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Lukasz Bratasz, Roman Kozlowski, Antonina Kozlowska and Bartosz Rachwal Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, ul. Niezapominajek 8, 30-239 Kraków, Poland Abstract ‘General’ moisture sorption and swelling/shrinkage patterns which would apply as a first approximation to any wood species constituting cultural objects were proposed. They were obtained from the experimental data measured for 21 historically important wood species used in the past for panel paintings and woodcarving. Information on further wood species of interest to the wood conservation community can be added to the database and used to constantly improve the general relationships.
Uncontrolled variations of ambient temperature and relative humidity have been the principal agents of deterioration for historic and artistic wooden objects. The variations in the environment induce physical damage to the wood due to its hygroscopic nature and dimensional response to the moisture sorption or desorption. Over the centuries, a great number of wood species have been used for constructional, utilitarian and decorative purposes with each geographic region, historic period and application field favouring specific woods for reasons of availability, ease of processing or fashion. Therefore museum collections or interior furnishings of historic buildings are mixture of various wood species having different responses to climatic variations. Wood variability within species and due to aging adds an additional dimension to the complexity of the problem. As a result, acquiring information on moisture sorption and related dimensional response by wood species present in a particular collection or building can be rarely possible due to high cost and long time necessary for the laboratory work, as well as a difficulty in withdrawal of samples from cultural objects. By necessity, the assessment of wood damage risk related to the fluctuating climate should be rather based on some general climate – wood relationships which for most practical purposes could be applied to mixed wood collections or furnishings. Therefore, the main aim of this study was to evaluate water vapour sorption and dimensional response for 21 historically important wood species used in the past for panel paintings and woodcarving and to propose a ‘general’ moisture sorption and swelling/shrinkage patterns which would apply as a first approximation to any wood species constituting cultural objects, as well as ranges of moisture uptake and dimensional response behaviour which can be expected.
2. MATERIALS AND METHODS
Wood species selected for this study are listed in Table 1. The selection was based on the list of types of woods used in the past for panel paintings and woodcarving published by Grosser and Geier  for softwoods, and by Grosser and Grässle  for hardwoods. The specimens were obtained from defectfree wooden boards seasoned for at least 3 years at room conditions at the restoration workshop of the National Museum in Krakow, Poland. Moisture adsorption and desorption isotherms were determined at 20oC and for a full range of water vapour relative pressures. The measurements were done gravimetrically with the use of a Sartorius vacuum microbalance. Typically, a 0.05 g piece of wood was weighed and outgassed prior to a measurement under a vacuum of a residual pressure less than 10-3 mbar. The aim was to move air out of the wood and to eliminate most of the species physisorbed during storage of the sample, especially water. Vacuum was maintained until a constant weight was obtained, then subsequent portions of water vapour were introduced, and the respective mass increases due to the sorption and the respective equilibrium pressures were recorded. Samples were considered to have reached equilibrium when the
weight changes were less than 0.05% in 40 minutes. The equilibrium moisture contents (EMC) were calculated on the basis of the initial weight of the out-gassed sample. The dimensional change of wood accompanying water vapour sorption was measured in the radial and tangential directions using two inductive transducers of accuracy 2 µm. The dimensions of wood specimens coincided with the principal anatomical directions in wood – radial 2 cm x tangential 2 cm x longitudinal 0.5 cm. The measurements were taken in a specially built specimen holder placed in a vacuum vessel. The vessel was connected to the same outgassing and water vapour dosing system which was used to determine water vapour sorption isotherms; in fact the two measurements were taken simultaneously. Both absorption and desorption branches of the sorption and dimensional change isotherms were recorded. The process was fully automated and rapid - measuring of 10 adsorption and 10 desorption points took on average 15 hours. After the measurements of dimensional changes induced by water vapour sorption and desorption, each wood specimen was immersed in distilled water until full saturation. At the saturation state, its dimensions were measured with a micrometer.
