Professional Documents
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Keywords: paper conservation, gellan Gellan gum and its application in wet conservation
gum, SEC, GC-MS, mechanical testing,
treatments
colourimetric analysis, pH, alkaline
reserve
Gellan gum is a high-molecular-weight polysaccharide produced by
Pseudomonas elodea. It is used as a gelling agent in food, biomedicine and the
Abstract pharmaceutical industry. The polymer is a linear anionic heteropolysaccharide
Wet treatments of works of graphic art should made of β-D-Glucose, α-L-Rhamnose and β-D Glucuronic acid repeating
be chosen by carefully assessing the extent units as the main monosaccharides. Gellan gum forms different types
of modifications caused on the original ma-
of gels depending on acyl contents (Figure 1) (Bajaj et al. 2007). The
terials. In order to optimise the presence of
water and minimise the impact on the paper deacylated type, selected for conservation purposes, forms hard and brittle
support, a new method was developed that gels in the presence of cations (especially Ca2+). The rheological properties
can be used for cleaning purposes, linings highlight a structure that has a very high degree of visco-elasticity and
removal, deacidification with calcium propi-
is film-forming, homogeneous, transparent and very stable both to high
onate Ca(C2H5COO)2 and reductive bleaching
with borane tert-butylamine (CH3)3CNH2 · BH3. temperatures and to pH variations (Sworn 2009). The sol-gel transition
Chemical and physical analyses (using gas process takes place by cooling a water dispersion of gellan gum heated to
chromatography coupled to mass spectrom- 100°C to 30-40°C until it becomes a solution. As well as being directly
etry, size-exclusion chromatography, colou-
influenced by temperature, the mechanism of gel formation is related to
rimetric analyses) were carried out to under-
stand which materials the gel can extract the presence of mono or bivalent cations in water; if necessary, a salt like
during the cleaning treatment and to verify calcium acetate Ca(CH3COO)2 or calcium bicarbonate Ca(HCO3)2 can be
colour modifications. In order to compare added to water. Studies are currently under way in order to select the best
the effectiveness of chemical stabilisation
buffer solution to stabilise the gel’s pH and achieve neutrality.
treatments conducted by immersion or by
gel contact, pH and alkaline reserve analyses
were performed. To ascertain whether the
use of rigid gels such as gellan gum and Agar
could result in increased fragility of the treat-
ed paper, mechanical testing was conducted
on treated and untreated paper samples.
Résumé
Figure 1
Les traitements humides des œuvres d’art
Primary structure of deacetylated gellan gum
graphique doivent être choisis en évaluant
avec précaution l’étendue des altérations
qui affectent les matériaux d’origine. Afin Cleaning, deacidification and reductive bleaching
d’optimiser la quantité d’eau employée et treatments
de réduire son impact sur le support en pa-
pier, une nouvelle méthode a été conçue, As a cleaning treatment, the gel can be applied directly to the recto of
utilisable en cas de nettoyage, de retrait a pre-wetted print work (Figure 2a) or by contact with the verso of a
des rentoilages, de désacidification avec du
drawing (Figure 2b) (Iannuccelli et al. 2010). Gellan gradually releases
propionate de calcium Ca(C2H5COO)2 et de
blanchiment réducteur avec du tert-butyla- water molecules into the paper, while the most common degradation agents
mine- borane (CH3)3CNH2 · BH3. Des analyses present on the paper are picked up by it.
1
Evaluation of cleaning and chemical
stabilization of paper treated
GRAPHIC DOCUMENTS with a rigid hydrogel of gellan gum
by means of chemical
and physical analyses
Resumen
Los tratamientos en húmedo de obras de arte
gráfico deberían elegirse cuidadosamente,
valorando el alcance de las modificaciones
causadas en los materiales originales. Para
optimizar la presencia de agua y minimizar el
impacto sobre el soporte de papel, se desa-
rrolló un nuevo método que se puede utilizar
para limpiar, eliminar revestimientos, desaci-
dificar con propionato de calcio, Ca(C2H5COO)2,
y realizar un blanqueamiento reductor con
terc-butilamina borano (CH3)3CNH2 · BH3. Se
realizaron análisis químicos y físicos (usando
cromatografía de gas acoplada a espectro-
metría de masas, cromatografía de exclusión
por tamaños y análisis colorimétrico) para
comprender qué materiales puede extraer
el gel durante el tratamiento de limpieza, y
para verificar modificaciones en el color. Con
el objetivo de comparar la efectividad de los
tratamientos de estabilización química por
inmersión o por contacto con el gel, se reali-
zaron análisis de pH y de reserva alcalina. Para
determinar si el uso de geles rígidos, como la Figure 2
goma gellan y el Agar, podrían causar una (a) Scheme of gel application on the recto of a print work; (b) scheme of gel application underneath a
mayor fragilidad en el papel tratado, se reali- drawing, using an interleaving tissue between the two surfaces; (c–d) Burin engraving Basilica S. Petri in
zó un ensayo mecánico en muestras de papel Vaticano (1626) by Giacomo Lauro before and after a cleaning treatment; (e) the clearly yellowed gel after
tratado y sin tratar. treatment; (f–g) close-up of the marks from the engraving printing ink and of the grooves created by them
over the gel after treatment
The yellowing of the gel after treatment is due to the migration of water-
soluble chromogenic components, likely including organic acids (R-COOH)
transferred into the gel from the paper support (Figures 2 c–e). Gellan performs
a cleaning process similar to washing, optimising the solvent power of water
which is introduced into the support very gradually, constantly and uniformly.
