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Radiation Physics and Chemistry 74 (2005) 426442 www.elsevier.com/locate/radphyschem

The characterization of artefacts of cultural heritage signicance using physical techniques

D.C. Creagh
Cultural Heritage Research Centre, Division of Science and Design, University of Canberra, Canberra ACT 2601, Australia

Abstract All societies attempt to preserve their cultural heritage because it is this that gives them their identity. How artefacts are identied as being of signicance to society, and how to preserve these for posterity, depend on the sophistication of those societies, their wealth, and the determination of members of the societies to preserve their past. If conservation or restoration measures are being undertaken complex analytical experiments must be undertaken beforehand to ensure that the work is being undertaken in an appropriate manner. These investigations may employ electromagnetic (IR, VIS, UV, X-ray, g-ray) or particulate (electron, proton, neutron, and ion beams) radiation. The use of many of these techniques is described in this paper in experiments on Australian Aboriginal bark paintings, a suit of armour belonging to a famous Australian outlaw, and the degradation of colour motion picture lm. r 2005 Elsevier Ltd. All rights reserved.
Keywords: Cultural heritage studies; Raman microscopy; Synchrotron radiation X-ray diffraction; Micro-X-ray uorescence spectroscopy; Electron microscopy

1. Introduction All societies attempt to preserve their cultural heritage because it is this that gives them their identity. How artefacts are identied as being of signicance to society, and how to preserve these for posterity, depend on the sophistication of those societies, their wealth, and the determination of members of the societies to preserve their past. The range of material which is deemed to be of cultural heritage signicance is vast, and, in this paper the results of three signicant, totally different, projects will be given. These projects were undertaken on artefacts from four major Australian national collecting institutions, the Australian Archives, the National Museum of Australia, the National Gallery of Australia, and the National Film and Sound Archive. The projects
E-mail address: dcreagh@bigpond.net.eu.

are: the conservation of Australian Aboriginal bark paintings, the metallurgy of Joe Byrnes armour, and the degradation of dyes in post-1970 motion picture lms. When conservation or restoration measures are being undertaken complex analytical experiments must be undertaken beforehand to ensure that the work is being undertaken in an appropriate manner. These investigations may employ a range of electromagnetic (IR, VIS, UV, X-ray, g-ray) and particulate (electron, proton, neutron, and ion beams) radiation (Creagh and Bradley, 2000). 1.1. Aboriginal bark paintings A signicant study has been made of the conservation of Australian Aboriginal works of art. The principal artform of the indigenous people of Arnhem Land, in Northern Australia, takes the form of painting on bark stripped from the Darwin stringy-bark tree (eucalyptus

0969-806X/$ - see front matter r 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.radphyschem.2005.08.011

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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 interpretation of the artist of his cultural identity. Much has been written on Aboriginal bark paintings (Chattaway, 1953; Coote, 1998) but much of what has been written has been inuenced more by the perceptions of curators than by scientic analysis. There is a strong interest in all aspects of the storage, conservation, transportation, and display of aboriginal artefacts to the public. The active participation by indigenous communities in this project (the Maningrida, Oenpelly, and Yirrkala communities in particular) is indicative of the signicance of the project to the indigenous communities. The three components of bark paintings of scientic interest are: the bark itself, the pigments, and the binders used to cause the pigments to adhere to the bark. Of these the least familiar component to readers from the Northern Hemisphere is perhaps the bark. The bark is harvested from the Darwin stringybark (eucalyptus tetradonta) usually at the end of the wet season (MarchMay). The time of harvesting depends on the whether the bush can be accessed by the community. Eucalyptus tetradonta is a tall straight-growing tree and carries its branches at the canopy. The size of the bark depends on the height and girth of the tree and the extent to which it is free from blemishes and growth twist. A typical bark is 4 m high, and perhaps 1.5 m in width. After harvesting the further treatment of the barks varies from community to community, artist to artist. At Yirrkala the bark is attened by weighting, but not generally red. At Maningrida and Oenpelly the bark may be red internally, externally, or both, and then attened by weighting. By ring is meant the lighting of a re of bush debris inside, or external, to the bark. Of signicance is the question as to what the processes of ring and/or attening does to the mechanical properties of the bark, especially to its reaction to variations of temperature and humidity since this determines the robustness of the painting with respect to its stored and displayed environments, and in its transport from one location to another. The adhesion of the pigments to the bark is inuenced by exure. The type of pigments and binders used by artists is idiosyncratic, and if a proper database were to exist, this could be used as a means of establishing provenance for a work. Techniques used in the study of aboriginal bark paintings include: Raman microscopy, time-lapse photography, micro-focus X-ray uorescence spectroscopy, synchrotron radiation X-ray diffraction and scanning electron microscopy. 1.2. Joe Byrnes armour Australians have always had a fascination with bushrangers, and the Natiuonal Museum of Australia,

