperature on oxidized substrates.56 Moreover, the traditional
deacidification treatments are usually performed through
immersion, and this implies poor control of the amount of
applied deacidifying agent.
The use of nonaqueous methods overcomes these drawbacks;
the commercial nonaqueous treatments that are nowadays
available are all based on solutions or dispersions of oxides and
carbonates precursors.57 For instance, in the case of paper
preservation, magnesium and calcium hydroxide nanoparticles in
propanol produce safe and stable deacidification, leaving a mild
alkaline carbonate buffer reserve against reoccurring acidity on
the treated document.10,50,52,54 Recently, alkaline earth metal
hydroxide nanoparticles dispersed in alcohols have been shown
to be an efficient deacidification system for paper and have
proven to be promising tools for the deacidification of
archeological wood. The application of these systems to
waterlogged wood deacidification has been investigated in the
context of the preservation of the Swedish 17th century warship
Vasa, whose timbers contain high quantities of sulfuric acid,
developed after salvaging from the oxidation of sulfur-reduced
compounds formed from bacterial activity.53,58
In the next sections, the main nanoparticles’ synthesis
pathways developed for application in the field of cultural
heritage conservation are briefly reviewed.
5117
Invited Feature Article
Calcium Hydroxide Nanoparticles. The preparation of
calcium hydroxide nanoparticles has been achieved either
through a breakdown process or by a bottom-up strategy. Fairly
stable dispersions of calcium hydroxide in alcohol were obtained
by grinding slaked lime (a putty lime produced by mixing calcium
oxide with excess water) with a mill. The breakdown process
leads to broad submicrometer/micrometer particle size dis-
tributions that were applied, for the first time, to the
consolidation of degraded frescoes in the cathedral of Santa
Maria Novella, Florence, Italy.47 Recently, an improved
preparation method based on the thermomechanical treatment
of slaked lime has been proposed, where the completion of lime’s
hydration is favored by high temperature and pressure.55 As a
matter of fact, the unreacted calcium oxide core in lime particles
undergoes a strongly exothermic reaction causing the
fragmentation of agglomerates that produces nanoparticles
with an average size of up to 300 nm, which are stably dispersed
in propanol. A different approach involves the building up of
particles (bottom-up procedure) in aqueous solutions48 or in
organic solvents.49 Control of the nucleation of particles over
their growth is achieved by a high degree of supersaturation that
is strongly dependent on temperature and pressure.59 Despite
the fact that these methodologies produce nanoparticles with a
smaller and narrower size distribution (ranging from 20 to 60 nm
for the synthesis in organic solvents and from 50 to 400 nm for
the synthesis in water), the required purification steps necessary
to eliminate the NaCl byproduct make these procedures time-
consuming. Nonetheless, stable dispersions of calcium hydroxide
nanoparticles in alcohol obtained from an aqueous homoge-
neous phase reaction have been applied in a variety of case
studies involving both consolidation48 and deacidification
purposes.50,53,58
A different approach to the synthesis of small calcium
hydroxide nanoparticles involves the use of alkoxides as reaction
intermediates; highly concentrated stable dispersions in alcohol,
not requiring any purification step after the preparation, can be
directly obtained by a high-pressure alcohol thermal reaction
starting from calcium and short-chain alcohols. Because of their
physicochemical characteristics, these particles are particularly
suitable for application on porous artistic substrates (Figure 9).
Moreover, the synthesis pathway can be potentially scaled up to
the industrial level. In contrast, traditional deacidification
methods (i.e., calcium hydroxide solutions) have been shown
dx.doi.org/10.1021/la304456n | Langmuir 2013, 29, 5110−5122
Langmuir Invited Feature Article

Figure 10. (A) Size distribution of Ca(OH)2 nanoparticles in 2-propanol obtained through high-temperature milling. (B) Size distribution of Mg(OH)2
nanoparticles in 2-propanol obtained through a homogeneous phase reaction with excess magnesium ions. (C) Size distribution of Ba(OH)2
nanoparticles in 1-propanol obtained through milling.

Figure 11. (A) Wall painting belonging to a Mesoamerican archeological site. (B) Details of a flaking surface exhibiting sulfate efflorescence. (C) The
same surface after the desulfation treatment with ammonium carbonate and the application of a mixed calcium and barium hydroxide nanoparticle
dispersion.

