Langmuir 2007, 23, 8681-8685 8681

Nanomagnetic Sponges for the Cleaning of Works of Art

Massimo Bonini, Sebastian Lenz,† Rodorico Giorgi, and Piero Baglioni*
Department of Chemistry and CSGI, UniVersity of Florence,
Via della Lastruccia 3 - 50019 Sesto Fiorentino, Florence, Italy
ReceiVed May 3, 2007. In Final Form: June 15, 2007

This letter reports the synthesis and characterization of functionalized magnetic nanoparticles associated with
chemical gels and their application to the conservation of cultural heritage. Magnetic nanoparticles, which are associated
with acrylamide ethylene oxide polymers, produce a sponge that can be loaded with oil-in-water microemulsions,
forming a magnetically responsive gel-like system and acting as a permanent hydrogel. The magnetic gel-like system
can be used for specific applications in detergents or in the release of the loaded material. The system can be magnetically
manipulated and cleaned from the loaded materials and then dried and reused for a different application. We report
an important application of this new nanomagnetic responsive material in the field of cultural heritage conservation.

Gel systems have been used in several applications since the
middle of the last century. Nowadays, they pervade our world
and are very popular in cosmetics, detergents, food, and
biomedical applications and in producing numerous products as
nanoparticles, dyes, and advanced ceramics using the sol-gel
method. Gels can be physical, where the fluid state can usually
be recovered by changing the temperature, or chemical, where
the gel state is obtained through a polymerization process.
An interesting application of physical gels in the field of
conservation science was first proposed by Wolbers for the
cleaning of artifacts (i.e., oil paintings). The use of solvents in
their gelated states partially overcomes the drawbacks in using
pure organic solvents to clean painted surfaces that deeply
penetrate the painted layer, possibly causing damage. Moreover,
the selectivity and the control of the cleaning procedure with
neat solvents are difficult to achieve,1-4 making problematic, in
many cases, the selective removal of undesired layers of material
from easel and wall paintings. Gels decrease the capillary
penetration of the solvent into the artifact and solvent evaporation
because it is immobilized within the gel network.5-7 The gel
cleaning technique is very versatile because several organic
solvents and many selective cleaning reagents (such as enzymes
and chelating agents)6 can be “gelated”. Therefore, it is possible
to achieve good selectivity in the removal of dirt, varnishes, and
synthetic polymers largely used in the past for the protection of
paintings and nowadays recognized as being deleterious to the
preservation of artwork.
Unfortunately, present gel technology is not without drawbacks.
The removal of gellant residues from the surfaces of works of
art usually requires the application of solvents,6 but very often
* Corresponding author. E-mail: baglioni@csgi.unifi.it.
† Present address: Max Planck Institute for Polymer Research, Acker-
mannweg 10, D-55128 Mainz, Germany.
(1) Clark, A. H.; Ross-Murphy, S. B. AdV. Polym. Sci. 1987, 83, 57.
(2) Guenet, J. M. ThermoreVersible Gelation of Polymers and Biopolymers;
Academic Press: London, 1993.
(3) Te Nijenhuis, K. ThermoreVersible Networks: Viscoelastic Properties and
Structure of Gels; Springer-Verlag: Berlin, 1997.
(4) Michalski, S. Cleaning, Retouching and Coatings: Technology and Practice
for Easel Paintings and Polychrome Sculpture; International Institute for
Conservation of Historic and Artistic Works: Brussels, 1990.
(5) Wolbers, R. C. Restoration ’92: ConserVation, Training, Materials and
Techniques, Latest DeVelopments; International Institute for Conservation of
Historic and Artistic Works: London, 1992.
(6) Wolbers, R. C. Cleaning Painted Surfaces: Aqueous Methods; Archetype
Publications: London, 2000.
(7) Dorge, V. ConserVation; Getty Conservation Institute Newsletter; 2000;
Vol. 15.3, pp 16-19.
gellant residues remain on and beneath the painted surface because
of the high viscosity of gels, which makes them difficult to remove
by simple washing. Moreover, they are often inappropriate for
porous substrates such as easel and wall paintings. These are
layered structures with variable composition and a painted outer
layer that is usually less than 1 to 2 mm thick. The large porosity
favors the entrapping of the solvent inside the pores, and cleaning
is a very difficult task. In this case, the gel formulation does not
represent a major advantage compared to pure organic solvents
that are still used to clean painted surfaces and to remove undesired
layers of material from easel and wall paintings.
