simonetta iannuccelli and silvia sotgiu

Wet Treatments of Works of Art on Paper with Rigid Gellan Gels

“What cannot he express in monochrome, that is with black the cleaning intervention
lines! Light, shade, splendour, the sublime, depths…”
Erasmus of Rotterdam, on the work of Albrecht Dürer Surface cleaning of a work of art on paper is the inter-
vention aimed at removing inorganic and organic substances
abstract which, over time, have deposited and been partly encompassed
within the paper’s surface. Given its completely irreversible
Since 2003, the ICPAL Laboratory for the Conservation of nature, the operation must be carried out by using the dif-
Library Materials in Rome has been developing a conservation ference in solubility between the substances present in the
method to carry out cleaning interventions on works of art on original materials and what has to be removed as a reference,
paper using rigid aqueous Gellan gels, a microbial exopolysac- and by carefully assessing the changes that can been seen on
charide that allows a constant and controlled release of water the work during the operation. While in other categories of
onto the paper. The adoption of this method, which has been artistic artefacts—such as movable paintings and frescoes—
modified by research carried out during cleaning interventions cleaning can be carried out selectively in line with the nature
on moveable paintings, is a result of the need to find a tech- and stratification of the materials that they are made of, an
nique that—in comparison to traditional ones—minimizes intervention on a work of art on paper is much more struc-
the effects of aqueous swelling, guaranteeing the maintenance tural as it involves the artefact in its entirety. The principal
of the codicological aspects of the artefact and which takes preservation issues that this type of work has for cleaning
into account that, in this type of work, paper not only plays are ascribable to the high hygroscopicity of paper which, as
the role of support for graphical media but is an integral part well as being one of the most important characteristics of
of the image itself. The mechanism of exchange that is estab- this material, is also responsible for the change in many of its
lished between the paper and the gel during treatment allows properties. For example, the interactions that are established
the effective removal not only of surface deposits but also of a between the surface of the works and the airborne particu-
part of the substances that are present within the paper that are late matter (PM) that is deposited on them over time, can be
responsible for its acid degradation. The effectiveness of this caused by various factors such as the nature and dimensions
technique in terms of cleaning (which is attested by the varia- of the particulate matter, the physical forces (Coulomb’s law,
tions in pH measured on treated works) can be equated to the ionic and weak secondary reactions such as hydrogen bonds
effectiveness of the traditional system of washing with water. and Van der Waals force) which develop to keep the PM on
The technique of rigid aqueous gel has also recently been used the surface and by several characteristics of the paper support.
on other types of more structural interventions, such as the The most influential of these are the chemical structure of
removal of auxiliary supports, the removal of adhesives using the paper support, the varying surface roughness and—above
enzymes and the preservation problems that are inherent to all—the degree of hygroscopicity. For example, in the pres-
modern graphic works, generally characterised by an intrin- ence of relatively high humidity (generally ≥ 65%), water
sic fragility and chemical instability. This paper illustrates the can condense between the airborne particulate matter and
results achieved on original works whose degree of opacity, the surfaces of the artefact, acting like an adhesive between
average pH value and degree of whiteness were measured them. Generally speaking, the more permeable the material
before and after treatment. is to humidity, the more hygroscopical the surface is and the
more easily water can condense on it in a way that holds the
Presented at the Book and Paper Group Session, AIC’s 38th Annual PM deposited there. Likewise, the more hydrophobic the
Meeting, May 11–14, 2010, Milwaukee, Wisconsin. paper, the less water will be able to act as an adhesive after

The Book and Paper Group Annual 29 (2010) 25

26 The Book and Paper Group Annual 29 (2010)

its condensation (Wolbers 2005, 13–20). Paper’s propensity inorganic materials, water—by acting as a highly dielectric
to absorb humidity is also at the heart of a further factor of medium—is also able to partially or completely eliminate the
degradation given that—over time—a consistent part of the aforementioned adhesive forces that fix the insoluble sub-
deposits that are initially present only on the outer layer of stances in the surface. However, the high level of porosity
the work, tend to penetrate into the paper support, transmit- and hygroscopicity that characterise paper, together with the
ted by the molecules of water that the material absorbs in its state of preservation and the morphological characteristics of
continuous attempt to reach hygrometric stability with its the original material, can pose a risk factor in the use of water
atmospheric surroundings. The effects of this phenomenon, (or other solvents) in its free state.
in most cases, consist of processes of chemical degradation
associated with structural and chromatic alterations that pro- traditional surface cleaning techniques
foundly modify the aesthetic aspect of the images (figs. 1–2).
In addition to guaranteeing the maximum level of aesthetic A traditional surface cleaning technique involves treating
legibility of the work, the cleaning intervention must in these the surface of the paper support with a hydroalcoholic solution
cases also ensure the chemical stability of the paper sup- applied with swabs. Although it is reduced by the presence of
port. Water, if used as a solvent, represents the ideal method alcohol, the heightened surface tension that characterises water
to satisfy these preservation needs. As well as performing gives the solution a limited washing power and very high sub-
its intrinsic dissolving power for hydrophilic organic and surface penetration, which do not allow us to check how many