to produce uneven depositions on cellulose fibers with particles
having diameters of several micrometers.60
Barium Hydroxide Nanoparticles. Barium hydroxide has
been used as a consolidant for carbonaceous materials since the
end of the 19th century.61 Ferroni proposed the use of barium
hydroxide aqueous solutions for the consolidation of frescoes
that were heavily damaged in the Florence flood of 1966.62,63 Its
use is recommended when large amounts of sulfates are present
in the wall painting matrix. Typically, a two-step procedure is
considered: (1) desulfation with an ammonium carbonate
solution loaded in a cellulose pulp poultice and (2) the
application of a Ba(OH)2 solution that fixes the residual soluble
sulfates into insoluble barium sulfate. Furthermore, the presence
of excess barium hydroxide converts the powdery calcium
carbonate (formed in step 1) into calcium hydroxide that reacts
with CO2 to reform a crystalline network of calcium carbonate
that acts as a binder, resulting in the consolidating action.
Besides, barium hydroxide can be used together with calcium
hydroxide nanoparticle dispersions for the consolidation of
heavily degraded and sulfated wall paintings. In fact, in this case,
Ca(OH)2 nanoparticles alone are not very efficient because the
consolidating action of calcium hydroxide is hindered by its
partial transformation to the more stable calcium sulfate. In this
case, the most simple and elegant solution is the application of
mixed calcium and barium hydroxide nanoparticle dispersions in
alcohol.
The synthesis of Ba(OH)2 nanoparticles from the aqueous
homogeneous phase reaction is hindered by the low degree of
supersaturation that can be achieved in water as a result of barium
hydroxide fair solubility (Ksp = 2.55 × 10−4). Instead, a
5118
heterogeneous approach based on the breakdown of Ba(OH)2
macrocrystals has been recently developed.55 Typically, the
milling of commercial barium hydroxide in 1-propanol leads to
fairly stable dispersions in alcohol for nanoparticles whose size
ranges from 200 to 400 nm (Figure 10).
Recently, mixed calcium and barium hydroxide nanoparticle
dispersions have proven to be highly effective in the
consolidation of mural paintings heavily contaminated by salts
(mainly sulfates and chlorides) in the Mesoamerican area (Figure
11).55,64 An additional advantage of the use of nanoparticle
dispersions of Ba(OH)2 in nonaqueous solvents is represented
by the very low toxicity as compared to that of aqueous solutions
of barium salts.
Magnesium Hydroxide Nanoparticles. Magnesium hydrox-
ide microparticles are employed in many industrial applications
as flame retardants and oxide precursors.65 In the past 10 years,
several “classical” synthesis pathways were modified and tailored
to produce magnesium hydroxide nanoparticles for the
conservation of cultural heritage. In particular, Mg(OH)2
nanoparticles, obtained via aqueous homogeneous phase
reactions and dispersed in alcohol, have been used for the
deacidification of paper, canvas, and wood.52,54,58,66,67 It was
reported that the particle size can be tuned from 50 to 300 nm by
changing the counterions’ nature52 and their concentration in the
chemical reaction.54 Despite the fact that these particles are
usually applied for deacidification purposes, they have been
recently considered for the consolidation of dolomite stones
(calcium−magnesium carbonate stones).64
By analogy to calcium hydroxide, magnesium hydroxide
nanoparticles can also be obtained from an alcohol thermal
dx.doi.org/10.1021/la304456n | Langmuir 2013, 29, 5110−5122
Langmuir
Figure 12. SEM images of the conversion of magnesium methoxide micrometer-sized particles into magnesium hydroxide nanoparticles. On the left,
octahedral-shaped magnesium methoxide micrometer-sized crystals. In the middle, the formation of hexagonal nanoplatelets of magnesium hydroxide
on {111} crystal planes during the hydration process of magnesium methoxide. On the right, magnesium hydroxide nanoparticles of about 100 nm after
the hydration reaction.
reaction starting from bulk metal. The conversion of a
micrometer-sized alkoxide intermediate (Figure 12) into nano-
metric magnesium hydroxide particles is favored by high pressure
and temperature, leading to stable concentrated dispersions in
short-chained alcohols.