Recently, the synthesis and characterization of new chemically
responsive organogels was reported.8 A polyallylamine (PAA)
gellant was used to prepare a new class of gels9 that behaves as
a “smart” system that can switch from solution-type to gel-type
rheological behavior by simple chemical action. PAA gels were
used for the cleaning of easel paintings with a satisfactory removal
of gel residues. However, these systems use weak acids to destroy
the gels’ network, and although the chemical action is moderate,
it must be controlled very carefully, especially if applied to
carbonatic material as wall paintings.
We pioneered the use of nanosystems in the conservation of
cultural heritage, and in particular, we devised micellar solutions,
microemulsions, and recently the use of responsive gels for
cleaning artifacts.9-12 Oil-in-water microemulsions (µE) and
micellar solutions13 were used to solubilize and remove aged
Paraloid B72 resin (acrylic and methacrylic copolymer) from
wall paintings that could not be removed by using traditional
cleaning methods.10-12
In this letter, we report on a new magnetically responsive
compartmentalized nanosystem. Functionalized magnetic nano-
particles have been chemically incorporated into a polyacrylamide
gel structure to obtain a chemical sponge that can be loaded with
microemulsions or micelles solutions (sketched in Figure 1,
hereinafter called a nanomagnetic gel) and can be used for several
different applications (i.e., biotechnology, cosmetics, detergents,
etc.). An important application to the conservation of cultural
(8) Terech, P.; Weiss, R. G. Chem. ReV. 1997, 97, 3133-3159.
(9) Carretti, E.; Dei, L.; Baglioni, P.; Weiss, R. G. J. Am. Chem. Soc. 2003,
125, 5121-5129.
(10) Carretti, E.; Dei, L.; Baglioni, P. Langmuir 2003, 19, 7867-7872.
(11) Carretti, E.; Salvadori, B.; Baglioni, P.; Dei, L. Stud. ConserV. 2005, 50,
1-8.
(12) Carretti, E.; Giorgi, R.; Berti, D.; Baglioni, P. Langmuir 2007, 23, 6396-
6403.
(13) Rance, D.; Friberg, S. J. Colloid Interface Sci. 1977, 60, 207

10.1021/la701292d CCC: $37.00 © 2007 American Chemical Society

Published on Web 07/11/2007
8682 Langmuir, Vol. 23, No. 17, 2007
Figure 1. Schematic representation of the process of loading the microemulsion into the nanomagnetic sponge structure. In the inset is a
representation of cross-linked particles (black spheres) bonded to MA residues (blue rectangles) and a PEG chain (red line); arrows represent
the binding group to the polymer network of acrylamide and bis-acrylamide.
Chart 1. Reaction Scheme of the PEG-Based Polymer (MA-PEG) Used to Cross Link Particles (Top)
heritage is highlighted here. We show how oil-in-water (o/w)
microemulsions can be associated with nanomagnetic sponges
to obtain a gel-like system for the cleaning of historical stones
or painted surfaces without undesired residuals on the works of
art. The nanomagnetic gel (i.e., the sponge loaded with a
microemulsion or micellar solution) can be shaped as desired
and applied to a specific area with fine spatial control of the area.
In addition, the nanomagnetic gel adhesion to the artifact can be
modulated by controlling the polymer cross linking during the
chemical synthesis of the sponge.
To the best of our knowledge, the nanomagnetic sponge loaded
with a micelle or microemulsion system to give a responsive
chemical gel represents one of the most advanced, versatile
systems for cleaning works of art, avoiding any side effects.
These responsive compartmentalized nanosystems are a real
breakthrough in the conservation of cultural heritage and represent
one of the few real applications of nanotechnology. They will
have a dramatic impact on the conventional methods used in the
conservation field and in several other fields where fine tuning
of the release or uptake of confined material is required.
The nanomagnetic sponge was obtained by cross linking
magnetic nanoparticles through a polymer network based on
polyethylene glycol (PEG) and acrylamide. A ferrofluid consisting
of positively charged CoFe2O4 nanoparticles in water (0.1 g/mL,
8 nm diameter) was obtained with minor modifications, according
to the method developed by Massart.14-17 To cross link the
particles, a PEG-based polymer (MA-PEG) was prepared through
the esterification of polyethylene glycol with maleic anhydride
(MA). The resulting MA-PEG molecules consist of carboxylic
groups at both ends of the PEG chain. It has been previously
shown that the binding reaction between magnetic nanoparticles
(14) Massart, R. C. R. Seances Acad. Sci., Ser. C 1980, 291, 1-3.
