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Journal of Cultural Heritage 11 (2010) 91–101

Original article

A methodological approach in the evaluation of the efficacy of treatments


for the dimensional stabilisation of waterlogged archaeological wood
Gianna Giachi a , Chiara Capretti b , Nicola Macchioni b,∗ , Benedetto Pizzo b , Ines Dorina Donato c
aLaboratorio di Analisi, Soprintendenza ai Beni Archeologici per la Toscana, 3, Largo del Boschetto, 50143 Firenze, Italy
b CNR–IVALSA, 10, Via Madonna del Piano, 50019 Sesto Fiorentino, Italy
c Dipartimento di Chimica Fisica “F. Accascina”, Università degli Studi di Palermo, viale delle Scienze, 17, Edificio, 90128 Palermo, Italy

Received 29 April 2008; accepted 22 April 2009


Available online 13 November 2009

Abstract
The aim of the work is to set up a methodological approach to verify the effectiveness of the treatments of decayed waterlogged archaeological
wood and to point out the proper thermo-hygrometric conditions for its preservation after treatment. The treatments were performed on wood
samples of maritime pine (Pinus pinaster Aiton), oak (Quercus sp. caducifolia), elm (Ulmus cf. minor) and strawberry tree (Arbutus unedo L.),
obtained from stems pertaining to the original vegetation found in the excavation site of the Ancient Ships in Pisa (Italy), and dated from seventh
century BC to second century AD The utilised products were: Polyethylene Glycols (PEG) of various molecular weights, a Polypropylene Glycol
(PPG 425), Trehalose (␣-D-glucopyranosyl-␣-D-glucopyranoside), and their mixtures, and also a Hydroxypropylcellulose (Klucel). The main
objective to be pursued by the treatments was considered the stabilisation of the original size and shape of samples. The various steps of this
approach were: the execution of a preliminary diagnostic survey on untreated samples; the characterisation of treatment solutions ‘as such’ to
establish the property to be monitored during the treatment; the evaluation of the main physical characteristics of wood after the treatment were
determined. Among the latter, the coefficient of dimensional stability during the exposure to a series of selected thermo-hygrometric conditions
and the retention of consolidants after the treatment. These two measurements allowed the definition of the ‘efficacy of a treatment’, ϕT , a new
parameter firstly utilised in this work. It measures the stabilisation capability of the percent unit of retained product, and its value permits to put
in evidence the consolidants that stabilise wood with the lowest amount of product. Conversely, it was not possible to measure the Anti-Shrink
Efficiency (ASE), one of the most utilised parameters for the evaluation of treatments, because of the serious distortions and fractures observed in
all the heavily degraded untreated samples.
© 2009 Elsevier Masson SAS. All rights reserved.

Keywords: Waterlogged archaeological wood; Treatments; Decay; Conservation; Consolidants; PEG; PPG; Klucel; Trehalose; Diagnosis on wood

1. Introduction and research aims Drying of waterlogged archaeological wood is a high-risk


procedure. The uncontrolled removal of water from of the weak
Generally, waterlogged archaeological wood preserves its cell walls, depending on the wood decay, may cause severe
original size and shape rather well, but this material has often wood shrinkage and collapse. In most events these phenom-
underwent severe cell wall decay. ena give rise to severe cracks and distortions with the loss of
The wood degradation can be due both to chemical factors the artefact’s shape and sometimes even the loss of the artefact
(such as pH, salinity of water permeating the sediments) [1] and itself.
biological agents [2,3]. It involves mass loss and, consequently, Moreover, when the wooden finds are complex structures,
the increase of wood porosity and permeability, so that the mate- such as shipwrecks, the wood must also maintain after dry-
rial becomes increasingly spongy and waterlogged [4,5]. ing enough physical integrity to preserve, at least partially, its
mechanical function.
Consequently, the conservation of waterlogged archaeologi-
cal wood involves the removal of water by means of treatments
∗ Corresponding author. whose goals, as suggested by Grattan and Clarke [6], can be
E-mail address: macchioni@ivalsa.cnr.it (N. Macchioni). summarised in:

1296-2074/$ – see front matter © 2009 Elsevier Masson SAS. All rights reserved.
doi:10.1016/j.culher.2009.04.003
92 G. Giachi et al. / Journal of Cultural Heritage 11 (2010) 91–101

Table 1
The utilised samples, impregnation solutions and drying methods.
Samples Impregnation solutions Acronym Drying method

– B5 Q2B C4A C4B 30% PEG 400 + 50% PEG 4000 in H2 O (two steps) HC Controlled drying
A6 B6 Q3A C4D C4C 20% PEG 1500 in PPG 425 20PP1500 Controlled drying
A7 B7 Q3B C7A C7B 20% PEG 4000 + 2% TREA in H2 O TP4000 Controlled drying
A8 B8 Q4A C7D C7C 20% PEG 400 + 2% TREA in H2 O TP400 controlled drying
A9 B9 Q4B C8A C8B 20% PEG 400 + 2% TREA in H2 O (TP400)FD Freeze-drying
A10 B10 Q5A C8D C8C 20% PEG 4000 + 2% TREA in H2 O (TP4000)FD Freeze-drying
A11 B11 Q5B C9A C9B 30% PEG 1500 in PPG 425 30PP1500 Controlled drying
A13 B13 Q6B C10A C10B 20% PEG 1500 + 2% TREA in H2 O (TP1500)FD Freeze-drying
A15 B15 Q9A C11A C11B 7% Klucel in H2 O (K)FD Freeze-drying
A20 B20 Q10 C14A C14B 20% PEG 600 + 2% TREA in H2 O (TP600)FD Freeze-drying

• the ability of the treatment to stabilise shape and dimensions


of the artifact;
• the ability of the artefact (by means of the treatment) to with-
stand the future preservation environment.