Figs. 1–2.  José de Ribera, Poeta, etching, sec. XVII. Simulation on the work of the effects caused by the penetration of the airborne particulate
matter (PM) within the paper support
Iannuccelli and Sotgiu Wet Treatments of Works of Art on Paper with Rigid Gellan Gels 27

of the dissolved substances remain on the surface and how

many—on the other hand—penetrate within the paper sup-
port. The scant opportunity to control the solvent and the high
hydrophilicity of the paper can provoke excessive swelling of
the cellulose fibres and thus cause tensions, deformations and
tide lines that are difficult to remove. An alternative to this
technique is based on the principle of the gelification of the
water with adhesive substances such as ethers of cellulose,
which are able to modify the surface properties of water in
a way that gives the solvent an increase in its washing power
whilst considerably limiting the aforementioned problems.
At low concentrations in water (1–2%) and applied with a
brush, these substances act as a mild surfactant that is able to
generate a foam that facilitates the removal of the unwanted
material (fig. 3). Particulate matter of varying origin, which has
more tenaciously penetrated the fibrous surface interlacing, Fig. 3.  Surface cleaning with aqueous gel of hydroxyethyl methyl
is trapped in the foam generated by the methylcellulose and cellulose
is then removed with hydrophilic cotton swabs. The opera-
tion unavoidably results in a high level of interaction with the
paper support which undergoes excessive physical-mechanical
stress, caused above all by the inevitable swellings produced
by the localised transfer of humidity, with the emergence of
tensions between the treated areas and the surrounding dry
areas. Furthermore, the use of the brush causes an inevitable
mechanical stress that can not always be adequately controlled
due to the development of the foam, which obstructs the
operator’s clear view of the support. With works in a state
of preservation that is already precarious, this technique can
also cause further damage such as the raising and ripping of
fibres which can cause paper delamination with a substantial Fig. 4.  The texture of a handmade sheet of paper pre-1635 (felt side)
decrease in its original thickness and coefficient of absorbency before (A) and after (B) surface cleaning with hydroxyethyl methyl
(fig. 4). A further disadvantage is posed by the difficulty that is cellulose at 2% in water followed by removal with a hydroalcoholic
found, at the end of the treatment, in removing the residues solution. Stereo microscope photograph (40x)
of a gel based on cellulose ethers. After the evaporation of the
solvent, these substances actually form an elastic and adhesive
film that sticks to the outer surface of the single fibres. Thus it
is necessary to systemically conduct washing, with the purpose
of removing tide lines that have developed in the bordering
areas between the treated and untreated areas and in order to
remove the residues of the gelling agent. Traditional washing
with a hydroalcoholic solution (80% water and 20% ethyl alco-
hol) applied with a swab does not always prove effective given
that the dilution of the “adhesive-gelifying agent” can promote Fig. 5.  Comparative table of refraction indices of cellulose, calcium
its further migration into the fibrous interstices of the paper. carbonate and dry carboxymethyl cellulose
In addition to the generic contraindications in terms of pres-
ervation that we have listed so far, this method is particularly cellulose) when dry in fact results as very similar to that of the
dangerous when it is used for the cleaning of graphic works of cellulose: when the ether spreads into the inter-fibre spaces it
art as it permanently alters the original morphology of the sup- gives it greater homogeneity because it seals the empty zones
port. As well as causing a lowering in the original porosity of previously occupied by air, creating ‘continuity’ between one
the support, the irreversible input of adhesive substances used fibre and another (fig. 5). This phenomenon makes the paper
improperly as gelling agents is also responsible for the loss of more compact and uniform from an optical point of view,
opacity of the paper because it lowers the optical discontinu- making it more transparent to light, to the detriment of the
ity. For example, the refractive index of CMC (carboxymethyl legibility of the image.
28 The Book and Paper Group Annual 29 (2010)

the aesthetic role of paper in the context

of graphical works

The irreversible changes that paper undergoes using the

aforementioned interventions jeopardise two of the funda-
mental functions that this material has for graphical works:
the role of support of the work—including its historical value
represented by a series of codicological elements contained
within it—and its role as the material that is essential, togeth-
er with graphical media, for bringing images to life. As can be
Fig. 6.  (A) Felt side of paper support; (B) Wire side of paper support.
seen in the precepts of ancient painting manuals, artists’
Digital video microscope (50x)
choice of materials to be used in their works was made in
relation to the graphic result that they wanted to achieve. The
choice of paper destined to support their graphical work, for
example, did not occur by chance but on the basis of very
precise technical characteristics such as the degree of white-
ness, brightness, compactness and uniformity of the
surface—all particularly accentuated on the felt side of the
sheets compared to the wire side, which is instead character-
ised by a high surface macro-roughness (fig. 6). Generally
speaking, very thick paper was used for drawings with inks or
pigments in solution, and thus the paper was very opaque and
was characterised by a consistent surface sizing. The more
homogenous side (the felt side) was used, as it allowed a better
distribution of the colours applied with the pen or with the
brush. If, on the other hand, the artist chose to use solid col-
ouring substances for his composition, the drawing was done
on the wire side of the paper as the roughness present on this
side facilitated the adhesion of the pigments to the paper sup-
port (Armenini 1988 [1586], 60) (fig. 7). With the advent of
printing between the 15th and 16th centuries, original engrav-
ing—both xylographic and chalcographic—took hold in the
search for the autonomous expressive qualities of every indi-
vidual technique, as engraving had now been released from
its traditional duties of text interpretation and the reproduc-
tion of pictorial works. The spread of this new artistic means
of expression caused further technical diversifications in the
field of the process of papermaking. As concerns engraving,
artists—for example—needed paper that had the best ability
to exalt the intrinsic singularities of the chosen techniques
and the chromatic performance of their compositions. In one
of the first “technical manuals” on the art of printing (Zonca Fig. 7.  Anonymous work from the early 16th-century, Testa di
1607, 77–78), thin paper is recommended for etchings, whilst donna. Natural pietra rossa on white paper
for burin engravings—characterised by very deep cuts—very
thick supports were recommended. For example, Albrecht and degree of whiteness that only paper made from raw mate-
Dürer used paper with different characteristics for his works. rials of excellent quality and rich in loading substances had.
According to studies carried out by Joseph Meder (Meder Thus the paper had to be obtained from a sufficiently refined
1971), the German artist used paper with the watermark of pulp that made it more uniform and compact, and which was
the Bull’s Head or the High Crown for his works commis- therefore better able to reflect the light in order to exalt the
sioned by the most prestigious of patricians (fig. 8), whilst in luminosity of the lighter tones achieved exclusively by
etchings by Rembrandt, paper with the Giullare (jester) water- exploiting the whiteness of the support. A good level of refin-
mark is recurring (Ash-Fletcher 1998) and present in many ing of the raw material was also essential in order for the
variations. The first essential characteristic was the brightness paper to have a degree of plasticity that was sufficient to
Iannuccelli and Sotgiu Wet Treatments of Works of Art on Paper with Rigid Gellan Gels 29

