CeROArt

Numéro 6  (2010)
Horizons

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Florence Gorel
Assessment of agar gel loaded with
micro-emulsion for the cleaning of
porous surfaces
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Florence Gorel, « Assessment of agar gel loaded with micro-emulsion for the cleaning of porous surfaces »,
 CeROArt [En ligne], 6 | 2010, mis en ligne le 17 novembre 2010. URL : http://ceroart.revues.org/index1827.html
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 Assessment of agar gel loaded with micro-emulsion for the cleaning of porous surfaces 2

Florence Gorel

Assessment of agar gel loaded with

micro-emulsion for the cleaning of porous
surfaces
Introduction
1 During my training at the Wereldmuseum of Rotterdam, I had the opportunity to experiment
with some mixtures made with agar and micro-emulsion. These experiments are reported in
this paper.
2 For the cleaning purposes, the nature of porous surfaces forced the conservators to look
at solubility, capillary action and evaporation rate of their materials and tools. The  use of
pure organic solvents can have the undesirable effect, typical of the surface considered, of
redistributing the dissolved material further within the porous matrix.
3 This research focuses on the removal of hydrophobic materials on a porous and hydrophilic
surface. We studied an agar gel loaded with a micro-emulsion. The agar gel was chosen for
its common use in cleaning and its safety, and the micro-emulsion for the good results in the
cleaning of porous paint layers. The purpose of the research was to improve the strength, the
capability to retain the solvents and the efficacy of the agar gel loaded with micro-emulsion
to remove wax, as well as to prevent the redistribution of this hydrophobic material into the
porous layer.

Materials and methods

Micro-emulsion
4 Materials: Reverse Osmosis water, sodium dodecylsulphate (SDS, Fluka, purum ≥ 96 %),
pentan-1-ol (Fluka, ≥ 99 %), Petroleum ether (Fishersci, 100/140 °).
5 Micro-emulsions are microheterogeneous liquid systems, which means structured systems
of colloidal dimensions formed when amphipathic substances are dissolved in solvents,
in appropriate concentrations1. Among these microheterogeneous systems we may list the
emulsions, the micro-emulsions and the micelles.
6 The first use of a micro-emulsion in the conservation field is mentioned by L. Borgioli for the
cleaning of the Masaccio’s frescoes in the Brancacci Chapel2. The cleaning of these paintings
includes the removal of hydrophobic impurities (wax) using micro-emulsions. The Micro-
emulsions were used later by E. Carretti for the removal of deteriorated organic materials, oil-
and acrylic-based materials from mural paintings3.
7 The most innovative aspects of the used of micro-emulsion are:
• A higher extracting efficiency of hydrophobic materials than emulsions.
• The redistribution of dissolved hydrophobic materials into the porous surface is avoided
by the hydrophilic barrier of the continuous phase since dissolution takes place within
the micelles aggregation.
• Micro-emulsion systems are thermodynamically stable throughout a wide range of
environmental conditions.
8 Oil-in-water micro-emulsions contain a continuous phase (water) and a dispersed phase
(aliphatic hydrocarbon) presents within the core of micelle aggregates of surfactant4. The
content of surfactant is much higher than the Critical Micelle Concentration.  It causes the
spontaneous aggregation of these molecules and reduces the interfacial tension between oil and
water. A micro-emulsion can contain a co-surfactant in order to maximize the concentration

CeROArt, 6 | 2010
 Assessment of agar gel loaded with micro-emulsion for the cleaning of porous surfaces 3

of the dispersed phase in the system and lower the interfacial tension between water and oil
droplets
Fig. 1 Oil-in-water micro-emulsion

Schematic representation of the micellar configuration into oil-in-water  micro-emulsion.