At the same time, treatments should satisfy safety rules for


operators and environment, should be economically feasible
and finally, should be reversible. The first point is ruled by
National laws (for example in Italy by D. Lgs. no. 25, 2002 and
D. Lgs. no. 65, 2003); the second one is quite difficult to assess
in advance, because it not only has to consider the prices of prod-
ucts, energy, instrumentation and so on, but also the maintenance
of the restored wood; the third point, regarding the reversibility,
is still nowadays a debated concept [7–9].
The literature gives a list of the goals to be accomplished,
but there are no standardised procedures to be followed in order
to measure the effectiveness of the treatments, therefore, a sort Fig. 1. An example of the distribution of wood samples from a disc.
of unitary approach would be useful because it would allow the
comparison of the results obtained from different tests.
The aim of this work is to set up a methodological approach, The wood samples were chosen after an optical examina-
in order to both verify the effectiveness of the waterlogged tion: a conifer, a diffuse-porous hardwood and two porous-ring
archaeological wood’s treatments and to point out the proper hardwoods were selected. Discs approximately 5 cm in thick-
thermo-hygrometric conditions for the treated artefacts. ness were cut from the stems and cubes with 5 cm edges were
This methodological approach was tested on a series of obtained from each disc. Each of the samples was marked with a
waterlogged archaeological wood samples treated by impregna- different letter and numbered according to its longitudinal posi-
tion techniques. The samples underwent a complete diagnostic tion in the stem. When more than one sample was obtained from
procedure in order to assess their state of preservation before the same disc, one more letter was utilised to distinguish them1
treatment. A certain variability of selected wood species and (Fig. 1).
conditions of decay were also chosen in order to have a good
range of representativeness. As for impregnation materials, some 2.2. Products used for wood treatment
Polyethylene Glycols (PEG), a Polypropylene Glycol (PPG),
the sugar ␣-␣-trehalose (TREA) and their mixtures, and also a All the wood samples, the impregnating agents and compo-
Hydroxypropylcellulose (Klucel) were utilised (see Table 1). sition of their mixtures, their acronyms and the drying methods
utilised are reported in Table 1. The wood samples were impreg-
2. Material and methods nated by immersion in:

2.1. Wood samples 1. aqueous solutions of PEG of various molecular weights. PEG
are extensively used for impregnation of waterlogged objects,
Samples were obtained from stems from the original vege- and the properties they give to the degraded wood are quite
tation found in the excavation site of the Ancient Ships in Pisa
(Italy), which can be dated to a time-span ranging from seventh 1 E.g. the pine stem was large enough to obtain four samples per disc marked
century BC to second century AD according to the archaeolog- by the second letters coming from A to D. So the sample C20A is from the 20th
ical stratigraphy. disc obtained from the pine stem (C) in the A portion.
G. Giachi et al. / Journal of Cultural Heritage 11 (2010) 91–101 93

well-known, both in terms of advantages and disadvantages temperature -38 ± 2 ◦ C; vacuum 10−5 –10−2 mbar; trap temper-
[1,10–14]; ature −40 ◦ C).
2. aqueous solutions of mixtures of PEG with TREA. The
TREA (␣-D-glucopyranosyl-␣-D-glucopyranoside) is a dis- 3. Wood characterisation
accharide of glucose, in which the absence of any internal
hydrogen bonds produces a certain flexibility around the glu- Wood characterisation was performed following the path
cosidic bond. Recent studies showed that TREA causes a established by the Italian standard UNI 11205:2007 [22], that
dramatic decrease of the ordered structure of water molecules is:
in its solutions due to the rupture of hydrogen bonds [15], and
this is thought to facilitate the removal of water molecules • identification of constituent wood species [23] by means of
during drying [16]; optical microscopy on thin sections of wood, along the three
3. mixtures at different concentrations of PEG 1500 in PPG 425. characteristic directions;
The PPG have lower hygroscopicity and viscosity than PEG • decay assessment by means of physical measurements of
with the same units of monomer. At room temperature (RT) Maximum Water Content (MWC), Basic Density (Db ),
pure PPG 425 is liquid, but its mixtures with PEG 1500, at Residual Db (RDb ) and total shrinkages along the three char-
the concentrations used in the present work, are solid [17,18]. acteristics directions [24–26];
Furthermore, PPG 425 has pronounced antibacterial proper- • dimensions were measured initially (at MWC) on all the
ties [19,20]; samples, then, at each stage, on the samples which were
4. aqueous solutions of Klucel. Klucel (MW 80,000) is a poly- still orthotropic. Reference values of basic densities of sound
mer obtained from the etherification of cellulose and it has wood have been taken from literature [27];
been successfully used in the consolidation of waterlogged • decay assessment by means of chemical measurements of
wood [21]. residual amounts of holocellulose (according to Norman and
Jenkins, as reported in [28]) and lignin (TAPPI T222 [29]),
The concentrations of the mixtures reported in points 2, 3 and their ratio H/L, which is considered as representative of
and 4 above were selected according to previous experiences the extent of the chemical decay.
[16,21].
Drying after treatment was carried out by a controlled proce- The wood species were:
dure (see Chapter 6.2) or by freeze-drying (Table 1). This latter
was performed by using an EC-Modulyo Freeze-Dryer (freezing • strawberry tree (Arbutus unedo L.) samples marked with A;

Table 2
Results of chemical and physical characterisation of selected wood samples. The values marked with * were measured with a helium-pycnometer by using the
methodology described in [35]. The other values were obtained through the water-displacement method [36].
Sample Wooden species Db of non-degraded Db of WAW (g·cm−3 ) RDb (%) MWC (%) H/L of WAW H/L of non-degraded
wood (g·cm−3 ) wood

A2 0.12 13.9 762 0.07


A4 0.13* 14.9 704 –
A16 Arbutus unedo 0.87 0.12 13.6 775 0.09 2.4
A30A 0.15 16.9 608 –
A30B 0.14 16.4 635 0.09
B2 0.15 26.7 591 0.10
B4 0.17* 29.8 549 –
Ulmus cf. minor 0.57 2.1
B17 0.14 24.6 649 0.14
B29 0.15 26.3 602 0.11
Q1A 0.35 51.6 224 0.10
Q1B Quercus sp. cad. 0.67 0.19* 28.4 472 – 2.1
Q18 0.17 26.0 515 0.18
C2A 0.26 49.9 315 0.48
C12A 0.13 24.0 727 0.07
C2B 0.15 29.5 570 0.42
C12B 0.27 52.0 301 0.49
Pinus pinaster 0.53 2.2
C3C 0.13* 24.5 689 –
C20C 0.24 46.1 350 0.57
C3D 0.23* 43.4 435 –
C20D 0.17 31.9 534 0.35

In the table, WAW is the Waterlogged Archaeological Wood. H/L of non-degraded wood was measured according to the same procedures as for WAW; MWC:
Maximum Water Content.
94 G. Giachi et al. / Journal of Cultural Heritage 11 (2010) 91–101

Table 3
Values of viscosity (η), surface tension (γ) and refractive index (nD ) of the selected impregnation solutions.
Impregnation mixtures η (cp)T = 45 ◦ C γ (dyn/cm)T = 45 ◦ C nD T = 25 ◦ C

20% PEG 400 + 2% TREA in H2 O 1.44 44.80 1.363


20% PEG 600 + 2% TREA in H2 O 1.63 48.87 1.363
20% PEG 1500 + 2% TREA in H2 O 2.40 53.80 1.362
20% PEG 4000 + 2% TREA in H2 O 4.66 57.66 1.426
20% PEG 1500 + PPG 425 32.59 34.00 1.443b
30% PEG 1500 + PPG 425 36.35 34.19 1.445b
7% Klucel in H2 O 49.99a 40.16a 1.341
a Measured at 30 ◦ C.
b Measured at 45 ◦ C.

