MRS Online Proceedings Library,

Cambridge Journals – published by Cambridge University press 2012

Gels for the Conservation of Cultural Heritage

Piero Baglioni1*, Debora Berti1, Massimo Bonini1, Emiliano Carretti1, Maria Del Carmen Casas
Perez2, David Chelazzi1, Luigi Dei1, Emiliano Fratini1, Rodorico Giorgi1, Irene Natali1 and
Marcia Carolina Arroyo1.
1
Department of Chemistry and CSGI, University of Florence, Via della Lastruccia 3,
50019 Sesto Fiorentino, Florence, Italy.
2
Facultad del Habitat, Universidad Autonoma de San Luis Potosi, Niño Artillero 150 - Zona
Universitaria, San Luis Potosi, Mexico.
*
Corresponding author

ABSTRACT

The consolidation of a pictorial surface or the removal of undesired material from the surface of
an artifact, are the most important and delicate operations in the conservation of cultural heritage.
In this contribution we report on the synthesis and characterization of two innovative systems for
the cleaning of works of art: i) highly viscous polymeric dispersions (HVPDs) of poly(vinyl
alcohol-co-vinyl acetate) random copolymer (PVAc), and ii) chemical gels from acrylamide -
N,N’-methylene bisacrylamide, loaded with innovative aqueous cleaning systems. These systems
were prepared, characterized and tested over artistic surfaces, such as wood and canvas.
Rheology and FTIR spectroscopy allowed the characterization of the materials, and provided
evidence that the systems allow an efficient cleaning of the substrates, without leaving residues.

INTRODUCTION

Historically, the cleaning of artworks’ substrates has had a fundamental role in the
activity of conservators and restorers, involving the usage of a wide number of techniques and
materials. As a crucial procedure in many restoration processes, cleaning has a twofold task.
While providing an aesthetic upgrade of the objects to their original look and beauty, cleaning
also ensures the removal of degraded coatings, varnishes, dirt, and other detrimental materials
that would otherwise enhance the degradation of the artistic surface [1,2].
In order to properly fulfill these tasks, the cleaning intervention needs to be as selective
and less invasive as possible. Chemical cleaning is usually coupled with mechanical action on
surfaces, so to remove layers of undesired material without inducing alteration on binders,
pigments, or even supporting substrates such as canvas or wood. Whenever the direct solving of
detrimental coatings is not possible, their swelling or softening, by means of solvents, is indeed
the preliminary step before their physical removal, using cotton swabs. As a matter of fact, the
swelling of coatings also grants a more gradual and less aggressive removal with respect to their
one-step solubilization, and is indeed generally addressed as a more careful procedure in
cleaning interventions.
 One of the major practical problems related to the usage of neat liquids, however, is due
to the lack of control in their application, resulting in aggressive or non-selective cleaning. As a
matter of fact gels, and in particular chemical gels, allow the retaining of liquids and their
controlled release on a surface, limiting the spreading of solvents through sensitive layers, and
the redissolution of the dissolved materials within porous matrixes. Moreover, the need for safe
and environmentally friendly products entails a control in the usage of volatile, toxic organic
solvents.
During the last decades, gel technology has provided strong support to the restoration
practice, through the development of several classes of materials that exhibit different applicative
properties [3-5]. The solvent gels, developed in the early 1990s improved the effectiveness of
chemical cleaning [3]. Recently, different kinds of organogels and hydrogels have been proposed
and tested for applications in cultural heritage conservation [5-9].
In this contribution we will focus on two systems, which exhibit different physical
properties and allow the usage of different cleaning fluids. The possibility of tuning the systems’
viscosity and density, ranging from “softer” to “harder” materials, accounts for both the
variability of the substrates to be treated and the numerous applicative methodologies. Moreover,
the different systems described in this work (a highly viscous polymeric crosslinked system and
a chemical gel) are suited for loading with several cleaning fluids, offering a wide range of
solvents and formulations. The broad polarity variation of the supported fluids reflects the need
for the removal of materials with different physico-chemical properties, spanning from
hydrocarbon-based coatings (waxes), to mixed sugar and protein material (animal or vegetal
glues), up to natural and synthetic varnishes (acrylic and vinyl). We developed systems that are
aimed at the swelling, rather than the direct solving, of detrimental coatings, in agreement with
well-established criteria in conservation practice.
The first system considered is an aqueous formulation of a poly(vinyl alcohol-co-vinyl
acetate) random copolymer (PVAc), cross-linked through the addition of borax. The copolymer
is a 73% PVAc, i.e. containing about 27% of vinyl acetate groups and 73% of vinyl alcohol
groups, hence it is indicated as 73PVAc. The hydroxyl groups are able to complex the borate
ions, originating a network of chains. The scheme reported in figure 1 describes the chemical
structure of the polymeric network, showing the crosslinking between the borate anions and the
73PVAc chains. As a result, PVAc-borax Highly Viscous Polymeric Dispersions (HVPD)
exhibit a very high shear elastic modulus, allowing a restorer to easily peel them from cleaned
surfaces, minimizing both the amount of residues left onto the paint surface [10] and the entity of
any additional rinsing needed. Peelability is an important feature, lacked by solvent gels that are
traditionally used in conservation, which might thus leave residues on the treated substrates
requiring a second cleaning intervention that could harm the substrates’ surface [11]. While the
presence of the hydroxyl groups in 73PVAc grants the cross-linking of the polymer’s chains, the
vinyl acetate groups allow the inclusion in the network of relevant amounts of organic solvents
that are normally used by restorers for cleaning purposes (i.e. acetone, ethyl-acetate, ethanol,
propanol, etc.). The included solvents can swell or solve a wide range of coating materials that
are retained by the highly viscous dispersions and retard evaporation, allowing a controlled and
safe cleaning procedure.
The second system considered is based on acrylamide gels, obtained by radical
polymerization of acrylamide, using N,N’-methylene bisacrylamide as a cross-linker. The gel’s
chain network consists of covalent bonds, which provide the system stronger cohesion forces
with respect to “physical” gels or viscous crosslinked polymer solutions as the solvent gels,
where links between polymeric chains are due to secondary bonds. This feature makes the
acrylamide gels particularly feasible for cleaning procedures, since they do not leave residues
upon application. Moreover, the hydrophilicity and good water retention shown by these gels
[12], allow their loading with water-based cleaning fluids, such as micellar solutions and
microemulsions [8].