Crédits: Holmberg, 1999
9 The dispersed phase forms micro-droplets in the continuous phase, coated by a mixed film
of surfactant and co-surfactant. The size and shape of the micelles are a function of the
concentration and structure (length and volume of the hydrophobic tail) of the surfactant;
the droplets diameters are typically from 5 to 50 nm5. In the case of SDS as the surfactant,
the micelles are spherical. The micelle size of SDS/Pentanol micro-emulsion, obtained from
small-angle X-ray scattering, is about 4 nm6.
10 Addition of co-surfactant is not needed to form micro-emulsion, although it is used to simplify
the work. The solvent Pentanol, a medium-chain length alcohol, changes the size of the
micelles: smaller with a low concentration, bigger with a higher one7. The Pentanol molecules
are located at the head at the surface of the micelle whereas the tail is penetrating the micelle
core in the case of an oil-in-water micro-emulsion.
11 In the case of oil-in-water micro-emulsions, the dissolution sites may be identified in several
regions8: between the hydrophilic groups and the first carbon atoms of the alkyl chains of
surfactants – in this region large aromatic molecules and long chain alcohol can be dissolved
–, within the core of the droplets – dissolution of aliphatic hydrocarbons in the case of oil-
in-water micro-emulsion –, and in the large hydrocarbon volume. The type of hydrophobic
sites exhibited by micro-emulsion explaines the high dissolving capacity of these systems.
Moreover micro-emulsion systems are strongly dynamic which means that the components
can show different kinds of exchange processes. The dynamic behavior of micro-emulsions
controls the exchange of solubility between droplets, and it has a strong impact on the chemical
reactivity of such systems9.

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 Assessment of agar gel loaded with micro-emulsion for the cleaning of porous surfaces 4

12 For conservation purposes, micro-emulsion with SDS (NaC12H25SO4), as an anionic surfactant,

and Pentanol (C5H12O), as the co-surfactant, were used.  The micro-emulsion is prepared using
the amount of materials indicated as in Table 1, the compositions are given in % of weight10.
The micro-emulsion is stable and transparent.
Table 1 Composition of the oil-in-water micro-emulsion

Co-surfactant
Continuous phase Dispersed phase
Surfactant (SDS)            (1-
RO water (Petroleum ether)
Pentanol)
µE1 85 4 6 5

Preparation of the gel

13 The name “agar” refers to a complex mixture of polysaccharide components, which may be
derived from certain genera of the Rhodophyceae group of red sea weeds11. The principal
gelling component is Agarose based on a disaccharide repeat unit
Fig. 2 Disaccharide repeat unit of Agarose

Credits: Clark, 1987

14 The thermoreversible gelation of Agarose occurs when hot Agarose solutions are cooled below
about 40°C. The Agarose network structure involves a double-helix formation
Fig. 3 Model for Agarose network formation

Credits: Clark, 1987

15 The agar gel is known to present large pore sizes which may allow the microemulsion to
migrate to the surface of the gel that is in contact with the porous surface.

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 Assessment of agar gel loaded with micro-emulsion for the cleaning of porous surfaces 5

16 In this research, in order to test the faculty of agar gel to be loaded with micro-emulsion, five
agar gels were be loaded with oil-in-water micro-emulsion and their properties were compared
with these of an agar reference gel. Agar gels of concentration 2 % (w/v) were prepared by
dissolving agar in Reverse Osmosis water. Each solution was heated over a hot plate in a
Pyrex beaker placed in a bain-marie at 90 °C during 5 minutes. Then the agar dispersion was
placed in an ice bath to rapidly cool down until a temperature of 40°C was reached. After
that, the micro-emulsion was gradually added to the agar gel and the whole preparation was
placed in the fridge. The agar reference gel without micro-emulsion was prepared using the
same procedure. The composition of the gels is given in Table 2. To evaluate the maximum
amount of micro-emulsion that could be loaded in the gel structure before detecting any phase
separation, several agar gels were prepared (by mixing) with different concentration of micro-
emulsion from 10 to 40 % w/v.
Table 2 Composition of agar gels (% weight)