• elm (Ulmus cf. minor) marked with B; tions of Klucel go beyond the “cloud point” [30]). The treatment
• maritime pine (Pinus pinaster Aiton) marked with C; with PEG 400 and 4000 was performed in two steps, as reported
• oak (Quercus sp. caducifolia) marked with Q. in [31]. In order to verify the effect of different drying meth-
ods, the treated samples were dried either by freeze-drying or
Because the decay of waterlogged archaeological wood by a controlled decrease of the relative humidity, following the
involves the loss of substance (mostly polysaccharides) and its sequence 85, 65, 45, 35% RH.
replacement by water, the increase of MWC, and/or the decrease
of Db , and the decrease of H/L indicate an increasing level of 6. Evaluation of the efficacy of the treatments
decay for the archaeological wood. In our case, the diagnostic
evaluations resulting from both chemical and physical charac- The efficacy of treatments was evaluated in terms of retention
terisations give comparable results for each wooden sample, as of impregnation products and moreover of equilibrium moisture
shown in Table 2. contents (EMC) and dimensional stability at different relative
Among the selected wood samples, strawberry tree and elm humidities. The collected data were also compared with the
are highly degraded, whereas pine is generally in better con- macroscopic observation of the shape of the samples.
ditions. Oak samples were also degraded: in this case, the
difference in physical measurements obtained in samples Q1A, 6.1. Retention of impregnation products
Q1B and Q18 evidenced a non-uniformity in the distribution of
decay. The retention of impregnation products, Y, was calculated by
means of the increase of weight of treated wood with respect to
4. Characterisation of the impregnation solutions weight of the same untreated sample, according to the following
equation:
The impregnation was carried out by immersion: in this case mAT − mANT
the penetration of the solutions into the wood is due to diffu- Y = 100 · (1)
mANT
sion and, even if to a lesser extent, to permeation [6]. In order
to determine the characteristic parameters for these processes, where mAT is the oven-dried mass of treated samples and
measurements of viscosity (η) and surface tension (γ) were car- mANT is the estimated oven-dried mass of the same samples
ried out. Moreover, refractive index (nD ) measurements were when non-treated. This latter was calculated by attributing to
utilised to follow the evolution of the process of impregnation:
this latter can be assumed as complete when the refractive index
of the solutions in which the sample is immersed approached to
the value of the treatment mixtures within the limits of the mea-
surement error. This condition was reached after renewing the
treatment solution several times. Measured physical parameters
for the mixtures are reported in Table 3, whereas an example
of the process of impregnation for one of the treated samples is
reported in Fig. 2.

5. Techniques of impregnation and drying of wood

The wood samples were immersed in the selected impreg-


nating solutions after their desalination in water, until a
Fig. 2. Refractive index of the impregnating solution vs. time (days) during the
conductivity ≤ 10 ␮S cm−1 was reached. The temperature was treatment of sample B8 (mixture TP400). In the specific case, the process of
45 ◦ C for all treatments, except for Klucel for which it was 30 ◦ C impregnation was done in three steps. The difference in measurements observed
(for higher temperatures and concentrations, the aqueous solu- in the step III is within the accuracy of the instrument.
G. Giachi et al. / Journal of Cultural Heritage 11 (2010) 91–101 95

Table 4
Values of MWC used in the calculation of mANT , of the retention of products, Y, of the ‘efficacy of treatment’, ϕT , and of β̄V for all the analysed samples. Missing
measurements are due to an excessive distortion of samples during the conditioning phases.
Treatment Sample MWC (%) Y (%) β̄V (%) ϕT (–) Treatment Sample MWC (%) Y (%) β̄V (%) ϕT (–)

A15 775 41 – –
B5 591 322 78.4 0.243 B15 649 33 – –
HC C4A 570 326 92.4 0.284 (K)FD C11A 727 75 88.6 1.190
C4B 315 159 84.1 0.528 C11B 301 10 92.8 9.324
Q2B 472 251 63.9 0.255 Q9A 472 75 79.3 1.064
A6 762 572 74.6 0.130 A13 775 187 – –
B6 591 468 85.3 0.182 B13 649 148 – –
20PP1500 C4C 315 235 89.7 0.382 (TP1500)FD C10A 727 177 90.2 0.509
C4D 570 482 84.8 0.176 C10B 301 62 78.6 1.275
Q3A 472 337 83.9 0.249 Q6B 472 103 75.6 0.733
A11 775 624 76.2 0.122 A20 775 178 – –
B11 649 518 86.3 0.167 B20 649 145 – –
30PP1500 C9A 727 626 86.3 0.138 (TP600)FD C14A 727 178 88.9 0.499
C9B 301 243 94.1 0.387 C14B 301 55 94.4 1.714
Q5B 472 371 79.0 0.213 Q10 472 140 73.1 0.521
A8 762 171 63.0 0.368 A9 762 161 65.6 0.407
B8 591 128 22.8 0.178 B9 591 131 – –
TP400 C7C 315 58 93.4 1.608 (TP400)FD C8B 301 50 94.1 0.572
C7D 570 115 60.7 0.530 C8A 727 164 96.0 1.927
Q4A 472 110 74.7 0.682 Q4B 472 125 79.5 0.635
A7 762 112 31.8 0.285 A10 775 238 82.3 0.346
B7 591 104 32.7 0.314 B10 649 211 – –
TP4000 C7B 315 69 91.8 1.329 (TP4000)FD C8C 301 84 93.7 1.120
C7A 570 135 75.4 0.559 C8D 727 245 87.9 0.359
Q3B 472 93 47.7 0.512 Q5A 472 126 82.1 0.654