works, the paper underwent heavy pressure of the ‘full’ zones

of the wooden matrices, thus giving it a structural deforma-
tion in the opposite direction to that of chalcographic works
and visible both on the recto and on the verso (fig. 9). The level
of refining however had to not be so forced as to totally uni-
form the dimensions of the fibres dispersed in water. This
phenomenon would have increased the transparency of the
support, compromising another important optical character-
istic required by the artists: the ability to sufficiently contrast
the graphical media on the recto, preventing the unwanted
phenomenon of visibility on the verso. An excessively refined
pulp would also have caused an increase in the points of opti-
cal contact between the cellulose fibres, which would result
in a material that was structurally more compact and homog-
enous but at the same time more transparent to light. Similarly
to what already occurred for drawings, paper used for original
engraving also fully took part in defining the chiaroscuro of the
Fig. 8.  (A) Albrecht Dürer, The Holy Family with two angels in a
vaulted hall (1503–1504), burin engraving; (B) High crown water-
image in terms of light or maximum luminosity (de Denaro
mark, Meder 20 1994, 104–112). In order to demonstrate this, we can refer to a
small but symptomatic variant introduced by artists in works
produced after the 16th century, relating to the placing of the
receive the printing marks: the permanent structural modifi- artist’s signature on the work. On drawings, this is no longer
cation caused by the pressing of the matrices on the paper present on the surface of the paper involved by the image but
which gives the final image an unmistakeable material aspect. is placed in very marginal areas of the sheets (just as happened
The paper was thus dampened before proceeding with the on paintings) or removed. In engravings, monograms or dates,
printing in order to increase its ductility and also to promote which were abbreviated according to the circumstances,
the absorption of the ink. This guaranteed the distinctness appeared within the engraved image in rocks or hanging from
and the legibility of the individual graphic signs which, trans- trees like ex-voti. In line with what was stated by Erwin
ferred onto the support, took on typical and clearly identifiable Panofsky about Albrecht Dürer’s work, there is thus the con-
conformations, according to the technique adopted by the jecture that “the artist urged the spectator to interpret the paper
artist (Griselini 1770, 22). In the case of chalcographical not only as the material sheet on which the characters could be
engravings, thin surface rises were obtained in line with the printed as if they were printed on the pages of a book, but as an
grooves of the metallic matrix in which the paper penetrated; imaginary plane of projection through which the pictorial
the surface layers of the paper therefore absorbed a more or space and its contents are seen” (Panofsky 1979, 111). During
less significant quantity of the ink that was deposited on it, the 16th century, the stylistic evolution of engraving tech-
creating the so-called ‘chalcographic relief ’, identifiable on niques, increasingly prone to emulating the effects of
the recto of the work and, in the case of more significant contemporary painting, radically transformed the traditional
stretches, even visible on the verso. In the case of xylographic link between the image and the paper support, giving the latter

Fig. 9.  (A) Salvator Rosa, Soldato, etching (sec. XVII), close-up of the chalcographic cut with a microscope (15x); Jacopo de’ Barbari, Venetie M.D.,
woodcut printed on six sheets (1500). Close-up of the printing ink marks on the recto (B) and on the verso of the woodcut (C)
30 The Book and Paper Group Annual 29 (2010)

the further function of ‘colour’. With the camaïeu and xylo-

graphical chiaroscuro, together with the varied range of grey
tones induced by the peintre-graveur in their chalcographic
engravings, the graphical developments covered almost all of
the surface of the supports with the intention of using paper
exclusively as a colour, using its white colour for the definition
of highlighting (Ficacci 2006, 45–49) which, in drawings, was
however produced with the positioning of pigmented layers
on top of each other (figs. 10–11). Before carrying out surface
cleaning, it is therefore necessary to carefully assess the level of
interaction that traditional techniques currently used can cause
on this type of work, even when they are carried out profes-
sionally. The uncontrolled introduction of sources of humidity
or additional substances that is seen in current methods can in
fact alter the original characteristics we have mentioned, relat-
ing both to the surface aspect and to the structural conformation
of the paper. These are aspects that, for the aforementioned
reasons, represent an undeniable priority. Although it is not
possible to prevent the material from coming into contact with
sources of humidity (above all when it undergoes a conserva-
tion intervention), it is nevertheless necessary to optimise the
use of water, minimising its impact on the paper. Thus experi-
mentation was begun on techniques that are alternatives to the
Fig. 10.  Ugo da Carpi, Diogenes, a woodcut after Parmigianino
ones described in this paper so far, aimed at the use of rigid
(1526–27), chiaroscuro woodcut on paper
aqueous gels, which have been successfully tested in other
conservation sectors (Anzani et alii 2007).