Agar RO water μE
Gelref
2 98 0
Gel 1
2 88 10
Gel 2
2 78 20
Gel3 2 68 30
Gel 4
2 58 40

Preparation of the samples

17 The agar-micro-emulsion gels were used to clean the surface of wood samples (1,5 x 5 x 0,5
cm3). This material was selected because of its porosity, allowing the trapping of materials
into the structure. Bees wax was chosen due to its common use in conservation treatments and
its solubility in hydrocarbon solvents. The wax was heated and applied on the samples with a
brush and then with a spatula in order to increase its penetration into the porous matrix. The
excess of wax was removed with only a thin layer of wax remaining on the samples.  The
cleaning test was performed by direct application of the reference gel and gels 1, 2, and 3
onto the area to be cleaned. The gels were stored during 24 hours before being applied on the
samples. Each gel was applied during 90 minutes on the samples.

Results
18 After adding the first drops of micro-emulsions in agar, the gels become milky and show a
high viscosity

CeROArt, 6 | 2010
 Assessment of agar gel loaded with micro-emulsion for the cleaning of porous surfaces 6

Fig. 4 Partial opacity in the agar-micro-emulsion gel with respect to the agar-gel
transparency

Credits: Fl. Gorel

19 For the agar-micro-emulsion gels, the gelation process occurs few minutes after the addition
of micro-emulsion. Gels 1 and 2 are homogeneous. Gel 3 shows a small quantity of solvent in
excess while the agar gel and the micro-emulsion are fully separated in gel 4. After 1 day of
storage, the gels 1, 2 and 3 exhibit a small amount of solvent in excess, a change of volume
and a good strength. Agar-micro-emulsion gels, unlike pure one, are partially opaque.
20 The capability of the gel to retain the micro-emulsion in its structure was studied using
the dehydratation curves. Three agar-oil-in-water micro-emulsion gels (1, 2 and 3), the agar
reference gel and the micro-emulsion were stored at ambient conditions (temperature: 25°C,
± 1°C, and relative humidity: 46%, ± 2%), and the evolution of their weights was measured12.
The Figure 5 shows no differences between the reference and the agar-oil-in-water micro-
emulsion gels, suggesting that the presence of the micro-emulsion does not affect the retention
properties of the agar

CeROArt, 6 | 2010
 Assessment of agar gel loaded with micro-emulsion for the cleaning of porous surfaces 7

Fig. 5 Dehydratation curves of agar-micro-emulsion gel and reference gel

Crédits: Fl. Gorel

21 For cleaning, after 90 minutes of time application of gels 1, 2 and 3, the surface seems to be
partially free of wax. This observation was confirmed by the UV inspection
Fig. 6 Observation under visible light and under UV light of the samples without wax, with
wax and after application of Gel2 and Gel3

Credits: G. Vanneste

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 Assessment of agar gel loaded with micro-emulsion for the cleaning of porous surfaces 8

Conclusion
22 Introduction of oil-in-water micro-emulsion in agar gel when the gel is already formed do not
prevent the gelation process of agar. The gel network is able to maintain its structure until 1,5
% weight of Petroleum ether. This is sufficient to dissolve bees wax due to the high extracting
efficiency of micro-emulsion.
23 The physical properties of the Agar gels are good enough for a conservation work when the
concentrations of micro-emulsion are between 10 and 30% but they should be applied on
the object during a long time. Moreover, agar gel allows the micro-emulsions to flow on the
porous surface and to wet it but maintains the micro-emulsion in its structure and prevents
the formation of rings. Evaporation of the solvents is slowed down and the gels can be used
for a long period.