Table 5
Equilibrium moisture content (EMC) of the air-dried samples in the entire RH cycle.
Sample Treatment EMC at different RH

85% RH 65% RH 45% RH 35% RH 45% RH 65% RH 85% RH

B5 31.94 8.13 2.76 1.89 2.39 4.33 12.81


Q2B 30.96 13.39 8.25 4.39 3.88 5.67 14.22
HC
C4A 30.03 6.62 2.92 2.35 2.97 5.27 13.51
C4B 32.83 8.36 2.66 1.62 2.12 4.08 12.31
A6 23.75 12.39 8.63 6.22 6.12 7.71 26.82
B6 22.71 10.78 6.77 4.86 5.18 7.51 26.82
Q3A 20PP1500 19.60 11.13 8.41 6.64 6.56 8.04 23.51
C4D 25.58 14.57 10.73 7.90 7.60 9.30 27.70
C4C 20.75 9.00 5.07 3.42 4.06 6.68 25.89
A7 25.20 7.32 3.69 3.01 3.65 5.83 13.88
B7 24.13 6.07 3.77 3.22 3.86 6.03 13.88
Q3B TP4000 27.51 12.49 8.35 5.79 5.82 8.13 17.19
C7A 18.29 6.62 4.18 3.44 4.34 7.26 17.35
C7B 15.52 7.87 4.97 4.11 5.16 8.54 17.56
A8 39.68 19.91 11.90 9.78 11.98 21.31 47.03
B8 30.17 14.22 7.82 6.38 8.41 15.80 40.35
Q4A TP400 29.28 14.10 8.17 6.23 7.76 14.34 34.50
C7D 30.21 13.82 7.15 5.48 7.73 15.89 43.68
C7C 24.67 12.40 6.75 5.26 7.26 14.07 34.17
A11 34.20 22.22 18.94 16.57 16.12 17.00 30.97
B11 31.05 18.70 14.68 12.05 11.84 13.69 28.22
Q5B 30PP1500 26.60 16.25 13.34 11.26 10.91 11.85 26.45
C9A 26.16 15.13 11.75 9.28 8.94 10.25 25.66
C9B 19.67 10.58 7.12 4.98 5.17 7.48 17.57
96 G. Giachi et al. / Journal of Cultural Heritage 11 (2010) 91–101

each sample the same MWC of the nearby sample utilised in Table 6
diagnostic evaluations. In particular, the following expression Equilibrium moisture content (EMC) of each freeze-dried samples at every RH
stage.
was used:
Sample Treatment EMC at different RH
mWNT
mANT =
1 + MWC 35% RH 45% RH 65% RH 85% RH

A9 6.79 9.15 17.90 49.52


where mWNT is the wet mass of untreated samples (i.e. the B9 6.51 8.65 16.14 43.53
mass of each sample before the treatment). The results are shown Q4B (TP400)FD 6.50 8.48 15.48 38.15
in Table 4, where the values of MWC utilised in the calculations C8A 6.15 8.70 17.59 47.72
are also reported. C8B 5.37 7.49 14.61 37.76
A10 2.82 3.39 5.25 12.35
B10 3.05 3.63 5.68 12.58
6.2. Equilibrium moisture content of treated wood Q5A (TP4000)FD 4.00 4.63 6.96 14.33
C8D 3.11 3.79 6.14 13.27
To evaluate the effect of the treatments with respect to mois- C8C 3.74 4.49 7.31 14.81
ture absorption, the treated samples were put in a climatic A15 11.66 12.15 15.56 23.13
chamber at 20 ◦ C, varying the RH values according to the B15 13.60 14.63 17.98 25.56
sequence 85, 65, 45, 35, 45, 65, 85% and reaching, in each step, Q9A (K)FD 11.57 12.15 15.01 20.80
the EMC [27]. Freeze-dried samples were subjected only to the C11A 7.08 8.22 11.59 18.30
C11B 8.79 9.93 13.30 19.83
remoistening phases (from 35 to 85%). In each step samples
reached the equilibrium after 15 to 30 days. The conditioning A13 3.93 4.79 7.58 34.82
B13 4.48 5.41 8.56 34.22
steps at different RH values were considered useful also for the
Q6B (TP1500)FD 4.20 5.11 8.38 35.48
assessment of the eventual behaviour of the treated wood after C10A 4.26 5.21 8.53 33.25
treatment. C10B 5.07 6.12 9.74 26.10
At the end of the whole climatic cycle, the samples were A20 5.40 7.39 14.46 39.48
completely dried in an oven at 103 ◦ C. In order to drastically B20 5.25 7.02 13.05 33.51
reduce the amount of time the samples were in the oven, thus Q10 (TP600)FD 5.50 6.91 12.04 27.00
minimising the degradation (and the subsequent loss of mass) C14A 5.44 7.33 13.86 35.94
of the impregnants, an intermediate equilibration step at 40 ◦ C C14B 5.38 7.04 12.50 29.41
and 18% RH was carried out. During all the drying phases, each
sample was maintained and weighed in a glass box in order to
avoid the release of consolidants due to their melting at high The shrinkage and swelling of the wood samples, grouped
temperature. per treatment, both for controlled drying (for the entire RH
Results for samples that underwent the entire RH cycle are cycle) and for freeze-dried samples are reported, respectively
reported in Table 5 whereas the results of freeze-dried samples in Tables 7–10.
are summarised in Table 6. Figs. 4 and 5 report the average movements of the pine sam-
ples in tangential direction, for the different treatments. For
some samples treated with PEG and TREA, passing from 85
6.3. Dimensional variations of treated wood

In order to calculate shrinkage and swelling of the treated


woods, measurement of the samples along the three principal
directions at each drying and remoistening step was carried
out.
In many cases, these measurements were very difficult
because of the severe distortions and deformations produced
(Fig. 3). Consequently, the results reported here exclude sam-
ples that have undergone great distortions and are considered
reliable only with dimensional changes greater than 2%. More-
over, considering that most of the untreated reference samples
collapsed even at humidities of 85%, it was impossible to mea-
sure their deformations, and hence the Anti-Shrink Efficiency
(ASE) [6] of treated samples could not be calculated.
Due to the decay of the cellulosic fraction, the most important
shrinkage and swelling were in radial and longitudinal direc- Fig. 3. Sections from two strawberry tree samples consolidated in a different
way: the right one shows a lower distortion, whilst the consolidation of the
tions, while the tangential direction was frequently affected by left one was less effective. The deformations on this latter prevented any mea-
the collapse of the cells, except for pine samples, which were surement of the shrinkage. Note that the two samples originally had the same
generally less decayed. dimensions (cubes, 5 cm side).
G. Giachi et al. / Journal of Cultural Heritage 11 (2010) 91–101 97