Figure 1. Representation of the chemical structure of a 73PVAc-based HVPD: the formation of

the network is induced by the presence of Borate Cross-Links. The picture (Bottom Left) shows
an example of a HVPD composed by 6 wt % 73PVAc, 1 wt % borax in water.

The efficiency of these nanostructured liquids in the removal of detrimental coatings of

degraded organic polymers is indeed of primary interest, since it grants good cleaning
performances while using very low weight content of organic solvents (in the range of
percentage units), which are stably dispersed in a continuous aqueous phase [13,14]. The loading
of these practically aqueous systems in acrylamide gels enables a controlled release, which is a
crucial factor when treating water-sensitive surfaces, providing thus a promising match for
conservation purposes.

EXPERIMENT

Preparation and characterization of PVAc-borax HVPDs

For the preparation of the highly viscous dispersions, 73PVAc was supplied as a random
copolymer by Kuraray Co. Ltd., PVA505 (Mw = 66611, 73% hydrolyzed); Methyl Ethyl Ketone
(MEK > 99.5%) and sodiumtetraborate decahydrate (borax > 99.5%) were supplied by Fluka and
Merk respectively, and used as received. Water was purified by a Millipore Elix3 apparatus (R ≥
15 MΩ cm).
The HVPDs, composed by 6 wt % 73PVA and 1 wt % borax, were prepared as follows:
the polymer was added to pure water or to a mixture of water and an organic solvent (in this case
MEK) and the system was heated at 90 °C for 30 mins in order to ensure a complete
solubilisation of the polymer. Then an aqueous solution of sodium borate (3 wt %) was added
drop-wise under vigorous stirring, inducing a drastic increase of viscosity. For all the systems
considered in the present paper, a concentration of 6 wt % 73PVAc was selected to grant that the
polymer was above its entanglement concentration (C* ≈ 4 w/w % for 73PVAc) [15].
Oscillatory shear measurements were carried out by means of a Paar Physica UDS200
rheometer working at 25 ± 0.1 °C (Peltier temperature control system), using a cone-plate
geometry (diameter 25 mm and cone angle 1°); the gap between the plates was 0.5 mm. After
their loading, all the samples were equilibrated for 30 min at 25 °C prior to carrying out the
experiments. Frequency sweep measurements, describing the trend of the elastic modulus G’ and
the loss modulus G”, as a function of the angular frequency ω of the applied oscillatory shear
stress, were performed within the linear viscoelastic range (5% strain) previously determined by
means of preliminary amplitude sweep tests.