and many regional museums have signicant holdings of bushranger artefacts. Bushrangers were outlaws: initially escaped convicts, but later, people at odds with the society of the day. Of these, the Kelly Gang, active in Victoria (Australia) in the 1880s, is probably the most notorious (http://www.nedkellysworld.com.au). The gang were horse thieves and police murderers. In its nal act of lawlessness the Kelly gang was involved in a gun-battle with police at Glenrowan in four suits of armour which they had fabricated. Over time stories have arisen about the fabrication of the armour. Amongst these were: that the armour was made from ploughshares; by blacksmiths in a smithy, using the blacksmiths forge; that all the wearers of the armour were actively involved in the gunght at Glenrowan. Neutron diffraction, X-ray diffraction, gX-ray uorescence spectroscopy, and optical metallography were used in an attempt to answer these questions. 1.3. Studies of the degradation of colour motion picture lm Film archives worldwide are responsible for the care of large collections of colour motion picture lms. These archives hold culturally important examples of 20th Century life and customs. In Australia, the National Film and Sound Archive, is responsible for about 88,000 colour motion picture lms, ranging from documentary lms to feature lms. To preserve this important part of our cultural heritage lm, archivists are confronted daily with the problem of the fading of the coloured dyes in these lms. Dye degradation can occur as a result of the exposure to light or, in the dark, as a result of heat, humidity or environmental pollutants. In this work we are interested in the mechanisms of dye degradation and specically in the acid hydrolysis of the azomethine dyes. We have used a wide range of analytical techniques, including Raman spectroscopy, a non-destructive technique, to study the China girl images in the leaders of motion picture colour lm to determine the chemical components present colours within the lm. Techniques to overcome uorescence from the dyes in the Raman spectra have been developed. Table 1 summarizes the types of radiation used in investigations described in this paper. In this paper the techniques described are ordered in increasing energy of the radiation used for illumination of the sample.

2. Experiments Because some of the techniques mentioned above may be unfamiliar to readers a brief description of the least known of them is given below.

428 D.C. Creagh / Radiation Physics and Chemistry 74 (2005) 426442 Table 1 Types of radiation used in the work described in this paper Energy range (eV) 0.54 Particle type em (photon) Interaction Absorption Inelastic scatter Elastic scatter Absorption Absorption Elastic scattering Absorption Secondary emission Elastic scattering Elastic scattering Elastic scattering Technique FTIR Raman Photography XRF Tomography SRXRD SEM/EDAX SEM/SEI SEM/BEI STEM Diffraction Used for the study of Pigments & binders Pigments & binders Appearance & shapes Atomic composition Internal structure Crystalline structure Atomic composition Surface morphology Surface morphology Crystalline type Crystalline structure


em (photon)


e (electron)


n1 (neutron)

2.1. IR and Raman spectroscopy Fourier Transform Infra-Red (FTIR) spectrometers are commonly used in most laboratories for the analysis of materials. An infrared spectrometer analyses the frequency of the infrared photons absorbed by the sample. Absorption occurs in transitions between vibrational modes of crystal structures and molecules within the sample. Measurement of absorption provides identication of the molecular species present in the sample by means of comparison of the band characteristics of the unknown species with those of standard materials. Most functional groups such as OH, NH, CQO have characteristic localized modes allowing for their easy identication on different samples. Other techniques use scattering rather than absorption of IR radiation, in particular, inelastic or Raman scattering. This technique is used extensively for the analysis of pigments and binders (Edwards et al., 1991). 2.1.1. Raman micro-spectroscopy Most of the incident radiation scattered by a sample is scattered elastically. However, a small part of the incoming radiation (approximately 1 part in 105) interacts with the sample and is scattered inelastically (Raman scattering) re-emerging with a different frequency (energy). A Raman spectrometer is congured to reject the elastically scattered, and accept only the inelastically scattered radiation. A Renishaw 2000 Raman microscope was used in this work with illuminating lasers operating at 632.8 and 780 nm. The choice of laser is dictated by the emission of uorescence by the specimen. As will be seen later this swamps the weak Raman scattering, and special techniques must be employed to retrieve the Raman signal. A microscope attachment to the Raman spectrometer facilitates the

study of very small amounts of material, or domains within materials, with high spatial resolution (1 mm), an important feature if the particular compounds to be identied are made from a mixture of compounds. The technique combines the desirable attributes of being non-destructive, reliable, sensitive, but largely immune to interference from other materials. The technique can be used in situ which makes it possible to study valuable artefacts for which sampling is forbidden. No two molecular structures produce the same Raman trace, and a particular combination of Raman peaks provides an unequivocal identication of the molecular species. Samples for Raman studies are often analysed without any prior sample preparation. Special microscope stages (for example xyz stages) can be used in the examination of medium sized or specialized objects. A special side xyz stage has been designed for use with the macro-point adaptor of the Raman microscope to enable the examination of large objects (Creagh and OtienoAlego, 2004). Fibre optic microscope objectives are available commercially to allow examinations to be made of objects to which access is difcult. 2.1.2. FTIR micro-spectrometry FTIR and Raman spectroscopy are complementary techniques. Vibrations which are strong in a Raman spectrum are usually weak in an infrared spectrum and vice versa. Qualitatively, antisymmetric vibrational modes and vibrations due to polar bonds (such as OH, NH, CQO) generally exhibit prominent infrared bands, while Raman tends to arise from vibrations involving more symmetrical bonds (such as CQC, CC, SS). As with Raman spectroscopy, complete compound identication is possible with FTIR by comparing band characteristics of the unknown species with those in commercial or in inhouse computer databanks.