rigid aqueous gels

Rigid aqueous gels or hydrogels, widely used and tested

in the cleaning of paintings following the work of Richard
Wolbers, are formed of long polymeric chains dispersed in
water. Given the hydrophilic nature and the particular type of
interaction with water, these are commonly defined as hydro-
colloids or substances that—in certain conditions—take on
specific structures capable of holding and trapping the mol-
ecules of free water that they are put into. In other words,
they are able to gelify, forming networks that hold water,
reducing its spread and stabilising its presence. Generally
speaking, the sol-gel transition of rigid gels follows the coil
to helix model when hot solutions are cooled at room tem-
perature. Hydrogels can be formed from various natural
composites, such as Agar agar (Campani et alii 2007) and
Gellan, a linear, anionic heteropolysaccharide produced by
a microorganism (Sphingomonas elodea). Its structure is based
on a tetrasaccharide repeating unit composed of (1-3)-β-D-
glucose, (1-4)-β-D-glucuronic acid, (1-4)-β-D-glucose,
and(1-4)-α-L-rhamnose as the backbone. Gellan gel in native
form is esterified with L-glycerate and with acetate at C-2 and
C-6 (approx. 50%) positions of the (1-3)-linked D-glucose,
respectively. Gellan gel forms different types of gels depend-
Fig. 11.  Raffaello Sanzio. Madonna, Bambino, Santa Elisabetta e ing on acyl contents (Bajaj et alii 2007, 341–345) (fig. 12).
san Giovannino (1507). Pen, watercolour inks and highlighting with The gelation process is generally considered to involve two
white lead
Iannuccelli and Sotgiu Wet Treatments of Works of Art on Paper with Rigid Gellan Gels 31

Fig. 12.  Primary structure of deacetylated Gellan gel

Fig. 13.  Gellan gel coil-helix transition scheme. The stabilisation of

the gel is caused by the presence of Ca++ ions. Image taken from M.
Caggioni, P. T. Spicer, D. L. Blair, Rheology and microrheology of a
microstructured fluid: The gellan gum case, in: “Journal of Rheol-
ogy”, 51–5 (2007) pp. 851–865

separate thermo-reversible steps. Molecules of Gellan gel are Fig. 14.  José de Ribera, Poeta, etching (sec. XVII). Top, a close-up of
in a disordered coil (single chain) upon heating in aqueous the work before treatment. Bottom, a sample of surface cleaning of the
work with Gellan at 3% on the left and Agar agar at 3% on the right
solutions. The molecules transform into an ordered double
helical conformation upon subsequent cooling, followed by
associations between the helices through weak interactions,
such as hydrogen bonds and Van der Waals forces (fig. 13). The
deacylated type forms hard and brittle gels in the presence of
cations (especially Ca++) that are able to promote and stabilise
the ordered ‘‘crystalline-like’’ structure of the gel at the end
of the transition process. The compactness of the molecular
structure, obtainable by hydrating low acyl Gellan gel in aque-
ous solutions containing Ca++ ions thus produces a gel with
a molecular weight equal to 2-3x105 Daltons. The rheological
properties highlight a structure that has a very high degree of
visco-elasticity, and is filmogenic, homogenous, transparent,
and very stable both at high temperatures and at pH varia-
tions (Sworn 2009, 204–227 and Shah-Jani 2009, 48–58). The
gelling agent, tested in terms of effectiveness and biocompat-
ibility (Pszczola 1993, 94–96), has a very widespread use in Fig. 15.  Comparison of percentages of increase in weight in samples
different production areas such as the food industry, as well as of Whatman paper (cat. no. 1001090) immersed in 200 ml of water
and placed in contact with Gellan and Agar agar at increasing concen-
the biomedical and pharmaceutical industries and in the field
trations, for 10 minute and 18 hours respectively. Readings carried
of biological and microbiological research. For the purpose
out with Wunder scales at 26°C and RH equal to 55%
of selecting the product that best responded to the require-
ments of a conservation intervention on paper, a series of
tests were carried out on samples of ancient paper, comparing the application of this technique is the necessity to be able to
Agar agar and Gellan, prepared at different concentrations, modulate the level of water transferred to the paper and to be
and applied to the surface to carry out contact cleaning. As able to monitor both the work and the process of extraction
well as being more transparent than Agar agar (fig. 14), the of the substances to be removed, the subsequent tests were
rigid gel obtained from Gellan was more effective in terms carried out with rigid Gellan gels. Between 2003 and 2008,
of water retention, above all at low concentrations of 1–2% cleaning interventions were carried out with Phytagel Gellan
(fig. 15). Given that one of the fundamental requirements for prepared at different concentrations (Iannuccelli-Sotgiu 2004,
32 The Book and Paper Group Annual 29 (2010)

Fig. 16. ���������������������������������������������������������������������������������������������������������������������������������������������
(A) a saline solution of calcium acetate at low concentrations in deionised water (0.4g/l); (B) addition
���������������������������������������������
of Gellan powder to the saline solu-
tion; (C) the complete hydration of the colloidal dispersion is obtained by heating the compound to boiling point; (D) pouring of the solution in a
basin (E) a gel obtained upon cooling of the hot solution