Preparation and characterization of acrylamide gels

Acrylamide (assay ≥ 99%), N,N’ methylene-bisacrylamide (assay ≥ 98%) and

N,N,N’,N’-tetramethylethylene-diamine (TEMED) (purity ≥ 99%) were supplied by Fluka,
Milan; Ammonium persulfate (APS) (purity > 98%) was supplied by Sigma-Aldrich, Milan;
Sodium dodecil-sulfate (SDS) (assay ≈ 95%), propylene carbonate (PC) (purity ≥ 99%) and
ethyl-acetate (EA) (purity ≥ 99.5%) were supplied by Sigma-Aldrich, Milan; 1-pentanol (purity
≥ 98.5%) was supplied by Merck. All the chemicals were used as received. Water was purified
by a Millipore MilliRO-6 Milli-Q gradient system (R > 18 MΩ cm).
The gel, composed by 5.28 wt % acrylamide 0.88 wt % N,N’ methylene-bisacrylamide,
93.84 wt % water, was prepared as follows: few milliliters of the monomer/cross-linker aqueous
solution were put in a plastic container, and nitrogen was flushed in the solution for 5 minutes to
remove dissolved oxygen. An aqueous solution of APS (100 µl, 3.28 mM) and TEMED (50 µl)
were added to the monomer/cross-linker solution, in order to initiate the radical
copolymerization. After 30 minutes at room temperature, the obtained hydrogel was washed ten
times with distilled water to remove the monomer residue.
For cleaning tests, the hydrogel was loaded with a micellar solution, based on SDS, 1-
pentanol, EA and PC, prepared as described in literature [13,14]. The choice of this EAPC
aqueous system (more than 73 wt % water) is due to its reported effectiveness for the removal of
degraded coatings of synthetic copolymers, such as acrylates and vinyls. The gel loading was
carried out by soaking the saturated gel in the micellar solution for 12 h.
Cubic blocks (9 cm3) of gel were loaded with the micellar solution, and tested over
canvas samples that had been treated with an acrylate and acrylate-vinyl adhesives (used for
canvas lining and restoration) and aged according to a procedure reported in literature [9].
Characterization of the canvas, before and after cleaning, was carried out through ATR,
using a Nexus 870 FT-IR Thermo Nicolet. A loaded gel cube was dried under vacuum in an oven
at 50˚C, and characterized through ATR, and the spectra were compared with those of the treated
canvas, in order to inquire the presence of residues due to cleaning.

DISCUSSION

The two proposed systems (PVAc-borax HVPDs and acrylamide gels) were characterized
using different techniques, due to the need to highlight, for each system, those properties and
factors that are crucially connected to a proper cleaning performance. Tests on different artistic
substrates and coatings were then performed, simulating typical cleaning interventions, and
assessment was carried out through both diagnostic techniques and feedback from professional
restorers.
i) PVAc-borax HVPD
Rheology measurements performed onto the PVAc-borax HVPD, allowed the prediction
of the effect of the components’ concentration on the system’s peelability from artistic surfaces
of interest. In this case, the attention was focused on the amount of MEK (a solvent largely used
in conservation for the cleaning of painted surfaces [16]) loaded in the HVPD.
Oscillatory shear measurements were carried out in order to obtain information about the
effect of the solvent on the rheological viscoelastic behavior of the 73PVAc HVPD. The profile
of the frequency sweep curves is typical of polymeric dispersions for all the formulations
investigated (in figure 2A the curves for the sample containing 5 w/w% of MEK are shown): at
high frequencies the elastic character prevails, as the storage modulus G’ is greater than the loss
modulus G’’, while at low ω values G” > G’ [17].
As indicated in figure 3A, G’ is almost independent from the frequency of the applied
oscillatory shear stress when ω is higher than 15 Hz. This asymptotic value can be approximated
to the system’s intrinsic elastic modulus G0 [18] that, in turn, is correlated to the density of the
cross-linking (ρcl) between the 73PVAc molecules, as expressed by equation 1:

G 0 = !cl k BT (1)

where kB is the Boltzman constant and T is the temperature (K) [19].

Figure 2. (A) Frequency sweep curves (storage modulus G’ (), loss modulus G’’ ()) for an
aqueous HVPD containing 6 wt % 73PVAc, 1 wt % borax and MEK (5 wt%); (B) trend of the
intrinsic shear modulus G0 as a function of the MEK content.

