Appl. Phys.
A 92, 217–221 (2008)
DOI: 10.1007/s00339-008-4485-3
r. belliu Excimer laser irradiation at 248 nm of wooden
l. toniutti
a. miotello archaeological objects and polymeric
p. mosaner
d. avi
consolidants used in conservation: a study
of cone formation and optimum cleaning
parameters
Department of Physics, University of Trento, 38100 Povo, Italy
Received: 13 October 2007/Accepted: 15 January 2008
Published online: 4 April 2008 • © Springer-Verlag 2008
ABSTRACT Samples of a prehistoric consolidated vegetable
basketry, coming from an important pile building in the North-
East of Italy (Fiavé Carrera, Trento), had been irradiated with
excimer laser pulses to remove the consolidant layer and re-
store the artifact. Some problems, related to the nature of the
consolidant resin, were found in the preliminary laser cleaning
process. The two main obstacles were related to the unknown
composition of the polymeric resin and to the irregular surface
morphology of the archaeological find. We observed that large
numbers of laser pulses, for selected laser parameters, strongly
modify the resin surface morphology with formation of a large
number of cones. After cone formation, the surface was so irreg-
ular that it was almost impossible to complete the laser cleaning
procedure. To find a solution to the problem, we here try to
understand the mechanisms of cone formation in the present
polymeric material. Scanning electron microscopy (SEM) and
Fourier transformation infrared spectroscopy (FTIR) have been
used to study surface morphology and chemical modification
after selected irradiation processes. To understand the influence
of laser irradiation on surface modifications and to establish
a cleaning procedure for this specific application, investigations
have been carried out separately on models of resin consolidants
and wood (both dried and buried wood sample). The consoli-
dants were commercial resins, typically used in archaeological
conservation (Plexisol and Paraloid), deposited on a silicon sub-
strate. Silicon was used because it is an appropriate substrate in
FT-IR analysis. Finally, we chose wood because of its wide use
in prehistoric artefact (Viburnum lantana).
PACS 81.65.Cf; 82.50.Hp; 87.64.Ee; 87.64.km
1 Introduction
In recent years, promising results have been ob-
tained with laser cleaning techniques in conservation of art-
works. Initially, laser beams have been utilized for cleaning of
stone sculptures and paintings, but subsequently other classes
of artworks have been treated, also because in museum col-
lections several kinds of materials may be encountered such
as plant fibers and wood, animal and insect tissue, minerals,
u Fax: +39-0461-881696, E-mail: belli@science.unitn.it
Applied Physics A
Materials Science & Processing
fossils, bones, animal, and human mummies leather and pa-
per [1]. With wood samples, some attempts have been made
using Nd:YAG laser on wooden panel [2], wooden ceiling [3],
totem pole [4], and architectural structures [5]; encouraging
results were obtained. Even if some of these works tested
several wavelengths, such as 532, 355 and 266 nm, with the
Nd:YAG the main wavelength used for the wood laser clean-
ing was 1064 nm.
Laser cleaning of a prehistoric consolidated wood bas-
ketry, coming from an important pile building in the North-
East of Italy (Fiavé Carera, Trento) was tested [6] and some
problems emerged. The archaeological sample under study
is highly complicated: it is old (16th–14th century BC),
fragile, and partially carbonized. In addition, no informa-
tion is available on the consolidation process, and the weave
of branches lead to a very irregular surface geometry. Be-
cause of these factors, previous effects produced by laser
irradiation remained unclarified. In particular, the forma-
tion of structures with a conical shape following a large
number of pulses at low fluences requires further inves-
tigation. In the present work, to make progress with the
cleaning procedure of the original sample [6], we performed
a systematic study of laser irradiation of modern wood
and consolidant materials to try to establish the relevant
mechanisms responsible for cone formation in our previous
experiment.
2 Experimental
Excimer laser irradiation of modern samples of
dried wood, carbonized wood, and consolidant resins has been
performed. The laser source was a KrF excimer laser with
a wavelength of 248 nm and pulse duration of 20 ns. The rep-
etition rate was fixed at 10 Hz. On the basis of previous ex-
perience of laser irradiation on organic materials [8], a wide
range of irradiation parameters (pulse energy density in the
range of 40 – 1400 mJ/cm2 and number of pulses between 10
and 10 000) was investigated. Morphological and chemical
surface modifications have been analyzed with scanning elec-
tron microscopy (SEM) and Fourier transformation infrared
spectroscopy (FTIR).