15–24). Subsequently two other brands of Gellan available on gum is so compact that, if the polymer is placed in water at
the market were tested: Gelrite and Gelzan CM, in addition room temperature, there is no homogenous colloidal disper-
to Phytagel. The aim was to widen the range of Gellans that sion. It is in fact necessary to heat the compound to boiling
can be used. Out of these three, Gelzan CM was chosen as it point to allow the complete hydration of its structure. While
offers greater transparency and better stability at equal con- it is still liquid and runny, it is poured into a specially chosen
centrations, as well as the capacity of gelifying deacidifying basin and allowed to cool. The gelification of the dispersion
aqueous solutions based on calcium propionate (Iannuccelli- happens rapidly once it cools to a temperature of between 40
Sotgiu 2010, 73–94). A valid alternative however is Kelcogel and 30 °C (fig. 16). Gel made in this way can be kept in the
GC-LA, which is equally effective and is much more eco- fridge for 1–2 weeks if it is sealed with waterproof cling film
nomical and produced by the same company (CP Kelco Inc. used for food conservation.
(http://www.cpkelco.com/products-gellan-gum.html).
surface cleaning with rigid gellan gels
rigid gellan gel preparation method
Once the physical-mechanical stability of the inks has
As the mechanism of gelation, in addition to being directly been tested, the application method for printed graphic works
influenced by temperature, is correlated to the presence of consists of directly placing the Gellan film on the recto of the
bivalent cations in water, it is necessary to gelify a saline solu- work, which is lying on a polyester sheet. In order to ensure
tion based on calcium acetate, Ca(CH3COO)2 (0.4g/l) which complete uniformity of contact between the two surfaces, we
provides the Ca++ ions needed to stabilise the structure taken suggest exerting light manual pressure using another polyes-
on by the polymer in the gel phase. The quantity of Gellan ter sheet placed on top of the gel. To contain the evaporation
powder, which is calculated according to the concentration of the water held in the Gellan film and keep the level of
that is desired, is then added to the saline solution. At low humidification constant over the entire surface of the work,
concentrations in water (1–4 %), Gellan gel forms a thermo- the ‘sandwich’ is placed under moderate pressure using a
versible gel in which temperature plays a fundamental role. sheet of crystal which—thanks to its transparency—allows
The three-dimensional network that characterises Gellan us to constantly monitor the treatment (fig. 17). Whilst the
Iannuccelli and Sotgiu Wet Treatments of Works of Art on Paper with Rigid Gellan Gels 33

Fig. 17.  Giacomo Lauro, Basilica S. Petri in Vaticano (1626), burin engraving. (A) before cleaning and (C) after treatment; (B) the clearly
yellowed gel after treatment; (D) scheme of the application of the gel on a burin engraving

gel gradually releases water molecules onto the underlying

paper, the most common degradation elements present on it
are picked up by the Gellan film which, following applica-
tion, visibly yellows (fig. 18). One of the possible causes of
this chromatic alteration is due to the migration of products
of the acid degradation of the paper and thus of water-solu-
ble organic acids (R-COOH) that are transferred into the gel
from the paper support, the final pH value of which is always
higher after contact with the film. The pH values of Gellan
prepared at different concentrations (2, 3 and 4%) were meas-
ured before and after application on paper supports that were
heavily oxidised or acid. The average difference of the pH
values of the gel were equal to one point, whilst the pH value
of the paper was raised by around one and a half points. The Fig. 18.  The process of exchange between a very acidic and oxidised
physical phenomenon that takes place during treatment in fact paper and a Gellan gel at 2%; (A) start of treatment; (B) after 5 min-
consists of a process of exchange between the paper and the utes; (C) after 15 minutes; (D) after 25 minutes. Macro-photographs
gel. In the initial phase, the water tends to spread spontane- taken with a video microscope (15x)
ously in the paper, solubilising acid degradation by-products
of cellulose. Subsequently, the concentrated solution of these the ICPAL Physics Laboratory on works that have undergone
products, present in the inter-fibre spaces of the paper support a simple cleaning treatment with the gel have highlighted
spreads according to the gradient of concentration from the that the intervention caused no significant variations to the
paper to the gel (Lienardy-van Damme 1990, 23–30). Thus original opacity of the supports that were treated, whilst there
the treatment is not only limited to the removal of PM, but was a moderate improvement in the level of brightness and a
most likely it is able to carry out a cleaning action that is simi- reduction in the yellowing measured according to the colour
lar to actual washing with water. Measurements conducted by coordinate system of CIELab (fig. 19). The method described
34 The Book and Paper Group Annual 29 (2010)

herein does not bring about structural or surface modifica- allows the gel to mould itself to the three-dimensional relief
tions to the paper supports as the cleaning intervention occurs of graphic print marks and to the surface texture of the paper
spontaneously following the mere contact of the gel with the (figs. 20–21). Neither of these suffer alterations following
paper, which in fact simply undergoes controlled humidifi- contact with the gel, on which we can observe the impression
cation. The safeguarding of morphological characteristics is of the codicological elements and printing marks. And finally,
further guaranteed by the visco-elasticity of Gellan gel. This after cleaning has taken place, the removal of a compact, non-
adhesive film does not cause substantial presence of residues
of gel on the support as is the case with cellulose ethers. Once
it has been used, the gel can be disposed of as biodegradable
organic waste. Gellan gel, which is in fact stable when it is in
dry powder form, is on the other hand easily biodegradable
in its gelified form, due to its high content of water and due
to the fact that it is essentially impossible to work in sterile
conditions when working on handmade artefacts in normal
working conditions.