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In a multicomponent sample the relative intensity of a functional group band is proportional to the quantity of its parent material in the analysis area. The limitation in spectral range (typically 6004000 cm1), Edwards et al. (1999), however, restricts the techniques ability to characterize most inorganic components, many of which exhibit spectral features below 700 cm1. In the work describer here a Bomem MB Series FTIR has been used with a Spectratech IR Spectrometer, which has an operating range of 5005000 cm1. In practice, if an FTIR spectrometer is used, microgram quantities of paint sample are required. This is ground with excess of KBr and pressed into transparent KBr pellets for analysis. With the FTIR Microspectrometer, spectra can now be taken using a nanogram sample by simply attening the specimen onto a diamond cell window. A sample of this size can be removed from the artefact using a tungsten needle under a microscope (typical of micro-sampling procedure for pigments on drawings) without causing damage visible to the naked eye. 2.2. Techniques using radiation in the visible region of the radiation spectrum In many experiments conventional optical microscopy has been used. The micro-Raman, micro-FTIR techniques, and micro-X-ray uorescence spectrometer use optical spectroscopy for preliminary examinations of the specimen and the location of regions of interest. As well, we have employed transmission optical microscopy to study the structure of bark samples. Time-lapse optical photography has been used to track the exure of bark paintings placed in an environmental chamber in which temperature and humidity could be controlled. The motion of the bark was recorded using colour calibrated Nikon Coolpix digital cameras, which have 4.2 MPx detector arrays. Optical metallographic techniques have been used to study the metallurgical microstructure of Joe Byrnes armour. In this case permission had to be sought from the owner to allow the surface etching of a 3 mm diameter to be preformed (Creagh et al., 2004). 2.3. Fluorescence analysis Whilst both micro-Raman and micro-FTIR can give identication of molecular species present in the sample, problems can occur with respect to exact identication of pigment. For example: the Raman technique can identify mineral types directly. It can, identify the mineral components in a white pigment to be kaolin, anatase, and quartz, for example. Both anatase and quartz are likely to be present in the forms of TiO2 and SiO2, respectively. But the composition of the kaolin, a clay mineral, can vary strongly from location to

location. To nd information on the impurities in the clay (which might be iron or manganese) an investigation of the atomic composition of the sample must be made. 2.3.1. Micro-uorescence spectroscopy Analyses such as those mentioned in the preceding paragraph can be made using the technique of X-ray uorescence spectroscopy. In this technique the specimen is irradiated by an X-ray source. This radiation causes the ejection of electrons from the innermost electron shells of the atoms in the sample into the continuum, and the subsequent rearrangement of electrons within the atom causes emission of X-rays (characteristic X-rays). The spectrum that results is unique to the atom emitting the radiation. In experiments involving the Aboriginal bark paintings a Kevex Omnicron microxrf spectrometer was used. This provides a nely collimated beam (able to be varied from 50 mm to 3 mm diameter) from a rhodium X-ray tube (operated at 50 kV and 1 mA) which illuminates the sample. The sample is carried in an xy stage and is positioned in the beam using an optical microscope, the output from which is read by a CCD detector and displayed on a TV screen. The uorescence radiation is detected by a liquid nitrogen cooled Si(Li) detector, and converted to electrons. The resulting electron currents are amplied and converted to voltage levels. Pulse height analysis is used to sort the pulses according to the energy of the uorescent X-ray. The resolution of the detector is 180 eV at 5.6 keV (Mn Ka). 2.3.2. gX uorescence spectrometry For very large specimens, and for specimens which cannot be removed from museum custody, analyses can be undertaken using a portable gX spectrometer. This is not a micro-spectrometer, and the beam diameter is xed at 1 mm diameter. For the study of Joe Byrnes armour a Thermo Metallurgist Pro Mercury II Probe was used. This has two g-ray sources: 109Cd (4 mCi at 80 keV), 55Fe (4.5 mCi at 6.40 keV). It is a hand-held device and in principle it can sample any surface in any orientation. A HgI2 detector is used, operated at room temperature. The uorescence spectrum acquires in the detector is amplied, passed through a multichannel analyzer, the output from which is fed into a lap-top computer. This contains programs which enable a full spectral analysis with full matrix corrections to be undertaken. The spectral lines are compared with an internal database for metals and alloys. 2.4. X-ray diffraction 2.4.1. Laboratory XRD Studies of the crystal structure of Joe Byrnes armour were undertaken using a Scintag diffractometer tted

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with a copper target tube, operating at 38 kV, 30 mA. The diffractometers was operated in the yy mode with a step scan size of 0.0501. The detector was a liquid nitrogen cooled solid state detector, the output of which was amplied and processed by a multichannel analyzer. A window was set such that only CuKa1 radiation was detected. The CuKb and uorescence radiation was rejected. 2.4.2. Synchrotron radiation X-ray diffraction The use of synchrotron radiation sources by materials scientists for cultural heritage studies is still comparatively new. Synchrotron radiation sources dedicated to the study of materials have been in existence for about 20 years. Synchrotrons which generate radiation in the X-ray region (the region used in most structural analyses) typically have energies greater that 2 GeV. For example: the Photon Factory at the Japanese Institute for High Energy Research, Tsukuba, Japan, operates with a circulating current of electrons (400 mA at 2.6 GeV) and produces useful maximum X-ray energies for a bending magnet in the range 4.520 keV; the Advanced Photon Source at Argonne, USA operates at 6 GeV and produces useful maximum X-ray energies in the range 480 keV). Synchrotron radiation sources are classied by the size of the spot which emits the radiation: values of about 40 nm rad are typical of a Second Generation machine; 15 or less are characteristic of a Third Generation machine. Whatever the energy to which the charged particle is accelerated the principles underlying the production of X-rays is the same. When a charged particle is accelerated (as it is when it is deected by a magnetic eld) it radiates energy in the form of electromagnetic radiation, the maximum energy of which is determined by the energy of the particle and the applied magnetic eld. The higher the particle energy and the stronger the magnetic eld strength, and the higher the maximum photon energy. To put this another way: the critical wavelength (lc 18.64/(BE2) is shorter. Here lc is in Angstrom, B in Tesla, E in GeV). See Creagh (2003) for further explanation. The principal properties of synchrotron radiation are as follows:

In some experiments white radiation is used and the photon energies are separated using energy dispersive analysis techniques. In the examples described here monochromatic radiation has been used. The production of monochromatic radiation and techniques for focusing the already highly collimated, high-intensity beams has been described in by Creagh (2003). Experiments described in this paper have been conducted either at the Photon Factory, KEK, Tsukuba, Japan (PF) (circulating electron energy of 2.6 GeV, and current 400 mA). In the experiments on pigments in Aboriginal bark paintings the vacuum diffractometer at the Australian National Beamline (ANBF/PF) at the Photon Factory was used. This is essentially a large (573 mm radius) Debye-Scherrer or Weissenberg diffractometer using imaging plates to detect the diffracted radiation. This system was used as conventional powder diffractometer. That is, nely powdered samples were placed in capillaries that were spun about their axis during exposure to minimize preferred orientation and grain-size effects. X-ray diffraction is used to determine the crystal structures and phase compositions of materials. In conventional XRD experiments only one capillary could be mounted measured at a time. By contrast the experiments at the ANBF/PF made use of an eight-position capillary spinning stage (Creagh et al., 1998) in the vacuum diffractometer operating with its Weisenberg screen. Seven specimens and one standard could be measured on one set of imaging plates. Exposure times were about 10 min per sample. For further information on the use of synchrotron radiation and its use in cultural heritage studies see http://srs.dl.ac.uk/arch/index.htm. 2.5. Electron microscopy 2.5.1. Scanning electron microscopy Scanning electron microscopy (SEM) has been undertaken to study the structure of barks to determine what, if any, changes occur when a bark is red. A conventional Cambridge SEM was used and specimens were usually carbon-coated. The production of specimens amenable to analysis by the SEM was difcult because of the brittleness of the bark. Lack of strength in the tangential direction made microtomy of the specimens difcult (Heady et al., 2003). 2.5.2. High resolution transmission electron microscopy The examination of the metallurgical structure of Joe Byrnes armour was undertaken using replica techniques using a TEM: JEOL 2000FX II operating at 200 keV. The region to be examined (typically 3 mm in diameter) was etched with nital to dissolve surface layers of the metal and leave and carbides standing proud of the surface. A softened acetate sheet was applied to the

 high intensity, especially if auxiliary bending devices   

such as wigglers and undulators are used (typically more than 108 more intense than a conventional laboratory source), emission over a broad spectral range (from IR to Xray energies; white radiation), high directionality (because of relativistic effects the divergence of the beams are typically less than 2 mrad vertically, 7 mrad horizontally), linear polarization in the plane of the orbit.

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surface, and, when hardened, the sheet was peeled off taking with it the topography of the surface and adhering carbides. The acetate replica was then coated with carbon, and the acetate lm was dissolved in acetone prior to the mounting of the replica on a TEM grid. The structure of the metallurgical structure of the surface was examined by electron microscopy and the chemical composition of any particles stripped from the surface by the replica was analysed using X-ray uorescence spectroscopy (referred to as EDAX). 2.6. Neutron diffraction Neutron diffraction experiments on the large pieces of Joe Byrnes armour were undertaken at the Australian Nuclear Science and Technology Organizations nuclear reactor HIFAR at Lucas Heights, Sydney, Australia. The Medium Resolution Powder Diffraction (MRPD) facility was used. For detailed information on this facility see http://www.ansto.gov.au/ansto/bragg/hifar/ med.html. The MRPD operates from the thermal neutron ux from the HIFAR reactor. Particular neutron wavelengths from the continuous spectrum of neutron energies can be selected using a monochromator which consists of eight germanium crystals, arranged in a vertically focussing conguration. The available neutron wavelength range is 0.20.5 nm. The wavelength used in this study was 0.16664 nm. In contrast to the XRD measurements in which only the sideplates of the armour would t into the diffractometers the large sample stage allowed the analysis of all the components of the armour. The detector system consisted of detector 32 independent 3He detectors channels giving medium spectral resolution from 41 to 1381. The diffractometer was set at a 0.11 scan step size, giving a typical data acquisition time of 2 h. The data was analysed using a Rietveld renement procedure (RIETICA Program), assuming pseudo-Voigt proles and using background renement. 2.7. The Rietveld technique The analysis of powder diffraction data from both X-ray and neutron experiments uses the Rietveld method (Rietveld, 1969; Young, 1993). The specimens are assumed to be a mixture of crystalline phases, each phase contributing its own pattern to the overall pattern. To determine the combination of phases present in the sample the Bragg equation 2d h k l sin y l (1)

the subsequent step is quantitative phase analysis which assesses the amount of each phase in the sample material, either as volume or weight fraction assuming that:

 each phase exhibits a unique set of diffraction peaks;  the intensities belonging to each phase fraction are
proportional to the phase content in the mixture. A full-pattern diffraction analysis can, in addition to the phase fraction determination, include the renement of structure parameters of individual mineral phases, such as lattice parameters and/or atom positions in the unit cell. The Rietveld method allows the renement of phase specic structure parameters along with experiment specic prole parameters by tting a calculated model pattern to the entire observed diffraction pattern using the least-squares algorithm which minimizes the quantity: X 2 D gi yobs ycal (2) i i .