The basic wood used in the prehistoric basketry is the
Viburnum lantana: we used the same kind of wood to pre-
pare samples for our investigation [6]. Pieces (3 – 4 mm diam-
218 Applied Physics A – Materials Science & Processing

eter) of the selected wood species have been dehydrated and
transversally cut in several portions of about 1 cm in length.
Some wood samples have been carbonized in a stove near em-
bers, paying attention to avoid direct contact with the flame.
To investigate the laser–wood interaction effects, irradiation
has been performed both on bark and on the surface of the
tangential wood section.
Two commercial acrylic resins (Plexisol 550 and Paraloid
B72) have been used as consolidants. These materials are
widely used in archaeological restoration treatments and they
have been analyzed in previous works. Optical absorption
measurements, made in both consolidants, by a UV/Vis spec-
trophotometer and a power meter [7] have shown a maximum
absorption value near 239 nm and an absorption coefficient
of about 2 × 104 cm−1 for both samples. The materials have
been diluted in suitable solvents and applied with a paint-
brush on silicon substrates (about 1 cm × 1 cm). Silicon is
an appropriate material for FT-IR analysis and is frequently
used as substrate. Aluminium substrate has also been tested
to exclude substrate influences on the laser-induced effects. In
addition, some dry and carbonized wood samples have been
consolidated by using a paintbrush with Plexisol 550 and Par-
aloid B72 to evaluate the effectiveness of the laser cleaning
technique.
After sample preparation, laser irradiations have been car-
ried out by systematically varying the laser parameters. Dur-
ing irradiation, the samples were fixed to proper handling
supports while a metallic mask with a circular hole (3 mm
diameter) was placed in front of the sample to ensure a homo-
geneous beam profile in the irradiated region.
A scan system was also implemented that consists of two
stepper motors that permit movements of the sample in two
orthogonal directions (both normal to the beam direction).
The scan rate depends on the number of pulses required in the
spot region.
SEM observations and FT-IR analyses have been per-
formed on both untreated and irradiated samples. To avoid
effects dependent on differences in sample conditions (such
as natural wood variability and manual consolidation proced-
ures), laser effects were always evaluated on the same sample.
Fourier transform infrared spectroscopy (FTIR, Brucker
Equinox 55) analysis in attenuated total reflection (ATR)
and transmission mode was made. The resolution is on the
order of 4 cm−1 for both analyses; the investigated ranges are
500– 7500 cm−1 and 370 – 7500 cm−1 respectively.
Scanning electron microscopy (SEM, Jeol JSM6300) on
non-conducting samples required the deposition of conduc-
tive films (carbon and gold) to avoid charging effects.
3.1 Investigation of cone formation in laser-irradiated
untreated woods
Wood samples have been irradiated with a laser en-
ergy density ranging from 40 up to 1300 mJ/cm2 , and the
number of pulses was in the range from 10 to 10 000. Three
different categories of laser-induced effects have been distin-
guished.
For the lowest value of energy density, namely 40 mJ/cm2 ,
and thousands of pulses, SEM observations revealed morpho-
logical changes, restricted to the very few surface layers, on
both external and internal wood.
At 80 mJ/cm2 , together with morphological surface
change effects, small cones with volcano-like structures [12]
have been induced on external wood. Cones have not been
formed on internal wood where again only surface morpho-
logical changes appear. This different behavior is documented
in Fig. 1, where a comparison of the two regions is presented.
To the naked eye evident darkening of the wood color is ob-
servable.
At 160 mJ/cm2 , conical structures different from those
previously mentioned have been formed both on internal and
external wood. At this energy, cones appearing in external
wood (Fig. 2a) showed a different morphology with respected
to those formed, with the same irradiation conditions, in in-
ternal wood (Fig. 2b). In fact, in this latter case, some pits
of different dimensions have been observed. They are consis-
tent with the anatomical Viburnum lantana elements (vessels,
FIGURE 1 (a) External wood and (b) internal wood after irradiation at
80 mJ/cm2 and 5000 pulses

3 Results

In archaeological research, it is difficult to find

wide bark because this material was usually discarded during
manufacturing process or removed in the course of the years.
