Journal of Molecular Structure 735–736 (2005) 267–270

www.elsevier.com/locate/molstruc

Water structure in polyethylene glycols for preservation of wooden

artefacts. A NIR-FT-Raman spectroscopic investigation*
M. Christensena, O.F. Nielsena,*, P. Jensenb, U. Schnellb
a
Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen, Denmark
b
Department of Conservation, The Natural Museum of Denmark, P.O. Box 260, 2800 Lyngby, Denmark
Received 14 September 2004; revised 20 October 2004; accepted 20 October 2004
Available online 8 December 2004

Abstract
The interaction between polyethylene glycol (PEG) and water in mixtures has been investigated with a particular emphasis on the
existence of ‘free’ water with a tetragonal bulk-like water structure. PEG is used in museum preservation of wooden objects, where free water
must be avoided due to the danger of further microbial growth, contractile capillary forces and aqueous transport in wooden
archaeological artefacts. A NIR-FT-Raman instrument with excitation at 1064 nm was used for this investigation. The OH stretch region
around 3200 cmK1 shows changes in intensity with changing water content and the R(n)-function
 was applied in order to observe free water
in the 100–300 cmK1 region. Mixtures of PEG and water were investigated with water contents ranging from 0 to 90% volume. It was found
that free water appears around 28–32% volume in a PEG 600 mixture.
q 2004 Elsevier B.V. All rights reserved.

Keywords: Polyethylene glycol (PEG); NIR-FT-Raman spectra; Free water

1. Introduction
Wooden artefacts are often found throughout Scandina-
via—from tools and weapons to entire ships. These items
give us a glimpse of our prehistory. Especially the Nydam
bog, located in Southern Denmark near the German border,
has played a dramatic role in Danish prehistory. It is famous
for its artefacts—especially the Nydam Boat. Between 200
and 600 AD the peat bog was a sacred lake into which the
equipment of the defeated warriors was lowered—tools,
weapons, and even ships! As such many important artefacts
from that period have been preserved in the bog. Although
the original excavations began in 1859 they ceased as a war
between Denmark and Germany broke out in 1864. Several
excavations followed. In 1989, the Danish National Museum
resumed the excavations and many important discoveries
*
Dedicated to Professor Hiroaki Takahashi on the occasion of his 70th
anniversary. OFN and his wife have many fond memories from pleasant
and relaxed meetings all over the world with Professor Takahashi and his
wife.
* Corresponding author. Tel.: C45 35320321; fax: C45 35320322.
E-mail address: ofn@kiku.dk (O.F. Nielsen).
0022-2860/$ - see front matter q 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2004.10.090
have been made during the 90’s, enhancing our under-
standing of the late Roman to Germanic Iron Age [1,2].
Even newer finds are often of significant cultural value,
like the Swedish ship ‘Vasa’ which sunk in 1628, but can
now be viewed in its former splendour [3].
Polyethylene glycol (PEG) is widely used in preservation
of the waterlogged wooden objects. Today a great deal of
emphasis is put on avoiding free water in these PEG
preserved wooden artefacts since, it may cause further
degradation due to microbial growth, contractile capillary
forces and aqueous transport. The present study is focussed
upon determining the amount of free water in PEG solutions
with water contents ranging from 0 to 90% volume.
2. Wood conservation in museum collections
When waterlogged wooden objects are excavated they
are often heavily degraded. Anoxic conditions are optimal
for storing these items—because most bacteria and fungi
require oxygen to successfully degrade the wood. Unfortu-
nately, some degradation is bound to occur. If the degraded
268 M. Christensen et al. / Journal of Molecular Structure 735–736 (2005) 267–270

wood is simply dried it will often collapse due to contractile

capillary forces, and may shrink due to removal of bound
water in the cell wall. Thus it is necessary to find an agent
with both stabilising and bulking capabilities. After
preservation it is important that there is no free water so
that microbial growth, contractile capillary forces and
aqueous transportation is limited. PEG is the most common
agent used.
PEG is made up of linear H(OCH2CH2)nOH units with a
varying average chain length. For the present study PEG
600 (570–630 g/mol) was chosen as it is a relatively long
molecule but still liquid at room temperature. The average
chain length of PEG 600 is 13 units.
The impregnation of the waterlogged wood starts by
lowering the wood into an aqueous solution of 10% PEG by
weight. The concentration is gradually raised to 40%.
After treatment with PEG the wood is freeze–dried to
remove the water.
It is of the greatest importance to be able to detect water—
especially free water—within the samples and preparatory
solutions. The term free water is used for water with a local
structure (order) as found in pure liquid water. A low-
wavenumber Raman band, mainly due to displacements of
the oxygen atoms shows the presence of free water, whereas
the OH-stretching region in the Raman spectrum is sensitive
to the total amounts of water—free and bound [4,5]. Recently
NIR-FT-Raman spectroscopy was used to determine the
presence of free water in normal and cancerous skin [6]. In
the present contribution NIR-FT-Raman spectroscopy will
be used to investigate PEG/water mixtures with particular
emphasis on determination of free water with a tetragonal
bulk-like structure.
3. Experimental
Fig. 1. NIR-FT Raman spectrum of pure water.
The spectrum of PEG 600 can be seen in Fig. 2. The most
intense band from the multiple types of CH-stretching
appears at 2874 cmK1. The OH-stretching bands expected
above 3000 cmK1 show too low intensities to be observed.
A series of spectra with water content from 0 to 90%
volume were recorded to roughly determine when free water
appeared. In addition, a more thorough examination at water
concentrations from 24 to 36% volume was conducted in
order to determine this point more accurately.
4.1. Water content 0–90%
For each spectrum 125 scans were recorded. This can be
accomplished in about 4 min per spectrum. A windowless
cell [7] was used to obtain the spectra since, only about 2%
water would evaporate during this short recording time.
The OH and CH stretching region is shown in Fig. 3.
These spectra have been normalised, using the CH
stretching vibration at 2950 cmK1 as a base standard.