The summation index i runs over all observed intensities yiobs. The weights gi are taken from the counting statistics. yicalc are the calculated model intensities dened by instrumental and structural parameters, the latter including weight fractions in a multiphase renement. By renement of reection prole parameters, crystallite size and micro-strain effects can be studied. The Rietveld routine calculates gures of merit that indicate the quality of the t of the entire model pattern to the entire observed diffraction pattern. A meaningful criterion is the weighted prole R-value Rwp: ( )1=2 2 Sgi yobs ycal i i Rwp (3) 2 Sgi yobs i which should converge to a minimum. There are a number of programs available, many of them public domain, which can be used for X-ray as well as for neutron diffraction data analysis, e.g. the GSAS General Structure Analysis System (Larson and Von Dreele, 1986; Rodriguez-Carvajal, 1993). The quantitative phase information is obtained assuming that the weight fraction, Wp, of the pth phase in a mixture is given by the normalized product: .X W p Sp Zp M p V p S Z MiV i, (4) i i i where Sp, Mp, Zp, Vp are the rened Rietveld scale factor, the mass of the formula unit (e.g. SiO2), the number of formula units per unit cell and the unit cell volume, respectively, of that phase p. The summation in the denominator accounts for all crystalline phases. Thus, in the case where not all crystalline components can be identied or in the presence of amorphous

is used to make a list of values of d h k l corresponding to the observed peaks. Association of measured peak positions with calculated or observed positions of pure single-phase ngerprints can be made using database search-match routines. Once the phases are identied,

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phases, the Rietveld analysis yields relative phase fractions only with respect to the crystalline phases contained in the model. The main advantages of quantitative phase analysis by the Rietveld method are as follows:


peaks and even peak clusters are handled without difculty. Preferred orientation of crystallites can be considered in the model.

 No internal standard is required.  Crystal structure models are included

explicitly. Structure parameters can be rened along with weight fractions of mineral phases.

It may happen that one or more phases have been identied using reection positions and extinction rules (yielding space group and lattice parameters), but structure models may not t the experimental data because, for instance, powder grains are not

Black Section (Lamp black)



Mineral Fe2O3 Synthetic Fe2O3 Red Section

Relative Intensity (arb. Units)












White Section Kaolin (anatase)

Synthetic Fe(OH) 3

Deep Yellow Section PVA

400 800 1200 1600 2000 400 800 1200 1600 2000

Raman Shift (cm-1 )

Fig. 1. One of the Aboriginal bark paintings studied in this work. A, B, C, D show Raman spectra of pigments in different positions on the painting.

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statistically distributed in the object or simply because there are no complete structure models available, as it is the case for some clay minerals like illite and kaolinite. The presence of amorphous phases in samples gives some difculty in the interpretation of scattering data using the Rietveld method. In general, in Rietveld analysis, the background is stripped from the overall spectrum mathematically. As yet no easy method exists for the quantitative interpretation of diffraction data in which there is a strong amorphous background.

3. Results 3.1. The study of aboriginal bark paintings 3.1.1. Raman microscopy of pigments in aboriginal bark paintings Using the macro-point adaptor for the Renishaw Raman Microscope each of the major colours present on an Aboriginal bark painting were positioned under the microscope and analysed (using a 20 microscope objective). The spectrum from the black sections (Fig. 1A) indicates the presence of lamp black, whilst that recorded for the white sections (Fig. 1B), suggests the presence of the clay mineral, kaolin, quartz, and anatase (TiO2, a white pigment). The Raman signatures (red lines) unequivocally show that mars red (synthetic iron (III) oxide) and mars yellow (synthetic iron(III) hydroxide) were used as the red and yellow pigments instead of the traditional mineral pigments (yellow and red ochres, respectively). (See Figs. 1C and D.) The Raman traces from the yellow sections of the painting also show peaks suggesting the presence of polyvinyl acetate (PVA, Fig. 1D) which is often used as a binder (Gatenby, 1996).

% Transmittance 500










Fig. 2. FTIR microscopy spectrum recorded on a nanogram sample taken from a bark painting. The spectrum contains absorption bands indicative of iron oxide and peaks characteristic of polyvinyl acetate.

3.1.2. FTIR microscopy of a sample from an Aboriginal bark painting The spectrum shown in Fig. 2 was recorded nondestructively on a nanogram sample taken from an Aboriginal bark painting by attening the specimen onto a diamond cell window. Samples of this size can be

Fig. 3. Micro-XRF spectra for white pigments from two paintings from different areas. (A) has more silicon but less iron and titanium than (B).

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removed from the artefact using a tungsten needle under a microscope (typical of micro-sampling procedure for pigments on drawings) without mutilating the object in anyway. The recorded FTIR spectrum contained absorption bands which were indicative of mars yellow (Fe(OH)3, synthetic yellow ochre: peaks at 3400 (broad, OH), 902 and 796 cm1) and peaks characteristic of polyvinyl acetate (2960, 2925, 2873 (CH), 1739 (CQO), 1433, 1375 (CH), 1240, 1118, 1024, 945 cm1 (CO)). Methods for preparing micro-samples (such as paint chips, scrapings, extracted components and thin sections) for non-destructive FTIR analysis are well documented (Baker et al., 1988).

3.1.3. Micro-XRF study of white pigments in Aboriginal bark paintings Raman microscopy has proved to be a good technique for the identication of mineral types. In Fig. 1 the basic constituents of the white paint were kaolinite, anatase, and silica. The question must now be asked: in what ways do pigments differ in paintings from the same region? Determination of the atomic composition may be able to give us a lead on this. Fig. 3 shows the spectra from white pigments from two paintings from the same region. Though each has essentially kaolinite, anatase, and silica as components, it is clear that Fig. 3A has more silicon but less titanium and iron than Fig. 3B.

Fig. 4. Synchrotron radiation X-ray diffraction pattern from a white pigment used by indigenous artists of the Arnhem Land region. The Rietveld t to the experimental points in shown in the upper graph. Below that are the positions of the diffraction lines for kaolin (K), quartz (Q), talc (T), and muscovite (M). The Rietveld calculation is a wholeof-pattern t to the experimental points. The bottom graph shows the difference between the observed and calculated values.