Table 7
Average radial shrinkage and swelling during controlled drying of the different samples for each treatment (pine samples excluded).
Treatment Deformations (%) at different RH

85% RH 65% RH 45% RH 35% RH 45% RH 65% RH 85% RH

HC 6.83 (1.14) 6.44 (1.93) 6.69 (0.50) 7.40 (2.09) 7.54 (2.04) 7.39 (1.01) 5.02 (1.60)
20PP1500 0.93 (3.80) 1.57 (3.73) 2.25 (6.29) 3.78 (5.51) 3.88 (5.01) 3.13 (5.20) 0.50 (4.34)
TP4000 17.33 (25.76) – – – – – –
TP400 17.80 (24.55) – – – – – –
30PP1500 2.65 (1.86) 2.64 (2.04) 4.17 (3.04) 3.22 (3.46) 3.57 (3.35) 3.61 (3.27) 0.02 (2.23)

Standard deviation in brackets.

Table 8
Average tangential shrinkage and swelling during controlled drying of the different samples for each treatment (pine samples excluded).
Treatment Deformations (%) at different RH
85% RH 65% RH 45% RH 35% RH 45% RH 65% RH 85% RH

HC 12.40 (11.01) 17.65 (12.95) 18.24 (11.63) 18.50 (10.88) 17.30 (11.06) 17.69 (10.31) 13.62 (10.16)
20PP1500 0.29 (3.45) 3.43 (3.16) 5.04 (4.19) 4.94 (4.90) 4.63 (5.43) 6.05 (5.24) 0.83 (8.11)
TP4000 34.86 (7.13) – – – – – –
TP400 17.31 (12.41) – – – – – –
30PP1500 1.43 (1.28) 5.07 (1.91) 5.09 (3.71) 8.50 (2.70) 8.90 (2.06) 8.56 (2.45) 4.56 (6.31)

Standard deviation in brackets.

Table 9
Average radial swelling of the different freeze-dried samples for each treatment
(pine samples excluded).
Treatment Swelling (%) at different RH

35% RH 45% RH 65% RH 85% RH

(TP400)FD 7.93 (6.37) 7.26 (3.32) 6.75 (2.31) 9.18 (9.52)


(TP4000)FD 4,98 (1.14) 3.81 (–) 5.06 (2.51) 3.47 (1.77)
(K)FD 5.10 (2.99) 3.55 (–) 3.21 (–) 3.06 (–)
(TP1500)FD 2.12 (2.24) 4.01 (–) 3.89 (–) 1.78 (–)
(TP600)FD 10.12 (–) 9.98 (–) 9.22 (–) 8.00 (–)

Standard deviation in brackets.

Fig. 4. Average tangential shrinkage and swelling of the pine samples, grouped
to 65% RH promoted such high deformations, that dimensional per treatment (controlled drying).
measurements were prevented.
compare visually the efficacy of each treatment on similar sam-
6.4. Macroscopic observation ples.
Only the most exemplificative cases of oak (Fig. 6) and of
All treated samples, after the end of the humidity cycles pine samples (Fig. 7) are shown. Cross sections allow to per-
and after oven-drying, were crosscut and scanned on a large
scanner in order to obtain a single picture after grouping
them by species. This way of grouping allows to directly

Table 10
Average tangential swelling of the different freeze-dried samples for each treat-
ment (pine samples excluded).
Treatment Swelling (%) at different RH

35% RH 45% RH 65% RH 85% RH

(TP400)FD 13.25 (4.66) 10.77 (3.55) 10.49 (3.63) 9.96 (4.33)


(TP4000)FD 9.06 (3.50) 10.55 (–) 8.20 (2.98) 6.47 (1.45)
(K)FD 12.69 (2.08) 9.99 (–) 11.38 (–) 7.45 (–)
(TP1500)FD 9.68 (11.76) 17.74 (–) 16.59 (–) 15.95 (–)
(TP600)FD 7.68 (–) 6.34 (–) 7.05 (–) 2.32 (–)
Fig. 5. Average tangential shrinkage and swelling of the pine samples, grouped
Standard deviation in brackets. per treatment (freeze-dried samples).
98 G. Giachi et al. / Journal of Cultural Heritage 11 (2010) 91–101