The increase of G0 observed upon the loading of MEK up to a concentration of 15 w/w%

(see figure 2B), indicates that MEK molecules have a structuring effect on the HVPD, inducing
an increase of the entanglement density (see equation 1). On the other hand, the increase of MEK
concentration does not affect the rheological behavior, since the profile of the curves, for
different formulations, does not change meaningfully.
The value of G0 has a fundamental applicative importance. The correlation between the
analytical rheological data and the macroscopic behavior of the system, exhibited during
cleaning tests, showed that a threshold value of 200 Pa is needed for an easy peeling of the
HPVD from treated substrates [20].
As a matter of fact, for all the investigated formulations it was observed that G0 is always
higher than 200 Pa (figure 2B). Accordingly, the systems exhibited good cleaning properties on
practical applications. Testing of the 73PVAc/MEK based HVPD was carried out on two
different substrates, i.e. a XVIth century religious wood paint, by Ludovico Cardi, and a
contemporary oil on canvas painting, by Marcel Burtin. The tests allowed checking the cleaning
efficacy of the HPVD and its removal from surfaces. The wood panel was affected by the
presence of a strongly yellowed surface layer, due to natural resins applied as a protective in a
previous restoration intervention. Such issues represent indeed recurring cases in the daily
practice of artworks curators. Figure 3A shows the portion of the wood panel where the cleaning
test was carried out, after 4 minutes of HVPD application, its removal, and mechanical removal
of the swollen resins. Figure 3B shows the one step removal of a HVPD from Burtin’s canvas
painting, with tweezers.
All the tests were carried out in cooperation with professional conservators who
supervised both the application and the removal procedure. Their feedback confirmed the
positive features of these cleaning systems, including the quick removal of coatings, the easy
removal of the HVPDs by peeling, the avoidance of residues left on the surface, and a controlled
cleaning action that did not affect the artwork’s substrate underneath the removed layers.
The assessment of the effectiveness of HVPDs was also carried out through scientific
tests on both the polymeric dispersions and the treated artistic surfaces, after cleaning
interventions [7].
Figure 3. (A) Detail of the XVIth century wood paint, by Ludovico Cardi, after the application
and the removal of a HVPD containing 6 wt % 73PVAc, 1 wt % borax and 15 wt % MEK. The
black circle encloses the test area. (B) Peeling of a HVPD (6 wt % 73PVAc, 1 wt % borax, in a
mixture composed by water and MEK 10:1) from the surface of the painting “Les Voiles” (oil on
canvas) by Marcel Burtin (1902-1979), by means of tweezers.
FTIR measurements performed on gilded wood, highlighted that no residues of the
HVPDs could be detected on the surface after their application and removal. Fluorescence
imaging showed that the viscous polymeric dispersions exhibited fluorescence after their
application on model films of shellac, leading to the assumption that the resin had partially
migrated inside the HVPD during the cleaning. Finally, the non-invasive character of cleaning
interventions with HVPDs was checked by inquiring the cohesion of the painted layer after the
swelling and mechanical removal of aged varnishes from a 15th century egg tempera wood panel:
cotton swabs were gently rubbed on the painted surface after the removal of the HVPD in order
to completely remove the swollen surface patina. No residues of pigments were analytically
detected on the swab roll and on the HVPD, confirming that the application of the polymeric
dispersions had not altered the painted layer.

ii) Acrylamide gel

Characterization and testing of the acrylamide gels were performed in order to check their
cleaning performances. These gels exhibit a high density and can be easily handled during the
different cleaning phases. Figure 4 shows a gel cube, loaded with the EAPC micellar solution, as
it was placed on an aged canvas model sample (treated with an acrylate-vinyl adhesive). In the
performed tests, the application of the loaded gel allowed the swelling and softening of the
adhesive coatings, enabling thus an easier mechanical removal of the films, with a decreased
stress on the cellulose fibers (see figure 4B). The formulation of gels with tunable density and
consistency is possible by changing the monomer/cross-linker ratios, so to adapt the systems to
different substrates. A good adhesion to the surface, and consequently an efficient wetting of the
detrimental coatings, can thus be granted for different kinds of surface morphologies and
geometries.
Depending on the type of applied adhesive on the works of art, the application of the gel
on aged canvas required from 30 minutes to 2 hours in order to have the adhesive films swelled
and eventually removed.
The gels showed a good retention of the aqueous fluid, limiting the wetting of the water-
sensitive fibers and avoiding the diffusion of the micellar solution along the plane of the canvas
surface.
Figure 4. (A) Cube (9 cm3) of an acrylamide gel, loaded with an EAPC micellar solution, placed
on a model sample of aged canvas treated with an acrylate-vinyl adhesive. (B) Cleaning area
after the removal of the gel. Details show the fibers texture before and after cleaning.