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Kaolin is a clay mineral which can contain iron and silicon in its structure (Deere et al., 1980). How much of the silicon peak, then, is due to the kaolin, and how much is due to free silica? And is there another iron-rich phase? The anatase component would seem to be a unique phase, but how did it get mixed up with the kaolinite? To answer these questions samples were taken to the Photon Factory for X-ray diffraction studies at the vacuum diffractometer at the ANBF. 3.1.4. Synchrotron radiation X-ray diffraction studies of the white pigments used traditionally in Aboriginal bark paintings The diffraction patterns from the white pigments from a number of sites used by indigenous artists in Arnhem Land had many lines, sometimes on a strong amorphous background. Figs. 4 and 5 are typical diffraction patterns (ONeill et al., 2004). The interesting feature of this study is that no anatase was found in any of the four locations used by indigenous artists. The diffraction patterns were analysed for composition using Rietveld analysis and Taylor (1991). As can be seen in Fig. 4, the Rietveld renement is reasonably good: perhaps as good as can be expected for whole-pattern tting to clay minerals. The compositions of these white pigments and the percentage compositions are shown in Table 2. The row shown as other includes as yet unidentied phases and the contribution of the amorphous scattered background. It is clear from this table that only Sample 1 has

components similar to those identied by Raman microscopy and Micro-XRF spectroscopy. Talc is a very soft mineral (Mho scale 2) and has very weak vibrational bands. Muscovite is present in the form of akes which are very thin, and like talc it has a weak Raman spectrum. It is not surprising that they were missed in the Raman analysis. What is surprising is the absence of anatase (TiO2) in all these pigments. And it is

Table 2 Compositions of white pigments used by indigenous artists in Arnhem Land Sample 1 Mineral Kaolinite Quartz Talc Muscovite Other Talc Hydroxyapatite Other Hundtite Quartz Other Talc Hydroxyapatite Other % composition 74 18 2 3 3 98 2 81 4 15 98 2

Fig. 5. Synchrotron radiation X-ray diffraction pattern from a white pigment used by indigenous artists of the Arnhem Land region. The Rietveld t to the experimental points in shown in the upper graph. Below that are the positions of the diffraction lines for undtite (H) and quartz (Q). The Rietveld calculation is a whole-of-pattern t to the experimental points. The bottom graph shows the difference between the observed and calculated values.

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not clear what is the source of the iron shown in Fig. 1. It could be an impurity phase in the kaolinite. One conjecture, bearing in mind that the red pigment was identied by Raman spectroscopy to be man-made and not the naturally occurring mineral, is that the artist mixed a modern white paint with the kaolinite ore to whiten it. 3.1.5. Study of the structure and mechanical properties of barks Optical and scanning electron microscopy of sample barks show that ring, especially ring inside and outside, has a marked effect on the structure of the bark. The starch grains in an untreated bark shown in Fig. 6(a) are seen to have broken down and ll the cavities after ring (Fig. 6(b)). The consequence of this is to make the bark more homogeneous and less susceptible to environmental changes. This is of signicance from the point of view of their transport

and storage. All barks uctuate dimensionally with changes of temperature and humidity, making the design of hangers and storage drawers complicated. Digital time-lapse digital photography has been used extensively to study the movement of barks (Creagh and Otieno-Alego, 2004). Determination of the point of zero exure is important from the point of view of establishing how best to mount the bark. In a typical test it was shown that the end of a 580 mm long bark painting moved more than 30 mm when the temperature and humidity varies from 27 1C, 37% to 181C, 63%. In a museum environment where the temperature and humidity are controlled the movement of the bark may not be of much consequence, but in uncontrolled storage, or in transit between locations, considerable movement may occur, to the detriment of the artefact. The question of whether a bark is more stable when it is unred, internally red, or internally and externally red has been resolved. The last-mentioned bark treatment is the best. The reason why this is so can be seen the scanning electron microscope images shown in Fig. 7, and the optical images (Figs. 6(a) and (b)). Fig 7(a) shows starch grains in the vertical vesicules of a bark, and Fig. 7(b) shows a horizontal cross-section of the bark. Heating causes the starch grains to burst and the contents of the grains ll the vesicules and spread out into the surrounding bark. This acts like a glue, and holds the fragile bark structure together, making a more rigid structure than that in case of the untreated bark. 3.2. Studies of Joe Byrnes armour 3.2.1. Neutron and X-ray diffraction studies Fig. 8 shows Joe Byrnes armour. As can be seen, it is very roughly made and clearly not the work of an armourer. Fig. 9 shows a neutron diffraction pattern of part of the armour, and the bottom pattern is the difference between the observed and the calculated diffraction patterns. The difference is due to lineshape effects due to surface strain. The steel is similar to entry 06-0696 in the JCPDS database. All the other parts of the armour are similar to those shown in Fig. 9. Conventional XRD, taken with the Scintag system, could only examine the side-plates. Lines from the steel and surface oxides were observed because of the limited depth of penetration enhances surface effects, whereas neutrons can penetrate the bulk material, and show the bulk properties. However, the XRD results are very similar to the neutron results, and conrm the similarity to 06-0696 in the JCPDS database, and a lattice parameter for the steel of (0.2867270.00034) nm.

Fig. 6. White light transmission optical micrographs of barks. (a) as received, (b) pressed and red. The effect of ring on the black starch grains in (a) can be seen. There are no black grains in (b).

3.2.2. Studies of composition using g-X-ray uorescence spectrometry Table 3 shows the result of the gX-ray uorescence spectrometry study of all the components of the armour.

D.C. Creagh / Radiation Physics and Chemistry 74 (2005) 426442 437

Fig. 7. Vertical (a) and horizontal (b) sections of a bark using a scanning electron microscope. Note the starch grains in the vertical vesicules.

Fig. 8. Joe Byrnes armour.