tures 20PP1500 and 30PP1500, that are satisfactory, and for


(K)FD on the oak sample, which obtained the best result relative
to the other treatments on oak. Regarding pine samples, there
is a difference among samples of group B/C, which were bet-
ter preserved, and those of group A/D. While for the former all
treatments behave very well without evident distortions, includ-
ing the untreated sample, for the group A/D the impregnation
appears to appreciably increase the stabilisation with respect
to the untreated sample, and there are minor differences among
treatments. In this latter case, only some mixtures failed partially
(TP4000, TP400).
However, for all the four considered species the direct
comparison between controlled drying and freeze-drying, only
possible with treatments TP4000 and TP400, evidenced that
freeze-drying allows for better results in terms of reducing exter-
Fig. 6. Sections of oak samples after treatment and oven-drying. Before treat- nal collapse and maintaining the initial geometrical shape of
ment all samples had similar dimensions (5 cm side cubes). Table 1 details the wooden samples.
treatment corresponding to each sample. Q15 is the reference untreated sample.
7. Discussion
ceive immediately not only the final dimensions of the samples,
but also to check opening and collapse as consequences of both The data give evidence that the consolidants mostly
the treatments and the conditioning. It is also possible that the determine the final physical behaviour (both in terms of absorp-
internal checks visible after the oven-drying phase are due to tion/desorption and shrinkage properties) of the treated samples,
the freeze-drying phase, but it was not possible to further inves- and in such a context the retention of impregnation products is
tigate this aspect due to the limited availability of samples. an essential property to be considered in order to evaluate the
However, this occurrence evidences a state of internal stress for results. Moreover, the main effect a treatment has to achieve
the involved samples. A similar behaviour was also observed in is basically to maintain the original geometric shape of finds.
some of the elm samples. However, an excess quantity of products implies inefficiencies
The appearance of collapse is particularly important, because in terms of costs and of increased final weights of treated objects.
the measured dimensional variations included the large inter- Therefore, the efficacy of a treatment has to be considered as
nal checks and consequently did not correspond to the effective related to its retention and has also to be regarded with atten-
dimensional variations, which occurred. tion: a treatment is more effective when it stabilises samples by
The macroscopic observations allow evaluation of the effect means of the lowest amount of retained impregnating product.
of each treatment on samples at different levels of decay. For This concept can be numerically quantified with the parameter
the most decayed species (strawberry tree, elm and oak) all the ‘efficacy of treatment’, ϕT , that can be defined by the following
considered treatments practically fail in their major task of the ratio:
dimensional stabilisation of samples, except for both the mix-
β̄V
ϕT = (2)
Y
where Y is the retention of impregnation products (see Chap-
ter 6.1) and β̄V is the complement to 100 of the shrinkages
measured for the samples. In particular, β̄V and can be calculated
as follows:
β̄V = 100 − (SL + SR + ST ) (3)
SL , SR and ST being respectively the maximum per cent lon-
gitudinal, radial and tangential shrinkages of each sample. It can
be noted that in undegraded wood, the sum of these three shrink-
ages is commonly referred as ‘volumetric shrinkage’, therefore
β̄V can be considered as a sort of coefficient of dimensional
stability for treated degraded wood samples.
Great caution has to be adopted in the measurement of β̄V ,
considering that the probable tangential collapse (see Chap-
Fig. 7. Comparisons among the pine samples from less decayed (B and C)
ter 6.4) can induce some appreciable errors. In some cases (A7,
and from more decayed (A and D) zones. Each couple, e.g. C4A and C4B,
had the same treatment (refer to Table 1). Before treatment all samples had A8, A15, B7, B8, B13, B15, Q3B and Q4A) we decided not to
similar dimensions (5 cm side cubes). C18C and C19A are non-treated reference discard measurements in order to have at least an approximate
samples. estimation of the effect of stabilisation.
G. Giachi et al. / Journal of Cultural Heritage 11 (2010) 91–101 99

Table 11
Equilibrium moisture content (EMC) of impregnating solutions and of untreated waterlogged wood at every RH stage. Sound wood values are from literature [27].
EMC at different RH

35% 45% 65% 85%


Pure consolidants PEG 400 6.03 10.40 24.12 70.61
PEG 1500 1.83 2.21 3.48 61.28
PEG 4000 0.61 0.78 1.21 3.72
PPG 425 5.96 6.85 9.45 16.87
TREA 0.54 0.58 10.73 10.81
Sound wood 7.00 8.00 12.00 16.00
Untreated archaeological wood Elm 8.57 9.33 11.95 16.67
Oak 14.04 13.71 16.19 21.34
Pine B/C 6.93 7.80 10.29 14.17
Pine A/D 6.89 7.71 10.21 14.88

The results of β̄V and ϕT for each treated sample are reported
in Table 4. From the results it appears that, independent of the
type of treatment, the highest values of the efficacy are associated
to pine samples of the group B/C (namely C11B, C8B, C14B,
C7C, C7B, C10B and C8C), that are in the best state of preser-
vation: even in cases of low retention of impregnation samples
they are very stable after drying. High values of the efficacy
of treatment are also associated with impregnation with Klucel
(samples C11A and Q9A): this implies that a limited amount of
product is sufficient in order to obtain a good effect of dimen-
sional stabilisation, in comparison with other less effective types
of treatment. Samples C11A and Q9A are also those with the
highest retention of impregnation products among the Klucel-
treated samples (Table 4). However, some problems occurred in Fig. 8. Graph of the retention of impregnation products vs. Maximum Water
the other samples of the same group and hence an additional Content (MWC) for all the impregnated samples. For the meaning of numbers
effort for the optimization of this treatment is needed. of each straight line see the text.
Conversely, the treatments that use only PEG and PPG
(20PP1500, 30PP1500 and HC) are those with the lowest values
of ϕT . This means that a greater amount of product is required and PPG 425 behave in a very similar manner (line 1 in Fig. 8)
for reaching an acceptable level of dimensional stabilisation. and show a higher amount of consolidants are introduced into
This implies potentially higher costs and higher final weights the wood with respect to all the other utilised solutions. The
of the treated objects (in some cases densities of 1000 kg/m3 same Fig. 8 shows, in decreasing order, the rate of substitu-
are reached), which make it necessary to mechanically support tion of the mixtures HC (line 2) and of PEG and Trehalose
them. (zone 3, enclosed in the two dotted lines). These latter behave
Finally, it is also noticeable that freeze-dried oak samples in a very similar way among themselves even by varying the
(Q9A, Q6B, Q5A and Q4B) are generally those with the second molecular weight of PEG. Obviously there are no appreciable
highest (after the pine B/C ones) values of ϕT . However, this differences among samples intended for freeze-drying and those
circumstance is probably more related to a specific way of col- for controlled drying, except for one sample impregnated with
lapse of oak wood cells after freeze-drying than to a real effective the TP4000 solution (namely A7) for which probably a problem
treatment process (Fig. 6). during the process of impregnation occurred. The mixture of
The retention of impregnation products is strongly related to Klucel penetrated very scarcely in the decayed wooden matrix
the MWC of the samples and therefore to their state of preser- (line 4), because of the lower treatment temperature and to the
vation. This occurrence is better represented in Fig. 8 where the low concentration used.
linear relationship between Y and MWC is evident. It should be The values of EMC of treated samples seem to be related to
noted that all the straight lines cross the origin. The slope of the hygroscopic characteristics of products, whereas the contri-
each straight line is correlated to the amount of water molecules bution of wood is only partial. Table 11 shows the EMC values
substituted by the products and it is proportional to the concen- of the pure consolidants compared to those of sound wood and of
tration of consolidants: it is lower for the less concentrated untreated and decayed waterlogged wood samples. In general,
mixtures, as in the case of (K)FD , and is higher for mixtures samples evidence a positive trend of EMC (vs. the product reten-
of pure consolidants, as in the case of 20PP1500 and 30PP1500. tion) for the mixture in which hygroscopic products are used,
In our experimental conditions, the two mixtures of PEG 1500 whereas an inverse trend is observed for the scarcely hygroscopic
100 G. Giachi et al. / Journal of Cultural Heritage 11 (2010) 91–101