Currently, magnesium hydroxide nanoparticles are mainly
used for the deacidification of paper and iron gall-inked
manuscripts,54,67 one of the more important open problems in
the field of paper conservation.68,69 As can be seen in Figure 13,
Figure 13. Corrosion of paper due to the presence of iron gall inks on a
historical manuscript (adapted from ref 54).
the synergistic effect of acidity and cellulose oxidation mainly as a
result of the free metal ions introduced into the substrate with the
application of the ink leads to the corrosion of cellulose fibers,
resulting in the loss of readability of the manuscript.
It has been demonstrated that the metal ion-catalyzed
oxidation (due to a radical formation mechanism) is enhanced
by acidity: this process has a high rate at pH values below 4.5
whereas the minimum catalytic activity of metal ions (iron and
copper) is in the 6.5−7.5 pH range.70 According to Strlič et al.70
and Baty et al.,57 the ideal requirement for a conservation
treatment of manuscripts is to stabilize the paper pH around
neutrality to hinder both acid-catalyzed hydrolysis and metal-
catalyzed oxidation. The application of alkaline earth metal
hydroxide nanoparticles dispersed in nonaqueous solvents
provides this feature, inhibiting the two different degradation
mechanisms through a single, simple, safe treatment that
gradually takes to a neutral pH, which results in a significant
increase in the inked-paper resistance to weathering. The
nonaqueous treatment54,67 prevented the leaching of water-
sensitive writing fluids and allowed an efficient distribution of the
deacidifying nanoparticles in the substrate. Moreover, the
5119
Invited Feature Article
reaction of nanoparticles with CO2 produces a carbonate buffer
to protect cellulose from aging.
The protective action of alkaline earth metal hydroxide
nanoparticles against ink corrosion was evaluated on paper
model samples featuring iron gall writing fluids. The degradation
of these systems was monitored before and after accelerated
hydrothermal aging (T = 90 °C, RH = 75%) by measuring the
cellulose degree of polymerization (via viscosimetric determi-
nations) and pH.54,67 In Figure 14, the comparison between the
Figure 14. Inked paper samples after artificial aging: (A) an unprotected
sample and (B) a sample treated with nanoparticles to protect it from
aging. Replica samples were made by the application of iron gall ink on
99.9% cellulose unsized Whatman paper (adapted from ref 54).
unprotected paper sample (i.e., not deacidified previous to aging
and having a pH of 3) and the sample neutralized with
magnesium hydroxide nanoparticles clearly shows how nano-
particle application protected the paper from ink corrosion. After
48 h of artificial aging, the unprotected sample exhibited severe
damage (e.g., brittleness) and could not be manipulated, whereas
sample B, treated with magnesium hydroxide nanoparticles,
retained its original mechanical properties.
Therefore, a single-step deacidification treatment, aimed at
stabilizing the pH around neutrality, can inhibit both metal-
catalyzed oxidation and the acid hydrolysis of paper, ensuring the
long-term preservation of iron gall-inked paper.
■ CONCLUSIONS AND OUTLOOK
In the past 15 years, colloids and material science generated a
number of innovative, functional, and fairly inexpensive tools for
the conservation of movable and immovable cultural heritage.
The use of materials compatible with those constituting the
works or art leads to the long-term stability of the treated artifact
whose useful life can be extended with strong societal and
economical benefits. Research in science of cultural heritage is
still far from being mature. The main possible future scenarios
include (a) new “green” surfactant-based self-assembled systems,
(b) water-in-oil, oil-in-water, and waterless cleaning micro-
dx.doi.org/10.1021/la304456n | Langmuir 2013, 29, 5110−5122
Langmuir
emulsions/emulsions for the treatment of highly sensitive
hydrophilic substrates (e.g., acrylic paintings), (c) organogels,
as a complement to the already popular hydrogels, to be used as
support systems for the above-mentioned fluids, (d) gels that are
responsive to an external stimulus, (e) nanoparticle dispersions
in apolar solvents for the deacidification of water-sensitive
substrates (parchment, leather), and (f) hybrid organic−
inorganic nanocomposite systems.
The new polyfunctional tools for the conservation of cultural
heritage might impact several fields, where the detergency and
chemical reactivity of the nanomaterials play a leading role.
However, the preservation and valorization of the cultural
heritage legacy lead to the outcome of consistent economical
resources (i.e., tourism) and, from a different point of view,
improve the image and perception of science and, in particular,
chemistry.
■
AUTHOR INFORMATION
Corresponding Author
*Tel: +39 0554573033. Fax: +39 0554573033. E-mail:
baglioni@csgi.unifi.it.