3. SORPTION ISOTHERMS
The sorption of water on wood can be described by sigmoid shape of the type II isotherm in the IUPAC 1985 classification . It indicates the monolayer-multilayer physisorption in which an adsorbed surface layer progressively thickens as the vapour pressure is increased up to the saturation pressure, close to which the adsorbed layer becomes a bulk liquid. The three-parameter GuggenheimAndersen-de Boer sorption equation  is used to interpret the sorption data for wood by expressing the equilibrium moisture content as a function of water vapour activity:
v(a0 ) =
vm cka0 (1 − ka0 )(1 + (c − 1)ka0 )
where a0 is water vapour activity taken equal to p/p0 where p is the experimental partial water vapour pressure and p0 its value at saturation (thus if RH is the relative humidity expressed as a percentage a0 = RH/100), v the amount water vapour sorbed by a gram of wood at water vapour activity a0, vm the monolayer capacity in the same units as v, c - energy constant related to the difference of free enthalpy of water molecules in the liquid state and in the monolayer, and k - the third parameter, characterizing the state of the sorbed molecules beyond the first layer. The usefulness of the GAB model in the wood science has been demonstrated . In the present study, the GAB constants were determined by a least-squares regression of the GAB relation for a0 < 0.85, identified as the applicability interval. The regression was performed separately for the adsorption and desorption branches. By way of example, the experimental data for water vapour sorption by the lime wood are compared in Fig. 1 with curves calculated using the GAB equation. RH scale is used on the ordinate axis of the plot. The GAB constants for adsorption and desorption for the lime wood, as well as 20 other wood species investigated, are given in Table 1. As one can see in Fig. 1, the applicability range for the GAB equation for the adsorption branch is 0.05<a0<0.85 and an upswing of the adsorption points above the upper limit of this range is observed. The shape of the isotherm has been interpreted in terms of 3 sorption stages occurring as the water activity increases: the direct adsorption of water molecules on the sorbent within a monolayer, the formation of the multilayer film of water molecules beyond the first layer, and the formation of the liquid-like water interacting insignificantly with the solid due to the increased distance. For the desorption branch, the hysteresis effect is observed i.e. higher moisture content after desorption when compared to that after adsorption at any given RH value. The applicability range for the GAB equation is wider and covers the highest RH range close to 100%. It can be seen that the monolayer value obtained for desorption is higher than the adsorption value (7 compared to 5 grams of water per 100 g of wood). Further research must elucidate if the effect can be explained by a real increase of the internal surfaces with more adsorption sites made available in the material or a delayed removal of water entrapped in the smallest capillaries and channels in wood on desorption.
Figure 1 – Adsorption and desorption isotherms of water vapour for lime wood at 20oC: solid line shows prediction of the GAB equation for adsorption (green) and desorption (red) branches.
The ‘general’ or ‘average’ water vapour sorption isotherm was calculated by fitting the GAB equation to the adsorption and desorption data for all 21 wood species and is shown in Fig. 2. The data for the least sorbing specimen (dark fossil oak wood) and the most sorbing one (mahagony) are given for comparison. The average values of the GAB constants calculated from the adsorption data were: vm = 6.83 g H2O per 100 g of wood (range: 5.65 – 9.13), c = 8.61 (range: 3.98 – 14.16), k = 0.66 (range: 0.45 – 0.74).
Figure 2 – The average adsorption and desorption isotherms of water vapour at 20oC: the adsorption data for the least sorbing (dark fossil oak wood) and the desorption data for the most sorbing (mahagony) wood species are shown for comparison.