consolidants2 . However these observations are less important if not applicable in all present cases because of the serious distor-
referred to the final purpose of stabilising wood dimensions, as tions and fractures observed in the heavily degraded untreated
evident in the case of sample Q9A, treated with Klucel: it shows samples, even at 85% RH.
values of EMC similar to those of untreated wood (these lat- The results of the present work evidenced that decayed sam-
ter are not reported in Table 11), with very good dimensional ples need to be treated if they would be preserved but, despite the
stabilisation. increase in their stabilisation, many treatments failed the purpose
Finally, it is useful to make a general consideration on the of maintaining the original shape. In the same way, freeze-drying
level of precision of measurements on impregnated products. It behaved better than controlled drying (for the same treatment),
is known that permanence at high temperatures alters the chem- but however in the extremely degraded samples it is still not
ical structure of PEG because of their thermal decomposition. sufficient for their good preservation. Moreover, in some of
This influences their weight due to the formation of volatile the samples, namely those of pine belonging to group B/C, the
compounds [32–34]. However, the oven-drying of PEG-treated shrinkage is relatively small and independent of the impregnant.
samples is considered a common approach (see for instance In addition, there is little distortion or fracturing after drying,
[10,11]) and additionally in our case this condition is essential thus allowing us to conclude that they could withstand drying
for the determination of all of the weight-related measurements without treatment if the normal dimensional variation is accept-
(EMC, retention of impregnation products, density, etc.). A able. The diagnostic analysis evidenced these samples were the
quantitative evaluation of the order of this error has been there- best preserved, and they still possess an appreciable amount of
fore carried out by drying out the pure products for four days at residual polysaccharides.
103 ◦ C (as for treated wooden samples) and we found that the The retention of the impregnating products, considered as the
comprehensive variation in weight is between 1 and 4% for PEG relative weight increase of wood due to the treatments, deter-
and PPG, and it is also less in the case of Trehalose. Consider- mines most of the moisture-related characteristics of treated
ing that this measurement includes the loss of humidity (most samples: it significantly affects the dimensional stability of the
of PEG are hygroscopic), we considered the size of this error as more degraded samples and, additionally, the EMC of treated
an acceptable value. wood basically comes from the behaviour of the impregnating
products, in relation to their retention. Moreover, this behaviour
8. Conclusions depends on the level of decay of wood and on the initial
concentration of treatment solutions: the more the volume is
In order to set up a methodological approach aimed at occupied by water (measured by the MWC) the more is the
comparing several techniques of conservation of waterlogged retention.
archaeological wooden objects, the stabilisation of the original However, we considered that a treatment is really effective
size and shape of some samples was considered as the main when it confers to the wood a good stabilisation with the minimal
objective to be pursued by the treatments. Two different tech- amount of product. For this reason a quantitative definition of the
niques of drying (controlled drying and freeze-drying) were also ‘efficacy of a treatment’, ϕT , is given, in which the stabilisation
taken into account. Considering that a bibliographic survey evi- of samples for unitary retention is considered. By this way, it was
denced that there is not a unique criterion for the evaluation observed that, independent of the type of treatment, the highest
of the final behaviour of the treated samples, a methodological values of the efficacy were associated with pine samples of the
approach was developed specific for the present material. This group B/C, which also were in the best state of preservation.
approach was based on the following procedure: High values of efficacy are also associated with some samples
treated with Klucel, even though problems are associated with
• the diagnostic analysis of untreated samples, in order to assess this product and therefore an optimization of the impregnation
their state of preservation before any treatments. The proper- process is required in this case. On the other hand, the less effi-
ties to be considered were selected according to the Italian cient treatments (lowest values of ϕT ) were associated with the
standard UNI 11205:2007 [22]; techniques that use only PEG and PPG, thus implying an ele-
• the characterisation of treatment solutions ‘as such’ and the vated amount of product required for reaching an acceptable
assessment of the progress of the treatment by measuring the level of dimensional stabilisation. Finally, it is also noticeable
refractive index during the impregnation; that freeze-dried oak samples are generally those with the second
• the evaluation of the main physical characteristics of treated highest values of ϕT .
samples during a cycle of variation of the ambient relative
humidity, namely their EMC and their dimensional stability, References
in terms of shrinkage/swelling behaviour.
[1] A. Unger, A.P. Schniewind, W. Unger, Conservation of wood artefacts,
Springer-Verlag, Berlin, 2001.
One of the most common methods for the evaluation of treat- [2] C.G. Bjordal, T. Nilsson, G. Daniel, Microbial decay of waterlogged
ments is measuring the ASE but, as it was highlighted, it was archaeological wood found in Sweden, Int. Biodeterioration Biodegrad.
4 (1999) 63–73.
[3] Y.S. Kim, A.P. Singh, Micromorphological characteristics of wood
2 The extent of hygroscopicity of consolidants were evaluated in comparison biodegradation in wet environments: a review, IAWA J. 21 (2000)
to the values of untreated wood at 65% RH. 135–155.
G. Giachi et al. / Journal of Cultural Heritage 11 (2010) 91–101 101