Notes
The authors declare no competing financial interest.
Biographies
Michele Baglioni, photographer
Left to right: Giovanna Poggi, Rodorico Giorgi, David Chelazzi, and
Piero Baglioni
Piero Baglioni has been the Chair of Physical Chemistry in the
Department of Chemistry at the University of Florence since 1994 and is
an MIT affiliate. He was appointed as visiting scientist/professor by the
Department of Chemistry of the University of Houston, the Weizmann
Institute, the Collège de France, and MIT. He is the Director of the
National Center for Colloids and Nanosciences (CSGI), and he is on
the advisory boards of several international journals and a member of the
scientific board of several national and international institutions and
societies. He is the author of more than 350 publications in books and
largely diffused international journals. He is also the author of 21
patents. In the field of conservation, he is a pioneer in the application of
colloids and soft matter to the conservation of cultural heritage. He has
produced several innovative methods for the consolidation and cleaning
of paintings and the deacidification of historical documents.
David Chelazzi, Ph.D. in science for cultural heritage conservation at the
University of Florence in 2007 and Master’s in chemistry in 2003, is
currently working as a postdoctoral fellow in the department of
chemistry at the University of Florence and CSGI. His main research
interests are the development of methodologies for the consolidation,
cleaning, and pH control of works of art such as wall and canvas
paintings, stone, paper, and archaeological wood. He is the author or co-
5120
Invited Feature Article
author of about 30 publications in the field of nanotechnology and
colloids science applications to the conservation of cultural heritage.
Rodorico Giorgi, Ph.D. in science for cultural heritage conservation at
the University of Florence and B.S. in chemistry, is currently a research
fellow in the department of chemistry at CSGI, University of Florence.
Giorgi’s background is in colloids science. His main research interests
are the development of methodologies for the conservation of cultural
heritage materials such as wall and easel paintings, stone, paper, and
archaeological wood. Giorgi is the author of about 80 publications in the
field of science for conservation.
Giovanna Poggi holds a Ph.D. in science for cultural heritage
conservation from the University of Florence and obtained a Master’s
in technology for the conservation of cultural heritage in 2007. She is
currently working as a postdoctoral fellow at CSGI in the development
and characterization of nanotechnology for conservation. Her research
mainly deals with the synthesis and characterization of nanoparticles and
their application to paper and wood deacidification.
■ ACKNOWLEDGMENTS
We thank all of the conservators involved in the application of the
conservation methodologies presented here to real case studies
for their help and, in particular, Tiziana Dell’Omo and Lucia Di
Paolo for the intervention in Nazareth (Israel) and Florence
Gorel for the experiments on Thang-Ka paintings. Moreover,
Ramon Carrasco Vargas (Proyecto Arqueologico Calakmul,
Mexico), Lilia Rivero Weber, Diana Medellin, Yareli Jaidar
Benavides, and Maria del Carmen Castro Barrera (Coordinación
Nacional de Conservación del Patrimonio Cultural, CNCPC,
Mexico), and Diana Magaloni (UNAM and Museo National de
Antropologia, Mexico) are acknowledged for the Mesoamerican
archaeological areas. CSGI, MIUR, and European Union
(project NANOFORART, FP7-ENV-NMP-2011/282816) are
acknowledged for financial support.
■ REFERENCES
(1) De La Rie, R.; McGlinchey, C. New Synthetic Resins for Picture
Varnishes. In Cleaning, Retouching and Coatings: Contributions to the
1990 IIC Brussels Congress; Mills, J. S., Smith, P., Eds.; International
Institute for Conservation of Historic and Artistic Works (IIC):
London, 1990; pp 168−173.
(2) Matte Paint: Its History and Technology, Analysis, Properties and
Conservation Treatment: With a Special Emphasis on Ethnographic
Objects; Walston, S., Bishop, M. H., Hansen, E. F., Eds.; Getty
Conservation Institute in association with the International Institute for
Conservation of Historic and Artistic Works (IIC): Marina del Rey, CA,
1993.
(3) Balbo, A.; Chiavari, C.; Martini, C.; Monticelli, C. Effectiveness of
corrosion inhibitor films for the conservation of bronzes and gilded
bronzes. Corros. Sci. 2012, 59, 204−212.