Notes
1 HOLMBERG, JÖNSSON, KRONBERG AND LINDMAN, Surfactants and Polymers in Aqueous Solution, John
Wiley and Sons, New York, 1999, pp. 365-380.
2 BORGIOLI L., CAMINATI G., GABRIELLI G., FERRONI E., “Removal of hydrophobic impurities from
pictorial surfaces by means of heterogeneous systems”; Science and Technology for Cultural Heritage,
4 (2), 1995, pp 67-74.
3 CARRETTI E., SALVADORI B., BAGLIONI P. and DEI L., “Microemulsions and micellar solutions for
cleaning wall painting surfaces”, Studies in Conservation, 50 (2), 2005, pp 128-136.
4 CARRETTI E., SALVADORI B., BAGLIONI P. AND DEI L., Op. cit., p. 129.
5 TONDRE C., “Dynamic Processes in Microemulsions”, Dynamics of Surfactant Self-Assemblies.
Micelles, Microemulsions, Vesicles and Lyotropic Phases, vol. 125, Boca raton, New York, 2005.
6 BONINI M., LENZ S., GIORGI R., AND BAGLIONI P., “Nanomagnetic Sponges for the Cleaning of Works of
Art”, Langmuir, 23, 2007, p. 8683, the droplet size of micro-emulsion of Nitrodiluente and Xylene in
water with SDS and Pentanol was obtained by small-angle X-ray scattering.
7 ZANA R.,Dynamics of Surfactants self-assemblies. Micelles, Microemulsions, Vesicles and Lyotropic
Phases, vol. 125, Boca raton, New York, 2005.
8 BORGIOLI L., CAMINATI G., GABRIELLI G., FERRONI E.,Op. cit., p. 70.
9 TONDRE C.,Op. cit.
10 Correspondence with K. Holmberg.
11 CLARK A. H. AND ROSS-MURPHY S. B., “Structural and Mechanical Properties of Biopolymer Gels”,
Advances in Polymer Science, 83, 57, Springer-Verlag, Berlin, 1987, pp. 122-125.
12 BONINI M., LENZ S., GIORGI R. AND BAGLIONI P.,Op. cit., p. 8684.

Pour citer cet article

Référence électronique
Florence Gorel, « Assessment of agar gel loaded with micro-emulsion for the cleaning of porous
surfaces »,  CeROArt [En ligne], 6 | 2010, mis en ligne le 17 novembre 2010. URL : http://
ceroart.revues.org/index1827.html

Florence Gorel
Diplômée de l’Institut national du patrimoine en restauration de peinture, Florence Gorel se
passionne depuis quelques années pour la peinture asiatique et le nettoyage des surfaces poreuses.
Ses recherches l’ont amenée à étudier les microémulsions, les gels et les éponges nanomagnétiques.
florence.gorel@gmail.com

Droits d'auteur

CeROArt, 6 | 2010
 Assessment of agar gel loaded with micro-emulsion for the cleaning of porous surfaces 9

© Tous droits réservés

Résumé / Abstract

 
Le système composé d’un gel d’agar-agar et d’une microémulsion présente plusieurs qualités
pour extraire des matériaux hydrophobes de couches poreuses. Les propriétés rhéologiques de
ce système sont adaptées à un usage en restauration et sont stables pendant plusieurs jours. Les
gels permettent la solubilisation du matériau à l’aide de faible quantité de solvant, l’empêchent
de créer des auréoles, permettent le contrôle de l’évaporation des solvants et ne laissent pas
de résidus de gel dans les pores.
Mots clés :  agar-agar, auréole, résidu, gel, surface poreuse, nettoyage, microémulsion

 
Agar gel loaded with micro-emulsion could be used to extract lipophilic materials from porous
surfaces. The physical properties of the gels are good enough for a conservation work. They
allow the micro-emulsion to flow on the porous surface and to wet it but maintain the micro-
emulsion in its structure and prevent the formation of rings. The evaporation of the solvents
is slowed down and the gels can be used during a long period.
Keywords :  ring, gel, residue, porous surface, cleaning, micro-emulsion, agar

ndlr : Institut National du Patrimoine – Contact : Patricia Vergez

CeROArt, 6 | 2010