Nuclear Instruments and Methods in Physics Research B 213 (2004) 670–676

www.elsevier.com/locate/nimb

The use of radiation for the study of material of

cultural heritage significance
D.C. Creagh *, V. Otieno-Alego
Cultural Heritage Research Centre, Division of Science and Design, University of Canberra, Canberra, ACT 2601, Australia

Abstract

For the indigenous people of Northern Australia the expression of their experience of life, their ‘‘dreaming’’, is in the
form of painting, usually on the bark stripped from trees growing in their tribal lands. These are often works of great
beauty and the major collecting institutions in Australia and elsewhere have significant holdings of Aboriginal bark
paintings. A wide range of analytical techniques (optical microscopy, FTIR microscopy, Raman microscopy, scanning
electron microscopy and energy dispersive X-ray spectroscopy, and synchrotron radiation X-ray diffraction) has been
used in a project to determine how best to conserve Aboriginal bark paintings.

2003 Elsevier B.V. All rights reserved.

Keywords: Cultural heritage; Aboriginal bark paintings; Raman microscopy; FTIR microscopy; Scanning electron microscopy; Energy
dispersive X-ray analysis; Synchrotron radiation X-ray diffraction

1. Introduction conservation, transportation, and display of Ab-

The art of the indigenous people of Arnhem
Land, in Northern Australia, principally takes the
form of painting on bark stripped from the Dar-
win stringy-bark tree (eucalyptus tetradonta).
Stylistically the subject matter is the same as found
in caves and rock shelters, and relates to the
‘‘dreaming’’ of the artist: the personal interpreta-
tion of the artist of his cultural identity. The major
collecting institutions, the National Gallery of
Australia and the National Museum of Australia,
have a strong interest in all aspects of their storage,
original artefacts to the public. The research was
conducted with the active participation of indige-
nous communities (the Maningrida, Oenpelly, and
Yirrkala communities in particular). In this paper
a brief outline of the techniques of producing bark
paintings will be given. Results will then be given
of studies using an array of analytical tools (opti-
cal microscopy, FTIR microscopy, Raman mi-
croscopy, scanning electron microscopy and
energy dispersive X-ray spectroscopy, and syn-
chrotron radiation X-ray diffraction) for the study
of the bark material, the pigments, and the binders
used to enable the pigments to adhere to the bark.

*
Corresponding author. Address: Division of Management 2. Experiments
and Technology, University of Canberra, Canberra 2600,
Australia. Tel./fax: +61-2-6201-2048.
E-mail addresses: dcreagh@bigpond.net.au; dudleyc@ise. The three components of bark paintings which
canberra.edu.au (D.C. Creagh). are of interest scientifically are [1,2]: the bark, the

0168-583X/$ - see front matter
2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0168-583X(03)01684-7
 D.C. Creagh, V. Otieno-Alego / Nucl. Instr. and Meth. in Phys. Res. B 213 (2004) 670–676 671