(4) Mahltig, B.; Swaboda, C.; Roessler, A.; Böttcher, H. Functionalising
wood by nanosol application. J. Mater. Chem. 2008, 18, 3180−3192.
(5) Stepien, P.; Kozlowsky, R.; Tokarz, M. Gypstop - Colloidal Silica
for Protective Coating of Porous Builiding Materials: Practical
Experience at the Wawel Castle, Cracow, Poland. In Structural Repair
and Maintenance of Historical Buildings III; Brebbia, C. A., Frewer, R. J.
B., Eds.; Computational Mechanics Publications: Boston, 1993; pp
304−310.
(6) Wheeler, G.; Mendez-Vivar, J.; Fleming, S. The use of modified Zr-
n-propoxide in the consolidation of calcite: a preliminary study focused
into the conservation of cultural heritage. J. Sol-Gel Sci. Technol. 2003,
26, 1233−1237.
(7) Baglioni, P.; Giorgi, R. Soft and hard nanomaterials for restoration
and conservation of cultural heritage. Soft Matter 2006, 2, 293−303.
dx.doi.org/10.1021/la304456n | Langmuir 2013, 29, 5110−5122
Langmuir
(8) Giorgi, R.; Baglioni, M.; Berti, D.; Baglioni, P. New methodologies
for the conservation of cultural heritage: micellar solutions, micro-
emulsions, and hydroxide nanoparticles. Acc. Chem. Res. 2010, 43, 695−
704.
(9) Carretti, E.; Bonini, M.; Dei, L.; Berrie, B. H.; Angelova, L. V.;
Baglioni, P.; Weiss, R. G. New frontiers in materials science for art
conservation: responsive gels and beyond. Acc. Chem. Res. 2010, 43,
751−760.
(10) Baglioni, P.; Chelazzi, D.; Giorgi, R.; Poggi, G. Nanoparticles for
the Conservation of Cultural Heritage: Paper and Wood. In Encyclopedia
of Surface and Colloid Science, 2nd ed.; Somasundaran, P., Ed.; Taylor &
Francis: New York, 2012; pp 1−16.
(11) Myakonkaya, O.; Guibert, C.; Eastoe, J.; Grillo, I. Recovery of
Nanoparticles Made Easy. Langmuir 2010, 26, 3794−3797.
(12) Allhoff, F.; Lin, P.; Moore, D. What Is Nanotechnology and Why
Does It Matter? From Science to Ethics; Wiley-Blackwell: Chichester, West
Sussex, U.K., 2010.
(13) Wolf, E. L.; Medikonda, M. Understanding the Nanotechnology
Revolution; Wiley-VCH: Weinheim, Germany, 2012.
(14) Favaro, M.; Mendichi, R.; Ossola, F.; Russo, U.; Simon, S.;
Tomasin, P.; Vigato, P. A. Evaluation of polymers for conservation
treatments of outdoor exposed stone monuments. Part I: photo-
oxidative weathering. Polym. Degrad. Stab. 2006, 91, 3083−3096.
(15) Horie, C. V. Materials for Conservation: Organic Consolidants,
Adhesives and Coatings, 2nd ed.; Butterworth-Heinemann: London,
2000.
(16) Wendler, E.; Klemm, D.; Snethlage, R. Consolidation and
Hydrophobic Treatment of Natural Stone. Durability of Building
Materials and Components - 5th International Conference on Durability
of Building Materials and Components; Brighton, England, Nov 7−9,
1990; Baker, J. M., Nixon, P. J., Majumdar, A. J., Davies, H., Eds.; Taylor
& Francis: London, 1991; pp 203−212.
(17) Havermans, J. B. G. A.; Dufour, J. Photo Oxidation of Paper
Documents. A Literature Review. Restaurator 1997, 18, 103−114.
(18) IDAP - Improved Damage Assessment on Parchment - Assessment,
Data Collection and Sharing of Knowledge; Larsen R., Ed.; Research
Report No. 18 EVK4-CT-2001−2006 EC Project, 2007.
(19) De Gennes, P. G.; Taupin, C. Microemulsions and the flexibility
of oil/water interfaces. J. Phys. Chem. 1982, 86, 2294−2304.
(20) Borgioli, L.; Caminati, G.; Gabrielli, G.; Ferroni, E. Removal of
hydrophobic impurities from pictorial surfaces by means of heteroge-
neous systems. Sci. Technol. Cult. Heritage 1995, 4, 67−74.