selecting the ‘ ideal ’ concentration

The water uptake of the support is inversely proportional

to the concentration of the gel: the greater the quantity of
powdered Gellan gel used—and thus the more tightly retic-
ular structure of the gel—the smaller the quantity of water
Fig. 19.  CIELab color variations measured with tri-stimulus Minolta transferred into the paper in the same time interval. From
CR200 chromo-meter on a burin engraving on paper by Giacomo
results shown in the graph (fig. 22), it can be seen that the
Lauro, Basilica S. Petri in Vaticano (1626)
percentage of increase in weight (P2-P1/P1x100) of samples
treated increases substantially with the decrease of the con-
centration of the biopolymer. Even after an extended contact
period of 18 hours, the quantity of water transferred into the
samples nevertheless results as less than what is absorbed by
a sample immersed in water for ten minutes. In any case, the
‘ideal’ concentration of Gellan gel depends on the degree of
wettability of any single paper to be treated. The degree of
surface porosity of the paper and its level of wettability in fact
depend on the type of fibre that make up the pulp, on the

Fig. 20.  (A) Giacomo Lauro, Basilica S. Petri in Vaticano (1626),

burin engraving on paper. Close-up of chalcographic engraving; (B)
Close-up of the gel at 2% which—following contact with the work—
shows the mirror image of the chalcographic engraving

Fig. 22.  Comparison of percentages of increase in weight in samples

of Whatman paper (no.001090) after contact with Gellan gel at differ-
Fig. 21.  A same piece of paper from
����������������������������������������
1635 before (left) and after treat- ent concentrations (w/gel x%) and after immersion in free water for
ment (right) with Gellan gel at 2% applied for 30 minutes. Images 10 minutes and for 18 hours. Readings taken with Wunder BH-150
taken with Dinolite video microscope (65x) scales (Max 150 g; d: 0,005 g) at 26°C and RH equal to 55%
Iannuccelli and Sotgiu Wet Treatments of Works of Art on Paper with Rigid Gellan Gels 35

extent and type of sizing present, as well as the level of refin-

ing of the cellulose fibres and the state of preservation of the
materials present. Thus it is useful to carry out a simple test of
the degree of wettability before choosing the best concentra-
tion of Gellan to be used and, if necessary, a humidification
treatment in an ultrasonic humidifier chamber can be carried
out if the paper is particularly hydrophobic.

the cleaning treatment on drawings

Conversely to the application method developed for print-

ed works, the cleaning treatment for drawings is carried out
by placing the gel on the verso of the work after verifying the
stability of graphical media to water (fig. 23). As a further
safety precaution, it is necessary to place a piece of Japanese
paper between the gel and the work as an interleaving tissue.
The latter does not interfere in the exchange process that
takes place during the treatment, thanks to its excellent per-
meability, but, at the end of the treatment, it will assist the Fig. 23.  Japanese paper placed on top of the Gellan gel (1%) placed
removal of the item from the gel surface. The technique also on a polyester sheet (A); placement of the work on the Japanese tissue
(B); removal of the work with the aid of Japanese tissue (C); place-
prevents the temporary fixing of any fragments with adhe-
ment of the work on a second gel with the aid of Japanese tissue (D)
sives that could cause a substantial change to the support’s
absorbency of water. Generally speaking, when using an
interleaving tissue, a low concentrated gel (about 1%) will
work more effectively to overcome the presence of an addi-
tional support. In any case, the gel concentration has to be
selected according to paper wettability, which can vary even
in a similar paper. In an attempt to counteract the unavoidable
stresses caused by different hygroscopic behaviour during the
wetting procedure on a series of drawings that showed prob-
lems of this sort, we used two gels at different concentrations
to ensure the uniformity in the imbibition phase, preventing
Fig. 24.  Close-up of the ‘contact angle’ test performed with two
the appearance of risky physical-mechanical tensions between
droplets of water on a 19th-century drawing (C); two Gellan gels
areas showing different hydrophilic levels (fig. 24). The con- prepared at different concentrations (A); both gels placed underneath
tact times depend on the characteristics of the works and the the work (B)
quantities of residues to be removed, taking into account that,
if necessary, applications using clean gel can be carried out
until no more yellowing of the film can be seen. humidification of the paper support. Traditionally, the inter-
vention is conducted via localised humidification with steam,
the removal of auxiliary supports with rigid produced by an ultrasonic generator, or with packs of gelified
gellan gels water. Both removal techniques inevitably result in a high
level of interaction with the work that is subjected to a sub-
During conservation treatments of graphic works, it is not stantial physical-mechanical stress, as all the materials present
uncommon to come across auxiliary supports applied with in it—original paper support, adhesive, strengthening mate-
amylaceous or protein adhesives. In these cases, their pres- rial or integral lining—tend to swell in their interaction with
ence brings about chromatic alternations associated with the water solvent and subsequently shrink in a different way.
structural modifications that—with the varying of thermo- The variations in size that are found in successive cycles of
hygrometric parameters of the conservation area—become swelling-shrinkage bring about structural deformations that are
the cause of deformations, tensions, as well as surface irreversible. The extent of these deformations depend on the
darkening of works to such a point that their use is com- degree of interconnection of the abovementioned constitu-
promised. Whenever the conservation intervention should ent materials, on the force applied during the operation of
require the removal of these and the subsequent removal of the separation of the various paper layers and on the pressure
the adhesives, rigid gels offer an effective technique for the used during the mechanical removal of the adhesive, as well
36 The Book and Paper Group Annual 29 (2010)