pigments, and the binders used to cause the pig-

ments to adhere to the bark. Of these the least
familiar component to conservators from the
Northern Hemisphere is the bark. The bark is
harvested from the Darwin stringy-bark (euca-
lyptus tetradonta) usually at the end of the ‘‘wet’’
season (March–May). Eucalyptus tetradonta is a
tall, straight growing tree, which bears its canopy
at its top. The barks stripped from the tree can be
4 m high and 1.5 m wide. The time of harvesting
depends on the whether the bush can be accessed
by the community. After harvesting the further
treatment of the barks varies from community to
community, artist to artist. At Yirrkala the bark is
flattened by weighting, but not generally fired. At
Maningrida and Oenpelly the bark may be fired
internally, externally, or both, and then flattened
by weighting. By ‘‘firing’’ is meant the heating of
the bark over a fire of bush debris, or placing the
burning debris inside the curled-up bark.
Of significance is the question as to what the
processes of firing and/or flattening does to the
mechanical properties of the bark, especially to its
reaction to variations of temperature and humid- Fig. 2. (a) Unfired bark (optical microscopy) showing starch
ity. Optical and scanning electron microscopy of grains. (b) Fired bark (optical microscopy). Note absence of
sample barks show that firing, especially firing starch grains.
inside and outside, has a marked effect on the
structure of the bark. Fig. 1 shows a scanning
electron microscope image of starch grains in more ‘‘homogeneous’’ and less susceptible to en-
vertical vesicles in a bark. The starch grains in an vironmental changes. This is of significance from
untreated bark shown in Fig. 2(a) are seen to have the point of view of their transport and storage.
broken down and fill the cavities after firing (Fig. All barks, however, fluctuate dimensionally with
2(b)). The consequence of this is to make the bark environmental changes, making the design of
hangers and storage drawers complicated. Time-
lapse digital photography has been used exten-
sively to study the movement of barks (Fig. 3).
Determination of the point of zero flexure is im-
portant from the point of view of establishing how
best to support the bark in a mounting frame.
A tribal artist will have prepared the flattened
bark surface prior to painting with binding mate-
rial. Prior to 1974 this may have been orchid juice,
but in recent times materials such as polyvinylac-
etate (PVA) have been used. A recent survey has
been undertaken by Gatenby [3]. There is a consid-
erable degree of variability in the binding material
Fig. 1. Scanning electron microscope image of starch grains in and pigments used by artists. Many traditional
a vertical vesicule in bark. artists still have their own source of pigments,
672 D.C. Creagh, V. Otieno-Alego / Nucl. Instr. and Meth. in Phys. Res. B 213 (2004) 670–676
Fig. 3. Time lapse digital photography of the edge of a typical
Aboriginal bark painting Showing the effect of variation of
temperature and humidity. Top: 37%, 27 C; centre: 50%, 25 C;
bottom: 60%, 25 C.
which they only use. Most do not share either
binders or pigments with others.
3. Studies of pigments and binders
A FTIR spectrometer is a very common ana-
lytical device for studying pigments and binding
agents. An infrared spectrometer analyses the
frequency of the infrared photons absorbed by the
sample. Absorption occurs in the vibrational
modes of crystal structures and molecules within
the sample. Measurement of absorption provides a
means of identification of the molecular species
present in the sample by comparison of the band
characteristics of the unknown species with those
of standard materials. Most functional groups
such as O–H, N–H, C@O have characteristic lo-
calized modes allowing for their easy identification
on different samples. Other techniques use scat-
tering rather than absorption of IR radiation, in
particular, inelastic or Raman scattering. We have
used this technique extensively for the analysis of
pigments and binders.
4. Raman microspectroscopy
Most of the incident radiation scattered by a
sample is scattered elastically. However, a small
part of the incoming radiation (approximately 1
part in 1010 ) interacts with the sample and is
scattered inelastically (Raman scattering) re-
emerging with a different frequency (energy). A
Raman spectrometer is configured to reject the
elastically scattered, and accept the inelastically
scattered, radiation. A microscope attachment to a
Raman spectrometer (Fig. 6) facilitates the study
of very small amounts of material, or domains
within materials, with high spatial resolution (1
lm), an important feature if the particular pig-
ments to be identified in a mixture of pigments.
The technique combines the desirable attributes of
being non-destructive, reliable, sensitive and lar-
gely immune to interference from other materials
within the matrix (other pigments and binders). It
can be used in situ which makes it possible to study
valuable artefacts for which sampling is forbidden.
No two unique molecular structures produce
the same Raman trace, and a particular combi-
nation of Raman peaks provides an unequivocal
identification of the molecular species.
FTIR and Raman spectroscopy are comple-
mentary techniques. Vibrations that are strong in a
Raman spectrum are usually weak in an infrared
spectrum and vice versa. Qualitatively, antisym-
metric vibrational modes and vibrations due to
polar bonds (such as O–H, N–H, C@O) generally
exhibit prominent infrared bands, while Raman
tends to emphasize vibrations involving more
symmetrical bonds (such as C@C, C–C, S–S). As
with FTIR, complete compound identification is
possible with Raman microspectroscopy by com-
paring band characteristics of the unknown species
with those in commercial or in in-house computer
databanks.
The objective lens of the microscope (Renishaw
2000 Ramascope) may be replaced by an adaptor
which views the sample sideways (a macropoint
adaptor) enabling the study of large objects placed
on an xyz stage to enable accurate positioning of
the object. Each of the major colours present on an
Aboriginal bark painting Fig. 4 was positioned
under the microscope and analyzed (using a ·20
microscope objective). The spectrum from the
black sections (Fig. 4(A)) indicates the presence of
lamp black whilst that recorded for the white
sections (Fig. 4(B)) indicates the presence of the
 D.C. Creagh, V. Otieno-Alego / Nucl. Instr. and Meth. in Phys. Res. B 213 (2004) 670–676 673