(21) Carretti, E.; Dei, L.; Miliani, C.; Baglioni, P.; Koutsoukos, P. Oil-
in-water microemulsions to solubilize acrylic copolymers: application in
cultural heritage conservation. Prog. Colloid Polym. Sci. 2001, 118, 63−
67.
(22) Carretti, E.; Dei, L.; Baglioni, P. Solubilization of acrylic and vinyl
polymers in nanocontainer solutions. Application of microemulsions
and micelles to cultural heritage conservation. Langmuir 2003, 19,
7867−7872.
(23) Baglioni, M.; Rengstl, D.; Berti, D.; Bonini, M.; Giorgi, R.;
Baglioni, P. Removal of acrylic coatings from works of art by means of
nanofluids: understanding the mechanism at the nanoscale. Nanoscale
2010, 2, 1723−1732.
(24) Baglioni, M.; Giorgi, R.; Berti, D.; Baglioni, P. Smart cleaning of
cultural heritage: a new challenge for soft nanoscience. Nanoscale 2012,
4, 42−53.
(25) Carretti, E.; Giorgi, R.; Berti, D.; Baglioni, P. Oil-in-water
nanocontainers as low environmental impact cleaning tools for works of
art: two case studies. Langmuir 2007, 23, 6396−6403.
(26) Rance, D. G.; Friberg, S. Micellar solutions versus micro-
emulsions. J. Colloid Interface Sci. 1977, 60, 207−209.
(27) Alba-Simionesco, C.; Teixeira, J.; Angell, C. A. Structural
characterization of glass-forming oil/water microemulsions by neutron
scattering. J. Chem. Phys. 1989, 91, 395−398.
(28) Baglioni, M.; Berti, D.; Teixeira, J.; Giorgi, R.; Baglioni, P.
Nanostructured surfactant-based systems for the removal of polymers
from wall paintings: a small-angle neutron scattering study. Langmuir
2012, 28, 15193−15202.
5121
Invited Feature Article
(29) Colafemmina, G.; Fiorentino, D.; Ceglie, A.; Carretti, E.; Fratini,
E.; Dei, L.; Baglioni, P.; Palazzo, G. Structure of SDS micelles with
propylene carbonate as cosolvent: a PGSE−NMR and SAXS study. J.
Phys. Chem. B 2007, 111, 7184−7193.
(30) Grassi, S.; Carretti, E.; Pecorelli, P.; Iacopini, F.; Baglioni, P.; Dei,
L. The conservation of the Vecchietta’s wall paintings in the Old Sacristy
of Santa Maria della Scala in Siena: the use of nanotechnological cleaning
agents. J. Cult. Heritage 2007, 8, 119−125.
(31) Dietemann, P.; Higgitt, C.; Kälin, M.; Edelmann, M. J.;
Knochenmuss, R.; Zenobi, R. Aging and yellowing of triterpenoid
resin varnishes − influence of aging conditions and resin composition. J.
Cult. Heritage 2009, 10, 30−40.
(32) Seves, A. M.; Sora, S.; Scicolone, G.; Testa, G.; Bonfatti, A. M.;
Rossi, E.; Seves, A. Effect of thermal accelerated ageing on the properties
of model canvas paintings. J. Cult. Heritage 2000, 1, 315−322.
(33) Down, J. L.; MacDonald, M. A.; Tétreault, J.; Williams, R. S.
Adhesive testing at the Canadian Conservation Institute: an evaluation
of selected poly(vinyl acetate) and acrylic adhesives. Stud. Conserv. 1996,
41, 19−44.
(34) Tétreault, J.; Stamatopoulou, E. Determination of concentrations
of acetic acid emitted from wood coatings in enclosures. Stud. Conserv.
1997, 42, 141−156.
(35) Carretti, E.; Dei, L.; Baglioni, P.; Weiss, R. G. Synthesis and
characterization of gels from polyallylamine and carbon dioxide as
gellant. J. Am. Chem. Soc. 2003, 125, 5121−5129.
(36) Carretti, E.; Dei, L.; Macherelli, A.; Weiss, R. G. Rheoreversible
polymeric organogels: the art of science for art conservation. Langmuir
2004, 20, 8414−8418.