The carbon content could not be determined. Generally the compositions are of a mild steel, but there are some peculiarities, viz.:

 All, except the helmet cylinder, the side plates, and

the rivets contain manganese, indicating that the date of production of the steel was post-1857 when Mushet introduced the use of manganese into the open hearth process to de-oxidize the melt. All, except the rivet, the Kiandra and modern mild steels, contain traces of arsenic, tin, and lead. TEM EDAX conrms the presence of these atomic species in the chestplate.


However, if it were made by a bullet the bullet was not made at the time of the siege (1880): tungsten was rst added to ball ammunition towards the end of World War I. It is possible to estimate the thickness of the lead and tungsten layer which is impregnated on the surface of the armour. The ratio of the intensities of the iron uorescence peak with and without the layer allows us to estimate the average thickness of the mark on the front of the breastplate to be 0.470.2 mm (Creagh et al., 2004). 3.2.3. Optical metallography and replica TEM Optical microscopy and TEM replica microscopy show that some of the chest protector has the original micro-structure, whereas other regions show the effect of heating. The absence of deformation of the pearlite colonies in the steel indicate this piece was hotworked. The fact that the pearlite laths are needlelike in Fig. 10 indicates that the temperature at which

The components of armour appear to come from plough shares, and other farm detritus. The mark on the front of the breastplate shows the existence of lead and tungsten. This mark is the only evidence that the armour might have been in a gunght.

438 D.C. Creagh / Radiation Physics and Chemistry 74 (2005) 426442

Fig. 9. Neutron diffraction pattern from the helmet, with the data points tted using the Rietveld technique, The lower curve is a measure of the difference between the calculations and the data points.

Table 3 Percentage compositions of principal atomic compositions of the steel components of Joe Byrnes armour Item HELMET HELMET BREASTPLATE BREASTPLATE BREASTPLATE BACKPLATE LAP PLATE SIDE PANEL 1 SIDE PANEL 2 RIVET MILD STEEL MILD STEEL Faceplate Cylinder General Mark, front Mark, back General General General General Typical Kiandra Modern Mn 0.32 0.33 0.27 0.48 0.32 0.31 Fe 96.56 94.6 96.85 75.35 97.88 96.56 94.29 95.33 98.14 97.65 98.6 94.57 As 0.17 0.1 0.07 3.15 0.17 0.10 0.11 0.25 Sn 1.80 2.6 1.48 1.14 0.48 1.80 2.6 2.6 0.47 1.34 2.15 W Pb 0.18 0.18 0.14 14.4 0.20 0.18 0.18 0.18 0.09


0.44 1.07

General means that the measurements have been made at a number of points on the item. Those items with a manganese composition came from material made after 1856. Note the signicant difference in the apparent composition between measurements made on the mark on the breastplate and that made at the back, behind the mark. This is due to the absorption of the FeKa uorescent radiation by the lead and tungsten.

the bcc-fcc phase transition (650-723 1C) was not reached. If this had occurred the laths would spheroidize. TEM conrms the conclusions reached from optical metallography, and, using energy dispersive Xray uorescence the composition of the steel is in

agreement with the results of gX-ray uorescence experiment. As well spheres of manganese were seen in the TEM replica. This, in conjunction with the fact that the pieces were not uniformly heated indicates that the metal was not

D.C. Creagh / Radiation Physics and Chemistry 74 (2005) 426442 439

worked in a smithy, where temperatures of 1100 1C might be expected.

3.3. Studies of the degradation of colour motion picture lm When the project to study the degradation of dyes in post-1970 colour motion picture lms was commenced it was expected, on the basis of work which had been undertaken on laminated plastic systems, that the we would have been able to extract the chemical information using confocal Raman spectroscopy. In this technique spectra are taken as the microscope is focused deeper and deeper into the specimen. However, the colour motion picture lm is a very complicated system as can be seen in Fig. 11. Each of the layers are typically 10 mm thick, and the amount of dye in each layer is very small. It was hoped that the research could be done nondestructively on the china girl image on the leader of the lms (Fig. 12). In the event the ouorescence from the specimen swamped the Raman signal, and it was necessary to remove a frame for destructive testing. A technique for micro-toming the image and extracting the dyes from the layers for Raman and FTIR micro-spectroscopy (DiPietro et al., 2005). Even with concentration of the extracted dye using Thin Layer Chromatography (TLC) there is a high uorescence background in the Raman spectrum (Fig. 13). This can be reduced considerably by using the technique of Shifted Subtracted Raman Spectroscopy (SSRS: Bell, 1998). Noticeable differences have been observed between new, aged, and articially aged lm stock in their FTIR spectra. (DiPietro et al., 2005). Identication of these differences is proceeding, and a technique of concentrating the dye using HPLC.

Fig. 10. Micrograph showing pearlitic laths, an indication that the steel has not been heated past 650 1C.

Fig. 11. Schematic representation of the crosssection of a colour motion picture lm. Film thicknesses are of the order of 10 mm.

Fig. 12. China girl image taken from the leader of a colour motion picture lm (post-1970).

440 D.C. Creagh / Radiation Physics and Chemistry 74 (2005) 426442

Kodak print 5384mod or 5386 (~1995) Raman spectra of the microtomed cross section 60000
cyan magenta



40000 Counts






1000 v (cm )





Fig. 13. Raman microspectra from the cyan, magenta, and yellow layers of Kodak colour motion lm stock (type 5386). Note that there is still a high uorescence signal relative to the signals from the dye.

This research study is in its early stages. Although the techniques used are now destructive, which in general is an anathema to conservators, work is concentrated on one image of many in the leader to the lm, and not on any of the images in the lm proper.