This feature is crucial in the cleaning of hydrophilic substrates, and designates these gels
as candidates for alternative options to the usage of waterless cleaning systems. A fundamental
stage of the study involved the evaluation of both the cleaning effectiveness, and the inquiry of
residues due to the application of acrylamide gels.
FTIR analysis was performed to provide evidence on both these aspects.
Figure 5 shows the FTIR spectra of an aged canvas sample treated with Plexisol® P550,
an adhesive based on a hydrocarbon solution of n-butyl methacrylate typically used in artworks’
restoration [21], before and after cleaning with the acrylamide gels and EAPC micellar solutions.
The spectrum of a sample of fresh, untreated cellulose is shown for reference. The most relevant
feature in the spectrum of the canvas treated with the adhesive, is the absorption band at 1724
cm-1, due to the stretching of the C=O group of the acrylate chains.
The strong decrease of this band in the spectrum of the cleaned canvas sample, confirmed
the quantitative removal of the adhesive from the substrate. The good match of the spectra of the
cleaned sample and fresh, reference canvas, provided further evidence of the cleaning efficiency.
Figure 6 shows the comparison between the FTIR spectrum collected on an acrylamide
gel, after drying, and the spectrum of the canvas aged sample after cleaning with the gel. The
most relevant spectral features in the gel spectrum are the absorptions at 1652 cm-1 and 1618 cm-
1
, due respectively to the C=O stretching (amide I) and NH2 bending (amide II) bands, and the
peak at 3194 cm-1, due to the symmetric NH2 stretching [22]. If gel residues were left on the
surface, the amide I and amide II bands would partially overlap with cellulose absorption around
1635 cm-1, due to absorbed water [23], producing shoulders.
Moreover, the NH2 stretching peak should produce a shoulder on the –OH stretching
broad adsorption of cellulose [23]. On the other hand, any shoulder was observed in the 3600-
2900 and 1690-1550 cm-1 regions of the samples’ spectrum after the cleaning tests, confirming
that the application of the acrylamide gel did not leave residues on the cellulose substrate.
The tests on model canvas samples were thus promising, and research efforts are now
being focused on the performances of these systems in the cleaning of more complex models and
real canvas paintings, the key factor being the retention of aqueous cleaning fluids by the gels, so
to avoid any damage to water sensitive layers all through the paintings’ cross-section.
Figure 5. FTIR spectra of an aged canvas sample, treated with Plexisol® P550, before (a) and
after (b) cleaning for 2 hours with an acrylamide gel, loaded with a EAPC micellar solution, and
gentle mechanical removal. (c) Spectrum of reference canvas.

Figure 6. (a) FTIR spectrum of an acrylamide gel, after drying in an oven under vacuum. (b)
Spectrum of an aged canvas sample, treated with Plexisol® P550, after cleaning for 2 hours with
an acrylamide gel, loaded with a EAPC micellar solution, and gentle mechanical removal.

CONCLUSIONS

Both the 73PVAc HVPDs and the acrylamide gels proved useful tools in the cleaning of
artistic substrates, providing a complete palette of smart materials for the preservation of Cultural
Heritage. The HVPDs characteristic peelability and compatibility with several classic solvents
(which are well retained in the polymeric dispersions), and the tunable consistency, easy
handling and good retention of water and aqueous cleaning fluids exhibited by the acrylamide
gels, all where highlighted as feasible features for the efficient cleaning of sensitive hydrophilic
surfaces, including canvas, wood and paper. Moreover, HVPDs and acrylamide gels do not leave
any instrumentally detectable residues on the treated substrates, granting a safer long-term
conservation after cleaning.
 These materials represent a significant advancement, to the best of our knowledge, with
respect to the state-of-the-art gelled systems, which are currently available to restorers and
conservators worldwide.