Percentages of increase in weight, measured on samples of Whatman paper
after gellan contact, show that the water uptake is inversely proportional
to gel concentration. Furthermore, the quantity of water transferred into
the sample treated with 1% gellan for 18 hours was lower than the amount
absorbed by the sample immersed in water for just 10 minutes (Table 1).
2
Evaluation of cleaning and chemical
stabilization of paper treated
GRAPHIC DOCUMENTS with a rigid hydrogel of gellan gum
by means of chemical
and physical analyses
Gellan can also gelify aqueous solutions containing both calcium propionate
and Borane tert-butylamine for a simultaneous treatment: in this case, a
deacidifying gel is prepared as described above (0.4 g/l calcium acetate,
3.5-5 g/l calcium proprionate) with the gellan required (20 g/l). Borane
tert-butylamine must be added at the end of the heating cycle using the
safety measures mentioned above.
A rigid gel of 2% gellan gum (Kelcogel® CG-LA) was applied for 30 minutes
on an ancient paper (17th century) to carry out cleaning treatment. Then
the rigid gel was put into a Buchner filter on a Buchner flask and it was
cleaned with a 0.15 M sodium chloride solution in distilled water under
vacuum conditions in order to release paper compounds trapped in the
gel after the treatment.
3
Evaluation of cleaning and chemical
stabilization of paper treated
GRAPHIC DOCUMENTS with a rigid hydrogel of gellan gum
by means of chemical
and physical analyses
Figure 3
Chromatogram of gellan gum (Kelcogel CG-LA) obtained by GC-MS analysis. The main monosaccharides
detected are rhamnose (Rha), glucose (Glu), glucuronic acid (AcGlcU), mannose (Man) and galactose (Gal).
Sorbitol is the Internal Standard
The sample (gellan gum in powder, 17th-century paper and the water extracted
from gellan gum after the cleaning treatment), after acid hydrolysis, is first
mercaptalated with a mixture of ethanthiol and trifluoracetic acid (2:1) and
then derivatized in the same schlenk tube. The obtained diethyldithioacetal
trimethylsilylates are analysed using gas chromatography-mass spectrometry
(Pitthard et al. 2001). Figure 3 represents the chromatogram of gellan
gum. These preliminary results show the presence of different kinds of
monosaccharides: rhamnose, glucose and glucuronic acid as the main
sugars; mannose and galactose in trace. Sorbitol 0.01M in water solution
was used as the Internal Standard. Figure 4 shows the main monosaccharides
detected in the paper sample (chromatogram a), namely: glucose, rhamnose,
mannose, xylose, galactose and glucuronic acid. The presence of different
sugars from glucose, such as the pentose sugar xylose, could derive from
hemicellulose (low molecular weight polysaccharides linked to cellulose
with hydrogen bonds) (Campanella et al. 2007). In the chromatogram
of the water extract from the gel used in the cleaning treatment (b), the
4
Evaluation of cleaning and chemical
stabilization of paper treated
GRAPHIC DOCUMENTS with a rigid hydrogel of gellan gum
by means of chemical
and physical analyses
Figure 4
Chromatogram (a): ancient paper (17th century); chromatogram (b): water extract of rigid gel (gellan gum)
obtained by GC-MS analysis. The main monosaccharides detected in the paper sample (chromatogram a)
are: glucose (Glu), rhamnose (Rha), mannose (Man), xylose (Xyl), galactose (Gal), glucuronic acid (AcGlcU).