Fig. 4. Raman spectra (red lines) of the pigments used on: (A) black, (B) white, (C) red and (D) deep yellow sections on a bark
painting. Reference spectra (black lines) are included for identification purposes.

clay, kaolin, with characteristic anatase (TiO2 , a
white pigment) peaks at 145, 395, 512 and 639
cm 1 . The Raman signatures (red lines) unequiv-
ocally show that mars red (synthetic iron(III) ox-
ide) and mars yellow (synthetic iron(III)
hydroxide) were used as the red and yellow pig-
ments instead of the traditional mineral pigments
(yellow and red ochres, respectively) (see Fig. 4(C)
and (D)).
The Raman traces from the yellow sections of
the painting also show peaks suggesting the pres-
ence of polyvinyl acetate (PVA, Fig. 4(D)), which
is often used as a binder in bark paintings [20].
The microscope has been used in the Direct
Imaging mode, in which the objective is defocused
and filters are used to select a dominant band for a
particular material, the result of which is an image
showing the location of materials of that type. It
has been used to investigate pigments embedded in
transparent or translucent medium such as natural
waxes, egg white, natural plant resins and gums
commonly used as binders on bark paintings. As
674 D.C. Creagh, V. Otieno-Alego / Nucl. Instr. and Meth. in Phys. Res. B 213 (2004) 670–676
well, confocal techniques have been used in con-
junction with a motorized xyz sample stage to map
particular materials in small samples.
In general Raman microspectroscopy has
proved to be an excellent technique for the ob-
jects examined in this project. Care had to be taken
to avoid sample fluorescence and the photo-de-
gradation of labile materials under laser illumina-
tion.
5. Fourier transform infrared (FTIR) spectroscopy
The spectrum shown in Fig. 5 was recorded
non-destructively on a nanogram sample taken
from an Aboriginal bark painting by simply flat-
tening the specimen onto a diamond cell window.
The recorded FTIR spectrum contained absorp-
tion bands which were indicative of mars yellow
(Fe(OH)3 , synthetic yellow ochre: peaks at 3400
(broad, O–H), 902 and 796 cm 1 ) and peaks
characteristic of polyvinyl acetate (2960, 2925,
2873 (C–H), 1739 (C@O), 1433, 1375 (C–H), 1240,
1118, 1024, 945 cm 1 (C–O)). Identification of the
binding medium by FTIR is sufficient only if the
general category of the binding medium is needed,
e.g. drying oil, wax, resin, gum or a proteinaceous
material. The technique cannot be used to char-
acterize these compounds further, with certainty.
Other destructive techniques such as GC-MS,
% Transmittance
500 1000 1500 2000 2500 3000
Wavenumber (cm-1)
Fig. 5. FTIR spectrum of a nanogram of sample taken from an
Aboriginal bark painting.
which unequivocally identifies the binding medium
must be used, and even then the degradation of the
binding agent may be such that identification of
the original binder may not be possible.
Raman microscopy can identify directly min-
eral types, but only in favourable circumstances
can it discriminate from minerals of the same kind
from different regions. For the white pigment in
the barks the clay kaolin is a common ingredient.
Kaolin has a wide range of compositions accord-
ing to location [4]. To distinguish the variation of
pigments from different regions other less direct
techniques such as micro-X-ray fluorescence
spectroscopy and synchrotron radiation X-ray
diffraction must be used.
Micro-XRF spectroscopy has been used to
identify the distribution of elemental abundance
on objects of moderate size using a Kevex Om-
nicron microanalyzer fitted with an xy stage [5].
The X-ray source is an side-window microfocus
rhodium X-ray tube. Elemental mapping with
accuracies close to that of micro-Raman mapping
is possible. Fig. 6 illustrates the difference be-
tween two white pigments taken from sites sepa-
rated in distance by 120 km. Sample A has more
silicon and titanium and less iron than Sample B.
But there is a question as to whether there is
another phase containing iron present in the
samples.