In the case under study, bark was preserved.
Laser–wood irradiations have been performed both on
bark and on the surface of the tangential wood section; in the
following, the terms “external wood” and “internal wood”
are used to indicate the bark and the tangential section, FIGURE 2 (a) External wood and (b) internal wood after irradiation at
respectively. 160 mJ/cm2 and 5000 pulses
BELLI et al. Excimer laser irradiation of wooden archaeological objects and polymeric consolidants used in conservation
FIGURE 3 External wood: (a) untreated and (b) after irradiation at
1300 mJ/cm2 and 10 pulses
rays, scalariform perforations) usually observable in the tan-
gential section. On the contrary, in external wood the cones
exhibit a relatively smooth surface and the apex angle appears
to be smaller. By increasing the laser pulse number, cone di-
mensions increase, while their tips are removed.
At 320 and 600 mJ/cm2 , cone formation was also ob-
served but a lower number of pulses is required to observe
effects similar to that of Fig. 2. By further increasing the num-
ber of pulses, surface morphological changes appear as previ-
ously described for low energy density.
FT-IR analyses (not reported) have not shown any varia-
tion in absorption peaks in connection to cone formation.
At the highest value of the laser energy density, 1300 mJ/
cm2 , and with a few laser pulses (10), only wood abla-
tion without surface morphological change is observed. In
Fig. 3 a comparison is made between non-irradiated and
irradiated samples. Cone formation or any other surface
modifications are not observed for this set of laser param-
eters. In addition, no color change appears to the naked
eye.
Irradiations performed on charcoal exhibit macroscopic
effects similar to that with 160 mJ/cm2 on the dry wood.
3.2 Investigation of cone formation in laser-irradiated
consolidant resins
The two utilized consolidant resins exhibit similar
behavior at low energy density (40 mJ/cm2 ) and thousands of
pulses. Laser irradiation induced a patterning of the surface, as
clearly visible in Fig. 4a.
For higher energy density different responses of the two
materials have been observed. Bubbles are formed in Paraloid
B72, with dimension on the order of tens µm (Fig. 4b). Bub-
bles explode by increasing the number of pulses. Different
from this, cracks are formed on the whole surface of the Plex-
isol 550 (Fig. 4c).
At 1300 mJ/cm2 an efficient removal of the consolidant
has been observed. FTIR spectra show the complete elim-
ination of Paraloid B72 absorption peaks (Fig. 5), after 10
pulses, due to laser ablation. The same result has been ob-
tained for Plexisol 550. To evaluate the thickness of the con-
solidant layer, cross-sections of silicon-consolidated samples
have been observed by SEM. The mean thickness is about
10 µm for both consolidants.
219
FIGURE 4 (a) Paraloid irradiated at 40 mJ/cm2 and 5000 pulses (the same
as for Plexisol). (b) Paraloid irradiated with 1000 mJ/cm2 and 5 pulses.
(c) Plexisol irradiated with 1000 mJ/cm2 and 5 pulses
FIGURE 5 Consolidated silicon substrate with Paraloid B72 A) before and
B) after irradiation
Aluminum substrates have been tested, but no differences
in the laser-induced effects have been noticed.
3.3 Investigation of cone formation in laser-irradiated
consolidated woods
Based on previous results, a selected combination
of energy density and pulses number has been tested to clean
a model sample featuring the consolidated archaeological
basketry. Figure 6a shows the surface of the modern consoli-
dated wood (the morphology is the same for both the consoli-
dants).
A few laser pulses with 1300 mJ/cm2 energy density per-
mit an efficient removal of the consolidant with neither mor-
phological nor chromatical variations of the irradiated wood
surface.
Laser irradiation produced the same effects on wood con-
solidated with the two types of resins. As reported in Fig. 6b
and c, the consolidants have been completely removed and
a wood surface similar to that observed in Fig. 3a is high-
lighted. No modifications visible to the naked eye have been
caused.