(37) Carretti, E.; Grassi, S.; Cossalter, M.; Natali, I.; Caminati, G.;
Weiss, R. G.; Baglioni, P.; Dei, L. Poly(vinyl alcohol)−borate hydro/
cosolvent gels: viscoelastic properties, solubilizing power, and
application to art conservation. Langmuir 2009, 25, 8656−8662.
(38) Baglioni, P.; Dei, L.; Carretti, E.; Giorgi, R. Gels for the
conservation of cultural heritage. Langmuir 2009, 25, 8373−8374.
(39) Angelova, L. V.; Terech, P.; Natali, I.; Dei, L.; Carretti, E.; Weiss,
R. G. Cosolvent gel-like materials from partially hydrolyzed poly(vinyl
acetate)s and borax. Langmuir 2011, 27, 11671−11682.
(40) Wolbers, R. Cleaning Painted Surfaces: Aqueous Methods;
Archetype Books: London, 2007; p 198.
(41) Stulik, D.; Miller, D.; Khanjian, H.; Khandekar, N.; Wolbers, R.;
Carlson, J.; Petersen, W. C. Solvent Gels for the Cleaning of Works of Art:
The Residue Question; Dorge, V., Ed.; The Getty Conservation Institute -
J. Paul Getty Trust: Los Angeles, 2004.
(42) Kizilay, M. Y.; Okay, O. Effect of swelling on spatial
inhomogeneity in poly(acrylamide) gels formed at various monomer
concentrations. Polymer 2004, 45, 2567−2576.
(43) Bonini, M.; Lenz, S.; Falletta, E.; Ridi, F.; Carretti, E.; Fratini, E.;
Wiedenmann, A.; Baglioni, P. Acrylamide-based magnetic nanosponges:
a new smart nanocomposite material. Langmuir 2008, 24, 12644−
12650.
(44) Pizzorusso, G.; Fratini, E.; Eiblmeier, J.; Giorgi, R.; Chelazzi, D.;
Chevalier, A.; Baglioni, P. Physicochemical characterization of
acrylamide/bisacrylamide hydrogels and their application for the
conservation of easel paintings. Langmuir 2012, 28, 3952−3961.
(45) Bonini, M.; Lenz, S.; Giorgi, R.; Baglioni, P. Nanomagnetic
sponges for the cleaning of works of art. Langmuir 2007, 23, 8681−8685.
(46) Domingues, J. A. L.; Bonelli, N.; Giorgi, R.; Fratini, E.; Gorel, F.;
Baglioni, P. Innovative hydrogels based on semi-interpenetrating
p(HEMA)/PVP networks for the cleaning of water-sensitive cultural
heritage artifacts. Langmuir 2013, 29, 2746−2755.
(47) Giorgi, R.; Dei, L.; Baglioni, P. A new method for consolidating
wall paintings based on dispersions of lime in alcohol. Stud. Conserv.
2000, 45, 154−161.
(48) Ambrosi, M.; Dei, L.; Giorgi, R.; Neto, C.; Baglioni, P. Colloidal
particles of Ca(OH)2: properties and applications to restoration of
frescoes. Langmuir 2001, 17, 4251−4255.
(49) Salvadori, B.; Dei, L. Synthesis of Ca(OH)2 nanoparticles from
diols. Langmuir 2001, 17, 2371−2374.
dx.doi.org/10.1021/la304456n | Langmuir 2013, 29, 5110−5122
Langmuir Invited Feature Article

(50) Giorgi, R.; Dei, L.; Ceccato, M.; Schettino, C.; Baglioni, P.
Nanotechnologies for conservation of cultural heritage: paper and
canvas deacidification. Langmuir 2002, 18, 8198−8203.
(51) Nanni, A.; Dei, L. Ca(OH)2 nanoparticles from W/O
microemulsions. Langmuir 2003, 19, 933−938.
(52) Giorgi, R.; Bozzi, C.; Dei, L.; Gabbiani, C.; Ninham, B. W.;
Baglioni, P. Nanoparticles of Mg(OH)2: synthesis and application to
paper conservation. Langmuir 2005, 21, 8495−8501.
(53) Giorgi, R.; Chelazzi, D.; Baglioni, P. Nanoparticles of calcium
hydroxide for wood conservation. The deacidification of the Vasa
warship. Langmuir 2005, 21, 10743−10748.