To determine whether this is so, and to deter-
mine the relative proportions in each phase, syn-
chrotron radiation XRD has been undertaken at
the Australian National Beamline, Beamline 20B,
Photon Factory KEK, Tsukuba, Japan, using
their vacuum diffractometer in conjunction with its
eight position capillary spinning stage and Weiss-
enberg slit. Results of these experiments have yet
to be analyzed in detail. They do confirm the
presence of kaolin, anatase, and a third phase,
possible to be related to goethite (FeOOH).
However exact determination of phase composi-
tion is compromised by the presence of a strong
amorphous background. Whether this is due to
structural disorder in the kaolin of the existence of
3500 4000
another (amorphous) compound has yet to be
determined. A new method of analyzing the
amorphous background is being developed to re-
solve this issue [6].
 D.C. Creagh, V. Otieno-Alego / Nucl. Instr. and Meth. in Phys. Res. B 213 (2004) 670–676
Fig. 6. Micro-XRF spectra from pigments from two pigments from different regions. Sample A has more silicon but less titanium and
iron than Sample B.
6. Conclusions
To study the Aboriginal bark paintings we have
had to employ a number of different techniques
with radiation having energies from <1 eV to 20
keV. Although we have excellent qualitative data
on pigment compositions the exact atomic com-
positions of pigments have yet to be determined.
Our study of the bark itself was more successful,
determining that firing both inside and outside the
bark leads to a more stable material for painting.
This information has been given to the indigenous
communities who depend on paintings for their
livelihood.
One very significant outcome of this project is
the influence it has had on the design of display
and storage of aboriginal bark paintings in the
new National Museum of Australia. As well the
renovation of their Mitchell storage facilities will
be influenced by the findings of the project.
Criteria for the design of packing cases for
transport of Aboriginal artefacts between muse-
ums within, and external, to Australia can be de-
veloped to ensure safe transport of these fragile
items. As well, criteria have now been established
675
to assist conservators in the preservation of Ab-
original artefacts.
Acknowledgements
The authors wish to acknowledge the support
of the Australian Research Council for financial
support for this project under the Strategic Part-
nerships Industry Research and Technology
(SPIRT) Scheme. They are indebted to Dr. Rodger
Heady for assistance with the SEM study of barks;
the Director of the NGA, Dr. Brian Kennedy, and
the Director of the NMA, Dawn Casey, for giving
financial support; Professor Colin Pearson, Janet
Hughes, Gloria Morales, Eric Archer, Mark
Henderson, Benita Johnson, and Anne IÕOns for
their advice and encouragement. They wish to
acknowledge the friendship of the Maningrida,
Oenpelly and Yirrkala communities, and the as-
sistance they afforded us in our fieldwork. Two of
the authors (D.C.C. and V.O.-A.) wish to ac-
knowledge funding from the Australian Synchro-
tron Research Program and the valuable
assistance of Dr. James Hester.
676 D.C. Creagh, V. Otieno-Alego / Nucl. Instr. and Meth. in Phys. Res. B 213 (2004) 670–676

References [4] W.A. Deer, R.A. Howie, J. Zussman, An Introduction to

[1] M.M. Chattaway, Aust. J. Bot. 1 (3) (1953) 402.
[2] K. Coote, Care of Collections, Conservation for Aboriginal
and Torres Strait Islander Keeping Places and Cultural
Centres, Australian Museum, 1998, ISBN 0-7313-1585-5.
[3] S. Gatenby, Master of Applied Science in the Conservation
of Cultural Materials Thesis, University of Canberra, 1996.
Rock-forming Minerals, Wiley, New York, 12th Ed., 1980.
[5] D.C. Creagh, V. Otieno-Alego, K. Roth, N. Smith, in: L.
Vanterdack (Ed.), Proc. 7th Int. Conf. on Non-destructive
Testing for the Diagnosis and Conservation of the Cultural
and Environmental Heritage, Antwerp, 2–6 June 2002.
[6] P.M. OÕNeill, M. Sterns, D. Creagh, Radiat. Phys. Chem.
(2004) in press.