as on the inhomogeneous quantities of water transferred onto carried out a test aimed at assessing the extent of the force
the areas that are individually treated. The aim of the use of required to separate the two or more paper supports to be
rigid aqueous gels for the removal of additional material, is separated. Subsequently, the mechanical removal of the adhe-
to keep the level of the humidification of the entire surface sive is carried out: the constant and uniform inflow of water
of the work uniform and constant throughout, avoiding the molecules from the gel under the work and the subsequent
risk of over- or under-dosage of water and the aforementioned decrease in the viscosity of the adhesive, allow the operation
consequences. Conversely to the function it has during the to be carried out quickly without tide lines or mechanical trac-
intervention of surface cleaning, the rigid gel in this case is tions, thus preventing irreversible distortions and any losses of
used exclusively as a reservoir for the constant and controlled cellulose fibres from the original support. However, although
release of molecules of water for the purpose of making all the this technique allows a raised hydration of the adhesive layer,
materials present in the work sufficiently hydrated through- the permanence in the layer of internal friction—which is
out the intervention. As a rule, the removal of additional somewhat high—prevents its complete removal.
supports is carried out immediately after the surface cleaning
intervention is completed, repeating the application of Gellan enzymatic gellan gels
film prepared at a concentration that is suitable for the nature
and quantity of materials that are to be removed. The coeffi- The operation of removing support material and the
cient of the diffusion of the water solvent within the work will subsequent removal of the adhesive can be assisted by the
in fact be substantially influenced by the percentage of water application of enzymes (hydrolases) that—as is well known—­
present in the gel, on the degree of porosity and wettability act as catalysts for hydrolysis reaction of specific substrates.
of the paper, on the presence of additional elements (original The enzymatic gels prepared over recent years and the geli-
sizing) and on the quantity and state of preservation of the fied enzymatic solutions with gelling agents of different types
adhesive present. In order to minimise mechanical tractions have several limits. Ready-to-use enzymatic packs (Schwarz
that—even if they are mild—could be caused on the original et alii 2003, 98–108) only act on amylaceous adhesives, and
surface, the Gellan film is in this case also applied to the recto other different types of gelling agents, like cellulose ethers,
of the work—placing a sheet of Japanese paper between the polyacrylic acid neutralised with sodium hydroxide and
paper and the gel which will then serve to lift up the work natural polysaccharide gums, require a subsequent phase of
once the operation is completed (fig. 25). The intervention is mechanical removal from the paper surface. The need to
however conducted on the verso, once the ‘sandwich’ has been remove residues of gelling agents can be eliminated by using
turned over using two sheets of Plexiglas and after having a rigid gel used as a carrier for enzymatic solutions (Campani
et alii cit, 16). The preparation of the enzymatic Gellan gel is
carried out only once gelification has taken place as the pre-
liminary phase of the hydration of the polymer takes place
around 90–100°C, a temperature that would denature the
protein molecules of the enzymes. The milligrams or the
grams of enzyme (Cremonesi 1999, pp. 46–48), calculated in
line with the total quantity of saline buffer solution (0.4g/l
calcium acetate and Trizma base or other buffers) which is
transformed into gel, are hydrated in a few millilitres of the
same solution. In this way, we obtain a concentrated enzy-
matic solution in a homogenous medium (water) which is
then deposited with a micropipette and distributed uniformly
over the surface of the gel using a synthetic brush. As a rough
guide, for a Gellan film at 3% made starting with 800g of pH
7 aqueous buffer solution and the surface of which is 20 x 30
cm, 5–6 ml of concentrated enzymatic solution are sufficient.
The intervention can be carried out only when the solu-
tion has been completely absorbed by the rigid gel. Initially
distributed only on the surface, the enzyme molecules tend to
spread throughout the microporous structure that character-
Fig. 25.  Positioning of Japanese paper and of the gel on the recto ises Gellan film via capillary action in the space of just a few
of a print (A); removal of the auxiliary support and of any previous minutes (fig. 26). The gel is placed directly in contact with the
conservation interventions, working on the verso and using the gel as adhesive layer to be removed for a period of time that varies
a humidifying support (B); mechanical removal of the adhesive (C) according to the thickness of the deposit, its nature and its
Iannuccelli and Sotgiu Wet Treatments of Works of Art on Paper with Rigid Gellan Gels 37

Fig. 26.  Distribution of the enzymatic solution and absorption by the gel (A-B-C); application of the gel (D) and the result of cleaning on the
reverse of a large-scale work (E)

state of preservation. At the end of the treatment, the by now and tert butyl aminoborane as a reducing agent. The latter
depolymerised adhesive can be easily removed using swabs can be used only if the graphical media that are present do
without any sort of mechanical traction. The residues of the not contain copper compounds. Again in this case, the wide
substances present on the support of the work—enzymes and range of stability of the pH of Gellan allows the use of deacid-
traces of depolymerised adhesive—can be easily removed by ifying aqueous solutions and reduction-oxidation agents in
applying another aqueous gel, or, if the state of preservation gel phase, which can be used separately, at the same time or
and the graphical media allow it, by washing on a sloping sur- in subsequent interventions. The reduction-oxidation gel is
face (Kirchner 2004, 124–135). prepared starting with the calcium acetate solution (0.4g/l) to
which the necessary Gellan powder is added, using however
chemical stabilisation of paper supports the forethought of inserting the tert butyl aminoborane (7g/l)
with gellan immediately after the dispersion has ended the heating cycle
in a microwave, an operation that requires the use of per-
Sometimes the precarious state of preservation of work sonal protective equipment and which is always conducted
necessitates an intervention for chemical stabilisation which, under a fume hood (fig. 27). The tert butyl aminoborane
as a rule, involves the carrying out of a deacidification and dissolves immediately and so it is possible to pour the com-
reduction-oxidation treatment. The products studied and pound into a basin—as is common practice—and wait for
used at ICPAL are calcium propionate as a deacidifying agent the sol-gel transition to take place once it has cooled. Even in
38 The Book and Paper Group Annual 29 (2010)