The main monosaccharides detected in gel extract (chromatogram b) are: glucose (Glu), rhamnose (Rha),
mannose (Man), xylose (Xyl), galactose (Gal). Sorbitol is the Internal Standard
The samples (3 × 3 cm) obtained from the same paper, before and after
treatment, were left in a flask containing 90 ml of a 0.15 M sodium chloride
solution in distilled water for four hours. The samples were then removed and
the solution concentrated on a Rotavapor. 2 ml of 0.15 M sodium chloride
solution in distilled water were added and after filtration the solution was
analyzed by size-exclusion chromatography in order to obtain information
about average the molecular weights of the hydrosoluble polysaccharide
fractions. For size-exclusion chromatography analysis, a column with a
diameter of 9 mm and a height of 25 cm was used. The stationary phase
used Sephacryl 400 HR -S 400HR-750 ML: Poly([allyl dextran]-co-N,N’-
methylenebisacrylamide), 25-75 μm in Ethanol 20% (Sigma Aldrich). The
mobile phase used NaCl (0.15 M) electrolyte solution. Standards used
were dextrans (Mw: 1400000, 410000, 150000, 50000, 12000).
5
Evaluation of cleaning and chemical
stabilization of paper treated
GRAPHIC DOCUMENTS with a rigid hydrogel of gellan gum
by means of chemical
and physical analyses
The collected fractions were treated with 95% sulfuric acid and 80%
phenol and then analysed by a double beam spectrophotometer UV-VIS
(Dubois et al. 1956).
Figure 5
Chromatogram of polysaccharide fractions of ancient paper before (NT-600) and after gel treatment (CRT-
600 GLL) obtained by SEC analysis
Figure 6
Calibration line obtained using dextrans of known molecular weight as standard
6
Evaluation of cleaning and chemical
stabilization of paper treated
GRAPHIC DOCUMENTS with a rigid hydrogel of gellan gum
by means of chemical
and physical analyses
Table 2
Elution peaks with their volume elution, molecular weight and DP of polysaccharide fraction from paper
samples
Mechanical testing
7
Evaluation of cleaning and chemical
stabilization of paper treated
GRAPHIC DOCUMENTS with a rigid hydrogel of gellan gum
by means of chemical
and physical analyses
• machine made paper dating from 1926 (50 g/m2, mechanical pulp,
pH 4,59, highly oxidized): Sample PB 1926.
• washing
All three papers were submitted to three treatments for 1 hour, either by
using the immersion method or by applying the gel. The results for pH
and alkaline reserve measurements are resumed in Table 3. Deacidification
treatment with calcium propionate through 2% gellan gum provides an
increase in pH values comparable to that achieved by immersion and,
furthermore, leaves an appreciable larger amount of alkaline reserve.2 The
contextual deacidification and reductive-bleaching treatment (calcium
propionate and Borane tert-butylamine) has practically the same effect.
The results for colourimetric analysis are resumed in Table 4. Also in
this case, the values of ΔE (but also ΔL, Δa and Δb) indicate that color
variations after the three treatments, performed by immersion and by
gel contact, are comparable despite the fact that the quantity of water
8
Evaluation of cleaning and chemical
stabilization of paper treated
GRAPHIC DOCUMENTS with a rigid hydrogel of gellan gum
by means of chemical
and physical analyses
Table 3
pH and alkaline reserve measurements taken before and after treatments (values are the average of five
measurements)
Table 4
Colourimetric variations (values are the average of seven measurements for every single sample)
9
Evaluation of cleaning and chemical
stabilization of paper treated
GRAPHIC DOCUMENTS with a rigid hydrogel of gellan gum
by means of chemical
and physical analyses
Conclusions
The aim of the studies conducted since 2003/2004 by the ICPAL on the
use of gellan gum was to develop an alternative method for the cleaning
of works of graphic art, limiting the morphological changes to works on
paper. The results of gas chromatography-mass spectrometry analyses of
ancient paper (17th century) and of gel used for cleaning treatment show
the presence of different kinds of hydro-soluble sugars which may be
attributed to the presence of cellobiose and hemicellulose.
Notes
1
The authors would like to thank Marion F. Mecklenburg, Senior Research Scientist at the
Museum Conservation Institute, Smithsonian Institution, in Washington, D.C., and Laura
Fuster, Associate Professor at the Universidad Politécnica de Valencia, for conducting
mechanical testing.
2
Common methods for immersion such as CaCO3 0,006N and Ca(OH)2 0,02N provide
values of 0.15% and 0.75% respectively.
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Evaluation of cleaning and chemical
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GRAPHIC DOCUMENTS with a rigid hydrogel of gellan gum
by means of chemical
and physical analyses
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