The R(n)-representation is useful for small peaks near the
Rayleigh line, because the Rayleigh line is converted to a
plateau [8,9]. This representation is defined in Eq. (1)

The examined PEG 600 (570–630 g/mol) samples were

 K eKhnc=kT
nð1 
ÞIðnÞ

obtained from Clariant and examined on a Bruker-IFS66 RðnÞ
 Z (1)
4
ðnl K nÞ
interferometer with a FRA 106 FT-Raman module and a
liquid nitrogen cooled Ge-detector. All spectra were
recorded with a Nd/YAG laser at 1064 nm at an output of In the above, nl is the wavenumber of the exciting laser
280 mW. The spectral resolution was 6 cmK1 after (9394 cmK1). n is the chosen Raman shift wavenumber
apodisation. Spectra were obtained in either a windowless and IðnÞ
 is the corresponding intensity. As usual k is
cell [7] or a quartz tube with a 2 mm inner diameter.

4. Results and discussion

The NIR-FT-Raman spectrum of pure liquid water is

shown in Fig. 1. Due to loss of detector sensitivity only the
symmetric OH stretching around 3250 cmK1 is seen in the
OH-stretch region. A notch filter cuts off the low-
wavenumber region at around 80 cmK1. Thus the Rayleigh
band maximum at 0 cmK1 is not seen, but even at Raman
shifts from 80 cmK1 and greater the Rayleigh band shows a
significant intensity. Fig. 2. Raman spectrum of pure PEG 600.
 M. Christensen et al. / Journal of Molecular Structure 735–736 (2005) 267–270 269

Fig. 3. Normalised spectra of PEG and water mixtures (CH and OH stretching area).

the Boltzmann constant while T is the absolute temperature
and c the velocity of light.
Prior to calculation of the R(n)-representation
 the
intensity minimum at about 380 cmK1 was subtracted
from the spectra.
After transformation of the spectra to the R( n)-  examination is required.
representation they were normalised using the PEG peak
at 295 cmK1 as a standard. The spectrum of pure PEG 600
was subtracted from all the spectra in a series.
The results of these studies are twofold. First of all it can
be seen from Fig. 3 that the OH stretching intensity
increases with an increasing water concentration. There is
certainly not a linear dependence of the increase of the OH-
stretch intensity with an increasing water content. However,
both free and bound water contribute to this band and no
distinction between free and bound water can be made. This
is not the case, where the oxygen motion at 180 cmK1 is
concerned. This peak appears at a certain concentration,
signifying free water (see Fig. 4) [5,7]. Secondly, by
observing the appearance of this peak, a rough determi-
nation of the point, where free water exists in the solution is
possible.
As can be seen in Fig. 4, the 180 cmK1 band appears in
solutions with water concentrations above 40% volume,
showing that free water is obviously present in the solution
this concentration or above, and may even be present at a
lower concentration. Thus, we should expect free water to
be present at a lower concentration than 40% volume. In
order to pinpoint the exact ratio a more thorough
4.2. Water content 24–38%
To improve the signal-to-noise ratio of the spectra another
series was recorded, this time using 2000 scans per spectrum.
Thus each recording takes about 50 min, meaning that water
would certainly evaporate from a windowless cell during the
recording. Since, a single recording is so time-consuming
only a small range of solutions, selected around the point,
where free water appears, were examined. To minimise water
evaporation the sample was contained in the quartz tube.
Since, the same tube must be used for each and every
spectrum in order to subtract the background, the cleaning of
the tube obviously adds to the time required to record the
spectra. As above spectra were converted using the R(n)- 
representation and the spectrum of pure PEG was subtracted.
It should be noted that the shape of the band at 295 cmK1
is altered with increasing water content. As a result of this

Fig. 4. R(n)
 transformed spectra of PEG and water mixtures.
270 M. Christensen et al. / Journal of Molecular Structure 735–736 (2005) 267–270
Fig. 5. R(n)
 transformed spectra of a narrow concentration range of PEG and water mixtures.
an indentation (seemingly a kind of ‘negative peak’) is seen
in Fig. 5 in the 220–280 cmK1 region. It is determined (see
Fig. 5) that free water appears around 28–32% volume.
5. Conclusion
Mixtures of PEG 600 and water (10–90% volume) were
investigated using NIR-FT-Raman spectroscopy. Using a
windowless cell a rough indication of the point, where free
water occurs was obtained. In order to find this point more
accurately, however, the mix must be contained in a quartz
tube during the recording of the spectra to avoid water
evaporation. In the current investigation free water appears
at 28–32% volume.
It was hoped that a distinction could be made between
free and bound water in the mixture, since, the presence of
free water is problematic in conserved wooden objects.
These studies have shown that Raman spectroscopy is a
usable method for determining free water content in PEG
solutions. This method will be useful both in future direct
studies of preserved wooden artefacts as well as in studies of
the method of preservation itself.
Acknowledgements
OFN wants to thank the Danish Research Academy for a
general grant during this study (grant no. 51-00-0312).
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