[4] J.I. Hedges, The chemistry of archaeological wood, in: R.M. Rowell, R.J. [19] F. Kawai, K. Hanada, K. Ogata, Bacterial degradation of water-
Barbour (Eds.), Archaeological wood. Properties, chemistry, and preserva- insoluble polymer (Polypropylene Glycol), J. Ferment. Technol. 55 (1977)
tion, Advances in Chemistry Series 225, Am. Chem. Soc, Washington DC, 89–96.
1990, pp. 111–139. [20] L.R. Dean, R. Mouzouras, A.M. Jones, E.B.G. Jones, Are polyalky-
[5] D. Fengel, Aging and fossilization of wood and its components, Wood Sci. lene glycols biodegradable? in: P. Hoffmann (Ed.), Proceedings of
Technol. 25 (1991) 153–177. the 4th ICOM Group on Wet Organic Archaeological Materials
[6] D.W. Grattan, R.W. Clarke, Conservation of Waterlogged Wood, in: C. Conference–Bremerhaven 1990, Bremerhaven, 1991, pp. 91–105.
Pearson (Ed.), Conservation of Marine Archaeological Objects, Butter- [21] I.D. Donato, P. Agozzino, Composti polimerici per il consolidamento di
worth, London, 1987, pp. 164–206. legni degradati Sci. Technol. Cult. Herit. 13 (2004) 71–81.
[7] A.Oddy, S. Carrol (Eds.). Reversibility-does it exist? British Museum occa- [22] UNI 11205:2007, Beni culturali – Legno di interesse archeologico ed
sional Paper number 135, British Museum Press, London, 1999, pp.1–5. archeobotanico – Linee guida per la caratterizzazione, UNI, Milano, 2007.
[8] G. Bonsanti (Ed.) Reversibilità? Concezioni ed interpretazioni nel restauro. [23] UNI 11118:2004, Beni culturali – manufatti lignei – Criteri per
Memorie del Convegno del 12/13 aprile 2002 al Politecnico di Torino. Utet l’identificazione delle specie legnose, UNI, Milano, 2004.
Periodici, Torino, 2002. [24] A.P. Schniewind, Physical and mechanical properties of archaeological
[9] G. Bisconssi (Eds.) La reversibilità nel restauro. Riflessioni, esperienze, wood, in: R.M. Rowell, R.J. Barbour (Eds.), Archaeological wood. Prop-
percorsi di ricerca. Atti del Convegno di Studi Scienza e Beni Culturali. erties, chemistry, and preservation, Advances in Chemistry Series 225, Am.
Bressanone, 1-4 luglio 2003, Edizioni Arcadia Ricerche, 2003. Chem. Soc, Washington DC, 1990, pp. 87–109.
[10] P. Hoffmann, On the stabilization of waterlogged wood with PEG II. [25] N. Macchioni, Physical characteristics of wood from the excavations of
Designing two step treatment for multi-quality timbers, Stud. Conserv. 31 ancient port of Pisa, J. Cult. Herit. 4 (2003) 85–89.
(1986) 103–113. [26] P. Jensen, D.J. Gregory, Selected physical parameters to characterize the
[11] P. Hoffmann, On the stabilization of waterlogged softwood with Polyethy- state of preservation of archaeological wood: a practical guide for their
lene glycol (PEG), four species from China and Korea, Holzforschung 44 determination, J. Archaeol. Sci. 33 (2006) 551–559.
(1990) 87–93. [27] G. Giordano, Tecnologia del legno, Vol. 1, Utet, Torino, 1981.
[12] P. Hoffmann, To be and to continue being a Cog. The conservation of the [28] B.L. Browning, Methods of Wood Chemistry, Vol. I and II, Interscience
Bremen Cog of 1380, Int. J. Nautical Archaeol. 30 (2001) 129–140. Publishers, John Wiley and Sons Inc, New York, 1967.
[13] P. Hoffmann, The Bremen Cog project. The conservation of a big medieval [29] TAPPI, 1996–1997, Standards Technical Association of Pulp and Paper
ship, La Chimica e L’Industria 5 (2006) 96–101. Industry, 360 Lexington AM., New York 17, N.Y.
[14] P. Hoffmann, On the stabilisation of waterlogged oakwood with PEG: [30] R.W. Butler, E.D. Klug, Hydroxypropycellulose, in: R.L. Davidson (Ed.),
molecular size versus degree of degradation. Les bois gorgés d’eau : étude Handbook of Water-Soluble Gums and Resins, McGraw-Hill Book Com-
et conservation ; Actes de la 2e conférence du groupe de travail Bois pany, New York, 1980, Chapter 13.
gorgés d’eau de l’ICOM = Waterlogged Wood: Study and Conservation, [31] P. Hoffmann, The conservation of the Bremen Cog–between the steps, in:
in: Proceedings of the 2nd ICOM Waterlogged Wood Working Group T. Daley, T. Grant, P. Hoffmann, J.A. Spriggs (Eds.), Proceedings of the
Conference–Grenoble 1984, Grenoble, 1985, pp. 95–115. 6th ICOM Group on Wet Organic Archaeological Materials–York 1996,
[15] M.E. Gallina, P. Sassi, M. Paolantoni, A. Morresi, R.S. Cataliotti, Vibra- Bremerhaven, 1997, pp. 527–545.
tional analysis of molecular interactions in aqueous glucose solutions. [32] A. Brownstein, The chemistry of Polyethylene Glycol, in: D.W. Grattan
Temperature and concentration effects, J. Phys. Chem. B 110 (2006) (Ed.), J.C. McCawley (Ed. special discussion), Proceedings of the ICOM
8856–8864. Waterlogged Wood Working Group Conference, 15–18th September 1981,
[16] S. Italiano, Consolidamento dei reperti lignei provenienti da siti sommersi, Ottawa, 1982, 279–285.
Master Thesis: Materiali e tecniche diagnostiche nel settore dei beni cul- [33] M. Bilz, L. Dean, D.W. Grattan, J.C. McCawley, L. McMillen, A study on
turali, 2004. the thermal breakdown of Polyethylene Glycol, in: P. Hoffmann (Ed.),
[17] D.I. Donato, P. Agozzino, D. Bulone, Physico-chemical characterisation T. Daley, T. Grant (Eds. special discussion), Proceedings of the 5th
of polymeric mixtures suitable for a conservative treatment of water- ICOM-WOAM Conference – Portland, Maine 1993, Bremerhaven, 1994,
logged wood, in: C. Bonnot-Diconne, X. Hiron, Q. Khôi Tran, P. Hoffmann 167–197.
(Eds.), Proceedings of the 7th ICOM-CC Working Group on Wet Organic [34] E. Bouquin, A. Crawshaw, Recent literature on PEG degradation,
Archaeological Material Conference = Actes de la 7e conférence du groupe in: P. Hoffmann, K. Strætkvern, J.A. Spriggs, D. Gregory (Eds.),
de travail Matériaux archéologiques organiques humides–Grenoble 1998, Proceedings of the 9th ICOM Group on Wet Organic Archaeo-
Grenoble, 1999, p. 322. logical Materials Conference – Copenhagen 2004, Bremerhaven, 2004,
[18] I.D. Donato, P. Agozzino, D. Bulone, Deteriorated woods consolidation: pp. 627–628.
physico-chemical properties of wood-polymer composites, in: J. Alpuente, [35] I.D. Donato, in press, Physical properties of waterlogged wood. Measure-
I. de Bustamante, O. García, P.L. López, A. Marcos, J. de Pedro, et al. (Eds.), ments with Accupyc 1330, Helium pycnometer. Proceedings of the 10th
Proceedings of the 3rd International Conference Science and Technology ICOM Waterlogged Wood Working Group Conference – Amsterdam 2007.
for the safeguard of Cultural Heritage in the Mediterranean Basin – 2000, [36] G. Tsoumis, Science and technology of wood, Chapman & Hall, New York,
Alcalà, 2001, pp. 1–6. 1991.

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