case of a group of drawings from the end of the 19th cen-

tury treated by positioning different gels at the same time (fig.
28). At the end of the intervention, the duration of which
was generally two hours, a rinsing treatment with a simple
aqueous gel was carried out in order to remove any residues
of tert butyl aminoborane. Due to the presence of tert butyl
aminoborane, the reduction-oxidation gel must be disposed
of as hazardous waste. When it is necessary to carry out a
deacidification treatment, a rigid deacidifying gel is prepared,
starting—as always—with a saline solution based on calci-
um acetate (0.4g/l) to which calcium propionate (3.5-5g/l) is
added, followed by the necessary Gellan, and the total com-
pound is then heated up in the microwave. The deacidifying
gel is slightly opaque but maintains its filmogenic and elas-
Fig. 27.  The tert butyl aminoborane (7g/l) is added under the fume tic quality (fig. 29). The treatment takes around two hours.
hood, when the hydration process of the Gellan is complete, using The ICPAL Physics Laboratory has tested the effectiveness
personal protective equipment of the gelified aqueous solutions of calcium propionate and
tert butyl aminoborane by conducting, amongst other things,
measurements of pH and alkaline reserve on different paper
samples from the 17th century, the 19th century and on
samples of Whatman and Fabria paper. The results of these
studies are in the publication phase.

conclusions

The aim of the studies on Gellan gel use conducted

between 2003–2004 by ICPAL was to develop an alternative
technique that could remove substances that cause degrada-
Fig. 28.  An example of localised oxidation-reducing treatment: (A) tion on works of art on paper without causing morphological
a rigid oxidation-reducing gel and a simple rigid aqueous gel made changes to the support. The gradual and controlled release of
according to a template; (B) positioning of the two gels under the water molecules from the gel to the paper, its capacity to absorb
drawing at the same time
hydrosoluble substances of degradation, the ease of applica-
tion and removal, and its visco-elasticity make it particularly
suitable for use in this field, ensuring the maintenance of the
overall function—both structural and aesthetic—of this type
of artefact. In experiments carried out in recent years, the
versatility of this material in other phases of conservation has
emerged, including the removal of auxiliary supports, its use
as a carrier for enzymatic solutions and for deacidification and
reduction-oxidation solutions. The results achieved in terms
of the variations of optical properties, as well as in terms of the
pH and alkaline reserve, are extremely encouraging. Future
developments of the research are being directed at identify-
Fig. 29.  The deacidifying gel positioned under the two drawings, ing the substances that the gel is able to remove from paper
using a sheet of Japanese paper as an interleaving tissue supports using Size-Exclusion Chromatography (SEC) and the
verification of the effects that it can produce on different types
the presence of tert butyl aminoborane, the gel maintains its of paper through mechanical testing. These studies are currently in
visco-elastic properties and its transparency. Application takes progress on treated paper samples, as well as on untreated samples, as
place by contact, using methods that vary according to the part of the research project ‘Gel rigidi polisaccaridici per il tratta-
graphic techniques present, as described previously for the mento di pulitura di materiale cartaceo’ (http://www .icpal.
cleaning intervention. The possibility to gelify deacidifying beniculturali.it/ progetti_ricerca.html). Partners involved in the
and/or reduction-oxidation solutions allows the carrying out project include the ICPAL Physics Laboratory and the ICPAL
of interventions also during chemical stabilisation, as in the Laboratory for the conservation of library materials (Istituto
Iannuccelli and Sotgiu Wet Treatments of Works of Art on Paper with Rigid Gellan Gels 39

centrale per il restauro e la conservazione del patrimonio Campani, E. et alii. 2007. L’uso di Agarosio e Agar per la pre-
archivistico e librario), the OPD (Opificio delle pietre dure— parazione di ‘Gel Rigidi’, Quaderni, 6, Cesmar 7, Padova,
Florence), Cesmar7 (Padua) and the University of Parma. Il Prato.
Bajaj, I. B. et alii. 2007. Gellan gum: fermentative production,
acknowledgments downstream processing and application. In Food Technology
and Biotechnology, 45, 4: 341–354. (http://www.ftb.com
We would like to sincerely thank all the partners involved .hr/45-341.pdf)
in the research project ‘Gel rigidi polisaccaridici per il tratta- Sworn, G. 2009. Gellan gum. In Handbook of hydrocolloids, 2nd ed.
mento di pulitura di materiale cartaceo’, especially Dr. Paolo By G. O. Phillips and P. A. Williams, Woodhead Publishing
Cremonesi, the scientific director at Cesmar7, and our col- Limited, Oxford Cambridge New Delhi. 204–227.
leagues at the ICPAL Physics Laboratory, Luciano Residori, Shah, D. P. - Jani, G. K. 2009. Modification and characteriza-
Daniele Ruggiero, Lorena Botti, Aldo Corazza, Matteo tion of Gellan gum. In Pharmaceutical Technology, 33, 7: 48–58.
Placido, and the freelance conservator Lorena Tireni, for their Pszczola, D. E. 1993. Gellan gum wins IFT’s Food Technology
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