FTIR spectra reported in Fig. 7 are related to the same
wood sample: untreated and after consolidant deposition (Par-
220 Applied Physics A – Materials Science & Processing
FIGURE 6 (a) Untreated consolidant wood surface. Wood surface after ir-
radiation at 1300 mJ/cm2 and 10 pulses: (b) on wood consolidated with
Paraloid; (c) on wood consolidated with Plexisol
FIGURE 7 A) Untreated wood. B) Consolidated wood. C) Consolidated
wood after irradiation at 1300 mJ/cm2 and 10 pulses
aloid B72) followed by laser cleaning. Although irradiation
with 10 pulses of consolidated wood produced spectra simi-
lar to that of the untreated wood, few differences could be
observed. Such differences are attributable to the ablation of
a thin surface layer of the external bark surface.
By comparing the spectra of laser cleaned wood with that
of a non-consolidated and irradiated wood (Fig. 8) a perfect
overlap of the absorption peaks is highlighted.
4 Discussion
Before looking at the cone formation, we briefly
comment on phenomena occurring on Paraloid and Plexisol
consolidants under laser irradiation as reported in Fig. 4.
In studies on PMMA, Rebollar [9] observed that laser
irradiation-induced cleavage of the polymer backbone and
COOCH3 separation, accompanied by the formation of
gaseous material in the form of bubbles. It is plausible that
similar effects also occur in our systems, and bubbles explode
because of the increasing pressure.
Several works on excimer laser irradiation of polymeric
materials reported on the formation of conical shape struc-
tures that are formed for a selected range of laser parameters
(fluence and number of pulses) [10, 11]. Hopp [12] proved
FIGURE 8 A) Non-consolidated wood after irradiation at 1300 mJ/cm2
and 10 pulses. B) Consolidated wood after irradiation at 1300 mJ/cm2 and
10 pulses
FIGURE 9 Advanced step of cone formation after laser irradiation at
320 mJ/cm2 and 2000 pulses
that the cone formation is related to the presence of particu-
late impurities on the surface of the irradiated polymer and
that volcano-like structures are formed at low laser fluences.
In addition, the cone formation occurs in a well established
range of the laser parameter values.
To explain cone formation, different mechanisms have
been proposed (see [10] and references therein). The best sup-
ported mechanism is connected to the shadowing effects of
the laser pulse because of the presence of particulate impuri-
ties [13]. However, processes related to the redeposition of the
ablated debris, beam non-uniformities, and radiation harden-
ing [14] have been suggested.
Our results show that the cone formation occurs within
a well established range of the laser energy density and that
the cone structure is induced by a combination of shadowing
effects, possibly due to particulate impurities on the irradiated
surface, and ablation of the surrounding area. This explana-
tion is clearly supported by the presence of both cones hav-
ing anatomical Viburnum lantana elements, reminiscent of
the untreated wood, and crater surrounding the cone (Fig. 9).
Cone formation in external wood appears at a laser energy
density lower than in the case of the internal surface. This be-
havior could be connected with different morphologies and
chemical compositions of internal and external wood, which
could influence the laser absorption.
BELLI et al. Excimer laser irradiation of wooden archaeological objects and polymeric consolidants used in conservation
5 Conclusions
vanni Kezich and Dr. Marta Bazzanella (Museum of S. Michele all’Adige,
Italy – www.museosanmichele.it) for supporting of research activity.
The morphology of the cones observed in the
present work is very similar to that reported in the litera-
ture of the laser-irradiated polymers. Here also, shadowing
effects combined with ablation processes are proved to be
the mechanisms responsible for cone structure formation.
In previous work on samples of prehistoric basketry [6],
the formation of cone structures was observed after laser
irradiation at 600 mJ/cm2 . Thermal stresses may also con-
tribute to cone formation on the surface of the unknown
consolidant. Thermal stresses are certainly operating in ir-
regular and non-planar irradiated surfaces, but the present
results obtained on model samples could suggest an ad-
ditional contribution due to the behavior of wood under
irradiation.
The systematic study reported in this work permitted the
establishment of a range of laser parameters (1300 mJ/cm2
energy density and 10 pulses) that seems to be promising for
the removal of the consolidant without apparent damage on
the wood.
In future work we plan to investigate the problems in-
volved in laser irradiation and conservation, in particular the
ageing process.
221
ACKNOWLEDGEMENTS The authors wish to thank Dr. Gio-
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