(15) Massart, R. IEEE Trans. Magn. 1981, 17, 1247-1248.
(16) Bonini, M.; Wiedenmann, A.; Baglioni, P. J. Phys. Chem. B 2004, 108,
14901-14906.
(17) Bonini, M.; Wiedenmann, A.; Baglioni, P. Physica A 2004, 339, 86-91.
Letters
and carboxylic acids take the complete coupling of the car-
boxylic headgroup over the surface of the particles.18 Therefore,
MA-PEG was directly reacted with the magnetic nanoparticles,
forming a slightly viscous magnetic fluid. Acrylamide and N,N′-
methylene bisacrylamide solutions were then added, and the
polymerization reaction was carried out at 42 °C for 4 h, with
ammonium persulfate as the radical initiator. Magnetic nano-
particles are embedded in the gel structure via reacting the double
bonds of acrylamide or N,N′-methylene bisacrylamide with the
double bond resulting from the esterification of polyethylene
glycol with maleic anhydride. (For further information, see
Supporting Information.)
At the end of the polymerization process, two phases were
obtained: an upper transparent liquid phase and a magnetic black
phase formed on the bottom of the vial. The magnetic phase was
simply collected by decanting the liquid phase with the aid of
a permanent magnet. The formed nanomagnetic sponge was found
to have a pH of ∼1. It was washed with distilled water until pH
5.5 was reached. To highlight the effect of the particles on the
structure of the polymeric sponge, a reference sponge without
magnetic nanoparticles was prepared using the same synthetic
procedure. The nanomagnetic sponge prepared as described shows
behavior that is typical of permanent hydrogels.
The gel formation is reversible. In fact, the nanomagnetic gel
can be freeze dried to obtain a magnetic powder that can be
rehydrated to reform the gel, as for permanent hydrogels. The
maximum swelling of the sponge (maximum amount of loaded
water) can be simply achieved by adding the sponge to a large
amount of water. Under these conditions, the nanomagnetic gel
sinks to the bottom of the container, but it does not break or
dissolve and it can be easily collected using a permanent magnet
or plastic tweezers. Because the sponge is a tightly bonded
structure, the consistency of the nanomagnetic gel is hard enough
(18) Sartoratto, P. P. C.; Neto, A. V. S.; Lima, E. C. D.; Rodrigues de Sa, A.
L. C.; Morais, P. C. J. Appl. Phys. 2005, 97, 10Q917.
Letters
Figure 2. SAXS curves of the microemulsion before being loaded
into the nanomagnetic gel structure and after being recovered with
the aid of a permanent magnet.
to be handled with tweezers and cut with a knife or scissors. This
behavior makes the gel suitable for several applications.
For specific application in the field of conservation science,
we loaded the sponge with a o/w microemulsion prepared
according to the literature procedure.10,13 The co-surfactant (1-
pentanol) was added dropwise to an aqueous solution of sodium
dodecyl sulfate at room temperature and stirred until a clear
solution was formed. An oil mixture of a nitrodiluent (commercial
mixtures of xylenes and chloro derivatives, which are solvents
that are used by restorers for paraloid removal), and p-xylene
was finally added at room temperature until a stable system was
formed. The microemulsion is constituted of nanometric droplets
(about 4 nm in radius, as obtained from small-angle X-ray
scattering) dispersed in the continuous water phase. As in the
case of water, the loading of the microemulsion into the sponge
structure was performed by simply adding a piece of nanomagnetic
sponge to a beaker containing the microemulsion. After 10 min,
the gel was collected with plastic tweezers and used to clean the
artwork. It is worth noting that the microemulsion droplets are
small enough to diffuse easily through the gel network. In fact,
polyacrylamide gels are known to present pores with sizes on
the order of hundreds of nanometers.19 Moreover, it has been
previously shown20 that polyacrylamide gels with a chemical
composition very similar to the one we discuss here are
characterized by the presence of inhomogeneities with a large
range of sizes, as estimated from 10 to 1000 Å. (For details of
the chemical composition, see Supporting Information.) There-
fore, the cleaning process mechanism of micellar solutions or
microemulsions, themselves or when they are loaded into the
magnetic gel, is the same. The inhomogeneities and the pores
of the polyacrylamide gel allow the microemulsion or micelle
droplets to migrate to the surface of the gel that is in contact
with the artwork, solubilize the material to be removed,
compartmentalize it in the droplet, and transfer it into the gel
structure.