(54) Poggi, G.; Giorgi, R.; Toccafondi, N.; Katzur, V.; Baglioni, P.
Hydroxide nanoparticles for deacidification and concomitant inhibition
of iron-gall ink corrosion of paper. Langmuir 2010, 26, 19084−19090.
(55) Giorgi, R.; Ambrosi, M.; Toccafondi, N.; Baglioni, P. Nano-
particles for cultural heritage conservation: calcium and barium
hydroxide nanoparticles for wall painting consolidation. Chem.Eur.
J. 2010, 16, 9374−9382.
(56) Strlič, M.; Kolar, J.; Zigon, M.; Pihlar, B. Evaluation of size-
exclusion chromatography and viscometry for the determination of
molecular masses of oxidised cellulose. J. Chromatogr., A 1998, 805, 93−
99.
(57) Baty, J. W.; Maitland, C. L.; Minter, W.; Hubbe, M. A.; Jordan-
Mowery, S. K. Deacidification for the conservation and preservation of
paper-based works: a review. BioResources 2010, 5, 1955−2023.
(58) Chelazzi, D.; Giorgi, R.; Baglioni, P. Nanotechnology for Vasa
wood de-acidification. Macromol. Symp. 2006, 238, 30−36.
(59) Arai, Y. The Preparation of Powder; Scarlett, B., Ed.; Chapman &
Hall: London, 1996.
(60) Hey, M. The use of the scanning electron microscope in
document restoration problems. Restaurator 1970, 1, 233−244.
(61) Lewin, S. Z.; Baer, N. S. Rationale of the barium hydroxide-urea
treatment of decayed stone. Stud. Conserv. 1974, 19, 24−35.
(62) Ferroni, E.; Malaguzzi-Valerj, V.; Rovida, G. Experimental Study
by Diffraction of Heterogeneous Systems as a Preliminary to the
Proposal of a Technique for the Restoration of Gypsum Polluted
Murals. Proceedings of the ICOM Conference, Amsterdam, 1969.
(63) Ferroni, E.; Baglioni, P. Experiments About the Method for the
Restoration of Sulfated Frescoes. In Proceedings of the Symposium
Scientific Methodologies Applied to works of Art; Parrini, P. L., Ed.;
Florence, Italy, May 2−5, 1984; Montedison Progetto Cultura: Milan,
1986; pp 108−109.
(64) Chelazzi, D.; Poggi, G.; Jaidar, Y.; Toccafondi, N.; Giorgi, R.;
Baglioni, P. Hydroxide nanoparticles for cultural heritage: consolidation
and protection of wall paintings and carbonate materials. J. Colloid
Interface Sci. 2013, 392, 42−49.
(65) Cao, H.; Zheng, H.; Yin, J.; Lu, Y.; Wu, S.; Wu, X.; Li, B. Mg(OH)2
complex nanostructures with superhydrophobicity and flame retardant
effects. J. Phys. Chem. C 2010, 114, 17362−17368.
(66) Giorgi, R.; Chelazzi, D.; Baglioni, P. Conservation of acid
waterlogged shipwrecks: nanotechnologies for de-acidification. Appl.
Phys. A: Mater. Sci. Process. 2006, 83, 567−571.
(67) Poggi, G.; Baglioni, P.; Giorgi, R. Alkaline earth hydroxide
nanoparticles for the inhibition of metal gall ink corrosion. Restaurator
2011, 32, 247−273.
(68) Henniges, U.; Reibke, R.; Banik, G.; Huhsmann, E.; Hähner, U.;
Prohaska, T.; Potthast, A. Iron gall ink-induced corrosion of cellulose:
aging, degradation and stabilization. Part 2: application on historic
sample material. Cellulose 2008, 15, 861−870.
(69) Kolar, J.; Možir, A.; Balažic, A.; Strlič, M.; Ceres, G.; Conte, V.;
Mirruzzo, V.; Steemers, T.; De Bruin, G. New antioxidants for treatment
of transition metal containing inks and pigments. Restaurator 2008, 29,
184−198.
(70) Strlič, M.; Kolar, J.; Šelih, V. S.; Kocar, D.; Pihlar, B. A comparative
study of several transition metals in Fenton-like reaction system at
circum-neutral. Acta Chim. Slov. 2003, 50, 619−632.

5122 dx.doi.org/10.1021/la304456n | Langmuir 2013, 29, 5110−5122