ACKNOWLEDGMENTS

The authors would like to thank Dr. Maria Matilde Simari (Soprintendenza Speciale per il Polo
Museale Fiorentino) and the International University of Art Foundation of Florence, for their
advising during the cleaning tests on the Ludovico Cardi’s panel. Mrs. Fabrizia Passeri is
acknowledged for having made available the painting by Marcel Burtin for tests. Thanks are due
to Michel Menu and Aurelia Chevalier (Centre de Recherche et de Restauration des Musees de
France C2RMF) for the experiments on canvas paintings.
CSGI (Consorzio Interuniversitario per lo Sviluppo dei Sistemi a Grande Interfase, Florence) is
gratefully acknowledged for financial support. This work has been also partly realized with the
financial support of TemArt; Programma Operativo Regionale—Regione Toscana, cofinanced
by Fondo Europeo di Sviluppo Regionale (POR CreO FESR 2007-2013).

REFERENCES

1. M. Baglioni, D. Rengstl, D. Berti, M. Bonini, R. Giorgi and P. Baglioni, Nanoscale 2,

1723 (2010).
2. E. Carretti, R. Giorgi, D. Berti, and P. Baglioni, Langmuir 23, 6396 (2007)
3. R.C. Wolbers, “Cleaning Painted Surface. Aqueous Method”, Archetype Publications,
London 2000.
4. P. Baglioni, L. Dei, E. Carretti and R. Giorgi, Langmuir 25, 8373 (2009).
5. E. Carretti, M. Bonini, L. Dei, B.H. Berrie, L.V. Angelova, P. Baglioni and R.G. Weiss,
Accounts Chem. Res. 43, 751 (2010).
6. E. Carretti, S. Grassi, M. Cossalter, I. Natali, G. Caminati, R.G. Weiss, P. Baglioni and L.
Dei, Langmuir 25, 8656 (2009).
7. E. Carretti, I. Natali, C. Matarrese, P. Bracco, R.G. Weiss, P. Baglioni, A. Salvini and L.
Dei, J. Cult. Heritage 11, 373 (2010).
8. M. Bonini, S. Lenz, R. Giorgi and P. Baglioni, Langmuir 23, 8681 (2007).
9. A. Chevalier, D. Chelazzi, P. Baglioni, R. Giorgi, E. Carretti, M. Stuke, M. Menu and R.
Duchamp in Proceeding of 15th Triennal Conference ICOM-CC (international Council
Of Museum – Committee for Conservation), New Delhi, India, Sept 22-26, 2008, Vol. 2,
pp 581.
10. L. Angelova, P. Terech, I. Natali, L. Dei, E. Carretti, R. G. Weiss, Langmuir 27, 11671
(2011).
11. D. Stulik, D. Miller, H. Khanjian, N. Khandekar, R. Wolbers, J. Carlson and W.C.
Petersen, “Solvent Gels for Cleaning of Works of Art. The Residue Question”, ed. The
Getty Conservation Institute, Los Angeles 2004.
12. M. Bonini, S. Lenz, E. Falletta, F. Ridi, E. Carretti, E. Fratini, A. Wiedenmann and P.
Baglioni, Langmuir 24, 12644 (2008).
13. M. Baglioni, R. Giorgi, D. Berti, and P. Baglioni, Nanoscale, DOI: 10.1039/c1nr10911a
(2011).
14. R. Giorgi, M. Baglioni, D. Berti and P. Baglioni, Accounts Chem. Res. 43, 695 (2010).
15. E. Carretti, S. Grassi, M. Cossalter, I. Natali, G. Caminati, R. G. Weiss, P. Baglioni and
L. Dei, Langmuir, 25, 8656 (2009).
16. C.V. Horie, “Materials for Conservation”, Butterworth-Heinemann, London 1987.
17. H.A. Barnes, “A Handbook of Elementary Rheology”, University of Wales, Institute of
Non-Newtonian fluid Mechanics, Cardiff, 2000.
18. S.R. Raghavan and E.W. Kaler, Langmuir 17, 300 (2001).
19. B.A. Schubert, E.W. Kaler and N.J. Wagner, Langmuir 19, 4079 (2003).
20. I. Natali, E. Carretti, L. Angelova, P. Baglioni, R.G. Weiss and L. Dei, Langmuir 27,
13226 (2011).
21. L. Osete-Cortina and M.T. Doménech-Carbó, J. Chromatogr. A 1127, 228 (2006).
22. R. Murugan, S. Mohan and A. Bigotto, J. Korean Phys. Soc. 32(4), 505 (1998).
23. P. Garside and P. Wyeth, Stud. Conserv. 48, 269 (2003).