Because the microemulsion could damage the gel structure
over time, the gel was always stored as dried powder or a hydrogel.
(19) Patras, G.; Qiao, G. G.; Solomon, D. H. Macromolecules 2001, 34, 6396-
6401.
(20) Benguigui, L.; Boué, F. Eur. Phys. J. B 1999, 11, 439-444.
Langmuir, Vol. 23, No. 17, 2007 8683
Figure 3. Dehydration curves of both magnetic and reference gels,
loaded either with water and a microemulsion.
Figure 4. Sequence illustrating the removal of the microemulsion-
loaded nanomagnetic gel from the surface of marble.
For this purpose, the microemulsion can be removed from the
nanomagnetic sponge after extensive washing with water or
simply by magnetic squeezing. Once cleaned, the nanomagnetic
gel can be dried and reused.
Interestingly, when the nanomagnetic sponge is loaded with
the microemulsion, both the gel and microemulsion retain their
structure. To show this, we have studied by SAXS the micro-
emulsion before being loaded into the nanomagnetic sponge and
the microemulsion recovered from a microemulsion-loaded
nanomagnetic gel. This procedure was imposed by the dominating
scattering of the magnetic nanoparticles embedded into the
polymeric matrix of the gel. The microemulsion was recovered
by applying a 1.4 T magnetic field to the nanomagnetic gel,
which causes the shrinkage of the gel and the release of the
microemulsion. SAXS results (Figure 2) demonstrated that the
structure of the microemulsion remains unchanged. In fact, SAXS
curves are almost identical, with a moderate shift in the position
of the interaction peak in the scattering vector that can be ascribed
to a slight change in the microemulsion concentration once the
microemulsion is recovered from the gel. (The Q-vector shift
reported in the Figure corresponds to about 3 Å in the correlation
distance.)
To evaluate the maximum amount of water that could be loaded
into the gel structure before detecting any phase separation, a
known amount of powder obtained from the freeze drying of the
nanomagnetic gel was fully hydrated. In both the reference (the
gel without magnetic nanoparticles in the framework) and the
8684 Langmuir, Vol. 23, No. 17, 2007
Figure 5. Microreflectance FTIR spectra: (a) quarry marble sample
without any treatment on the surface; (b) the same surface treated
with a very thick layer of paraloid B72; (c) reference sample of
paraloid B72 as a pellet; and (d) marble surface after complete removal
of the thick paraloid B72 layer using the nanomagnetic gel. The
thick layer of paraloid B72 completely hides signals coming from
calcium carbonate (calcite) (image b). The efficacy of the novel gel
is highlighted by the complete disappearance of polymer and the
recovery of the marble signals (image d).
Figure 6. (A) SEM picture of a marble surface treated with paraloid
B72 before cleaning and (B) after cleaning. (C) Mapping of calcium
(green spot) through EDS (Cameo software) before cleaning; (D)
30 min after nanomagnetic gel application; and (E) after the complete
removal of the polymer.
magnetic gel, the amount of water in the fully hydrated gel was
slightly higher than 90% by weight. No significant differences
were found for either the reference or the magnetic gels loaded
Figure 7. Application of the nanomagnetic gel to a fresco painting realized in the laboratory for testing the gel efficacy for paraloid B72
removal. Left panel: white glaze shows the area treated with Paraloid, and the circle shows the area that will be used for gel treatment (grazing
angle light). Center panel: gel treatment (normal light). Right panel: area cleaned by the removal of paraloid B72 (grazing angle light).