Table 1: GAB constants for water vapour adsorption and desorption isotherms for 21 species of wood as well as their coefficients of tangential and radial dimensional change Species vm*10-2 Softwoods pine (Pinus spp.) Japanese cypress (Chamaecyparis obtusa) spruce (Picea spp.) larch (Larix decidua) fir (Abies spp.) Hardwoods sycamore (Acer pseudoplatanus) oak (Quercus spp.) dark fossil oak wood rosewood (Dalbergia spp.) walnut (Juglans spp.) cherry (Prunus avium) lime (Tilia spp.) sour cherry (Prunus cerasus) elm (Ulmus procera) poplar (Populus spp.) mahogany (Swietenia mohagoni) beech (Fagus sylvatica) birch (Betula pendula) willow (Salix spp.) apple (Malus domestica) ash (Fraxinus excelsior L) Average 7.25/10.07 7.58/10.19 6.82/7.96 7.07/7.33 7.40/11.35 6.67/12.49 6.19/11.1 7.57/11.13 6.11/9.84 5.88/10.41 5.91/8.64 4.51/7.69 6.80/8.15 5.65/9.07 5.95/8.13 7.80/11.18 6.98/11.92 6.67/10.60 6.59/9.07 6.83/14.95 6.63/6.54 6.83/9.36 Adsorption/desorption c 13.5/8.21 4.38/7.41 k 0.49/0.44 0.63/0.53 Dimensional change coefficients tangential radial 0.38 0.23 0.34 0.45 0.32 0.38 0.33 0.62 0.21 0.25 0.30 0.29 0.31 0.27 0.28 0.36 0.30 0.20 0.35 0.29 0.13 0.12 0.14 0.13 0.12 0.19 0.19 0.39 0.33 0.14 0.14 0.19 0.16 0.17 0.12 0.11 0.17 0.21 0.07 0.20 0.21
10.04/12.49 0.74/0.70 9.89/9.05 0.74/0.72 8.90/7.55 0.66/0.50 9.01/7.01 7.36/7.26 7.36/12.50 9.31/7.38 7.35/4.36 9.89/7.01 7.42/4.70 8.74/9.83 14.16/7.03 9.58/7.88 10.00/7.86 7.11/4.88 7.85/5.64 8.03/7.03 7.70/5.15 8.92/8.32 8.61/7.59 0.58/0.30 0.72/0.51 0.45/0.24 0.66/0.53 0.69/0.56 0.72/0.66 0.79/0.66 0.69/0.71 0.74/0.66 0.73/0.68 0.65/0.59 0.70/0.53 0.71/0.57 0.73/0.66 0.73/0.64 0.68/0.20 0.66/0.57
4. Dimensional change isotherms
The amount wood specimens swell or shrink was measured as relative dimensional change versus RH. The relationships were described by fitting the polynomial of degree 3 to the adsorption (swelling) and desorption (shrinkage) data. As for the sorption isotherms, the ‘average’ swelling and shrinking isotherms were calculated by fitting the data for all 21 wood species and they are shown for the tangential and radial directions in Fig. 3. The constant coefficients of the polynomial a0 to a3, for the swelling and shrinkage, are listed in Table 2.
Table 2: The constant coefficients of the polynomial predicting the average swelling and shrinkage isotherms.
swelling tangential swelling radial shrinkage tangential shrinkage radial
a0 -0.0088 -0.0031 0.0131 0.0051
a1 4.8412 3.0628 5.2690 3.5639
a2 -5.1062 -3.1238 0.6517 -0.6023
a3 6.0800 3.2034 -0.4018 -0.0461
Figure 3 – The average dimensional change isotherms for the adsorption and desorption of water vapour at 20oC.
A convenient way of expressing swelling and shrinkage behaviour of individual wood species is to plot dimensional change as a function of EMC. By way of example, such relationship is shown in Fig.4 for the tangential and radial directions in the lime wood. All the experimental points for the EMC values between 0 and 25% were obtained by adsorption and desorption of water vapour at varying RH whereas the last point corresponds to a wooden specimen fully saturated under distilled water. Generally, the measurements did not show any differences between the dimensional change values at the same EMC but obtained after adsorption or desorption. In this way, the so-called secondary effects of moisture sorption on dimensional changes  proved insignificant at least for any practical purposes. .
Figure 4 – Dimensional change of lime wood in the radial and tangential directions plotted as a function of the equilibrium moisture content.
The three parameter sigmoid function was used to interpret the individual swelling and shrinkage data:
d ( EMC ) = d max
EMC n k n + EMC n
where EMC is the equilibrium amount of water vapour sorbed, d the relative dimensional change at a given EMC and dmax reflects the maximum dimensional change for wood saturated with water. The function shows an early exponential growth at low EMC, then slows to a linear growth for the broad medium part between approximately 5-15%, and then approaches a constant value as the capillary system of wood is saturated with water. The dimensional change coefficients were determined by the linear fit across the linear range of the plots and are given in Table 1.
In addition to individual sorptive characteristics and dimensional responses of wood species, constituting cultural heritage objects, ‘general’ moisture sorption and swelling/shrinkage patterns which would apply as a first approximation to any wooden furnishings and collections were proposed. They were obtained from the experimental data measured for 21 historically important wood species used in the past for panel paintings and woodcarving. Information on further wood species of interest to the wood conservation community can be added to the database and used to constantly improve the general relationships.
A substantial part of this research was done within the project ‘Sensor systems for detection of harmful environments in pipe organs’ (SENSORGAN), supported financially by the European Commission 6th Framework Programme.
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