Letters
with the microemulsion. The capability of the gel to retain the
solvent in its structure was studied by mixing 90 wt % solvent
(either water or a microemulsion) and 10 wt % sponge obtained
from the freeze-drying of the gel. The samples were stored in
a humidity-controlled chamber (relative humidity 50%), and their
weight was checked during time. In this way, dehydration curves
were obtained for the hydrated reference gel, the hydrated
magnetic gel, the microemulsion-loaded reference gel, and the
microemulsion-loaded magnetic gel. In Figure 3, the percentage
by weight of the solvent against storage time is shown. No
differences between the reference and the magnetic gel, loaded
with water or the microemulsion, have been found, suggesting
that the presence of magnetic particles does not affect the water-
retention properties of the gel. However, the similarity in the
dehydration behavior indicates the active role of magnetic particles
in solvent adsorption. In fact, the composition of the sponge is
different between the reference and the magnetic gel. The
inorganic content of the magnetic powder (the dried nanoparticle
sponge) is around 28%, whereas the reference powder is entirely
organic. Interestingly, for loaded nanomagnetic gels we should
expect a very fast decrease in the solvent content corresponding
to the evaporation of the volatile organic component in the
microemulsions (i.e., p-xylene and nitrodiluent). This effect is
indeed reported in Figure 3, but it is much slower than expected
for a pure solvent or a microemulsion: the solvent content of
microemulsion-loaded gels and water-loaded gels equalizes after
about 10 days, indicating that the evaporation of the volatile
fraction is consistently slowed down by the confinement effect
played by the gel structure. In terms of the usability of the
microemulsion-loaded nanomagnetic gel, these results show that
the system is stable for several days (i.e., much longer than the
typical application time of such systems in cultural heritage
conservation, usually from a few minutes to hours).
The nanomagnetic gel loaded with the microemulsion was
used to clean the surface of a marble sample (5 × 5 × 2 cm3)
that was selected because of the white color that emphasizes the
possible presence of black magnetic nanoparticle residuals on
the surface. Paraloid B72 is the most widely used resin for the
consolidation and protection of paintings and stones. Unfortu-
nately, Paraloid B72 tends to yellow and lose its chemical and
mechanical properties after natural aging, producing consistent
damage to artifacts.21-23 The marble sample selected for the
experiment was treated 8 years ago by brushing with a p-xylene
solution of paraloid B72 and was stored at ambient conditions.
Letters
The surface before the nanomagnetic gel application appeared
glassy and yellowed. The removal of the resin was performed
by direct application of the microemulsion-loaded magnetic gel
onto the area to be cleaned. After the desired application time
(variable from 10 min to 2 h), the gel was removed with the aid
of a permanent magnet (see the sequence in Figure 4). It is worth
noting that no contact between the magnet and the artifact is
necessary to remove the gel, making the cleaning process
particularly appropriate for the cleaning of precious artifacts.
The efficiency of the removal process was investigated by means
of microreflectance FTIR. A comparison of spectra (Figure 5)
collected before and after the treatment showed that signals from
the acrylate at 1751 cm-1 completely disappeared after the
cleaning. In addition to FTIR, the SEM analysis and, in particular,
the mapping of X-ray emission collected by an EDS system
(energy-dispersive X-ray spectrometry) provided clear evidence
that no residuals of the magnetic nanoparticles were present on
the cleaned surface and that the polymer was completely removed
(Figure 6). The nanomagnetic sponge was also used to clean the
surface of a damaged fresco, showing that this formulation can
be applied to this kind of artwork as well (Figure 7).
(21) Price, C. A. Stone ConserVation: An OVerView of Current Research;
Getty Conservation Institute: Los Angeles, 1996.
(22) Horie, C. Materials for ConserVation: Organic Consolidants, AdhesiVes
and Coatings; Butterworth-Heinemann: London, 1987.
(23) Feller, R. L. Accelerated Aging: Photochemical and Thermal Aspects;
The Getty Conservation Institute: Los Angeles, 1994.
Langmuir, Vol. 23, No. 17, 2007 8685
In conclusion, a new magnetic responsive sponge has been
synthesized. The sponge can be loaded with common solvents
or with more sophisticated dispersed systems, such as micro-
emulsions or micellar systems, and can be easily manipulated,
cut with a knife or scissors to the desired shape, and magnetically
or mechanically removed from the region of application. The
loaded phase (microemulsion or micelle) retains its original
structure and properties. The overall system is particularly efficient
in the uptake and release of the material contained in the loaded
phase. We highlighted here the application to cultural heritage
conservation, but it can be used in a large number of practical
applications. The nanomagnetic gel represents the most advanced
and versatile system for cleaning and will have a dramatic impact
on the conventional methods used in the conservation field and
in several other fields where fine tuning of the release or uptake
of confined material is required.
Acknowledgment. Thanks are due to David Chelazzi for the
FTIR analysis, Emiliano Fratini for SAXS experiments, and
Michele Baglioni and Giacomo Pizzorusso for assistance with
the application tests. Financial support from MIUR (PRIN-2006)
and CSGI is acknowledged.
Supporting Information Available: Preparation of the magnetic
nanosponge. This material is available free of charge via the Internet
at http://pubs.acs.org.
LA701292D