4. Conclusions Examples have been given of the use of diverse types of radiation for the solution of problems confronting art curators and conservators. One very signicant immediate outcome of the Aboriginal bark painting project has been the inuence 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 the both the National Gallery of Australias storage facilities will be inuenced by these research results. Criteria for the design of packing cases for transport of Aboriginal artefacts between museums within, and external, to Australia can be developed to ensure safe transport of these fragile items. As well, criteria can now be established to assist conservators in the preservation of Aboriginal artefacts. The information gained in the project has been given to the indigenous community to assist them in the preparation of their art works.

Examples have been given of the use of the new, developing techniques of synchrotron radiation for the characterization of museum artefacts. In particular Rietveld analysis has been shown to be a very useful technique for the study of small powder specimens. From the study of the metallurgy of Joe Byrnes armour we can answer some of the questions which the general public has been asking for nearly a century, and give the answer that:

 The armour was made from old plough shares and   

other scrap steel such as would be found around a farm. Because the temperature was less that 600 1C (dull red heat) it is most likely that it was fabricated in the bush, over a bushre. Because of the crudeness of the hammer blows it is certain that unskilled workers were involved. The mark at the front of the armour may be from a bullet, but the impact did not happen at the time of the siege at Glenrowan.

Research into colour motion picture lm is only just beginning to yield results. It has been included in this paper to show the complexity of the problems which face scientic conservators, and the breadth of

D.C. Creagh / Radiation Physics and Chemistry 74 (2005) 426442 441

knowledge a scientic conservator must have to solve problems aficting the collections for which they are responsible.

Acknowledgements The author wishes to acknowledge the support of the Australian Research Council for nancial support for this project under the Strategic Partnerships Industry Research and Technology (SPIRT) and the LINKAGE Schemes. Without the diligent support of the Research Associates, Kylie Roth, Nicola Smith, and Giovanna DiPietro the projects would not have been as successful as they have been. I am indebted to Dr. Rodger Heady for assistance with the SEM study of barks; the Director of the National Archives of Australia, the Director of the NGA, and the Director of the NMA, and the Director of the National Film and Sound Archive, for their nancial support. I wish to acknowledge the friendship of the Maningrida, Oenpelly and Yirrkala communities, and the assistance they afforded us in our eldwork. The synchrotron radiation data was analysed by Paul O Neill, whose tenacity and thoroughness has led to a heightened understanding of the way indigenous people collect and mix pigments. As well, Dr. Metta Sterns (Chemistry, Australia National University) gave willingly of her time to assist in the resolution of the data. I wish to acknowledge funding from the Australian Synchrotron Research Program and the valuable assistance of Dr. James Hester at the Australian National Beamline Facility at the Photon Factory. I am indebted to Rupert Hammond for allowing us to examine Joe Byrnes armour, for which he is custodian. The research on this armour was undertaken at Ansto, and I am most grateful to the Director of that institution for allowing us to use their facilities. I am indebted to Drs. Gordon Thorogood (XRD), Michael James (neutron diffraction), Graham Smith (optical metallography) and David Mitchell (TEM) for their contributions to the experimental programme at Ansto. David Hallam (National Museum of Australia) was of great assistance in organizing the research program on the armour, and was a senior member of the research team. The assistance given by Dr Sally Stowe (Research School of Biological Science, Australian National University) and Dr. Richard Webster (Research School of Chemistry, Australian National University) in developing techniques for the analysis of the dyes in the motion picture lm is gratefully acknowledged.

Baker, M.D., Endt, V., Hopwood, W., Erhardt, D., 1988. FTIR microspectrometry: a powerful conservation analysis tool.

In: Rosenberg, S.Z. (Ed.), Preprints of papers presented at the 16th Annual Meeting of the AIC. The American Institute for Conservation of Historic and Artistic Works, New Orleans, Washington, DC, pp. 113. Bell, S.E.J., 1998. Analysis of luminescent samples using subtracted shifted Raman spectroscopy. Analyst 123, 17291734. Chattaway, M.M., 1953. The anatomy of bark 1The genus of Eucalyptus Australian. J. Bot. 1 (3), 402433. Coote, K., 1998. Care of collections. In: Conservation for Aboriginal and Torres Strait Islander Keeping Places and Cultural Centres. Australian Museum, ISBN: 0-7313-1585-5. Creagh, D.C., 2003. Monochromators and lters. In: Prince, E. (Ed.), International Tables for Crystallography, vol. C, third ed. Kluwer, Amsterdam, pp. 236141 (Section 4.2.5). Creagh, D.C., Bradley, D. (Eds.), 2000. Radiation in Art and Archaeometry. Elsevier Science BV, Amsterdam. Creagh, D.C., Otieno-Alego, V., 2004. The use of radiation for the study of material of cultural heritage signicance. Nucl. Instrum. Methods B 213, 670676. Creagh, D.C., Foran, G.J., Cookson, D.J., Garrett, R.F., Johnson, F., 1998. An eight position capillary sample spinning stage for the diffractometer at BL20B at the photon Factory. J. Synchrotron Radiat. 5 (3), 823825. Creagh, D.C., Thorogood, G.T., James, M., Hallam, D.L., 2004. Analyses of Joe Byrnes armour. In: Hallam, D.L., Ashton, J.A. (Eds.), Proceedings of International Conference on Metals Conservation, METAL 04: ICOM-CC. National Museum of Australia, Canberra, Australia, pp. 207214 48 October 2004. Creagh, D.C., Thorogood, G.T., James, M., Hallam, D.L., 2004. Diffraction and uorescence studies of bushranger armour. Radiat. Phys. Chem. 71 (3-4), 841842. Deere, W.A., Howie, R.A., Zussman, R., 1980. Introduction to the Rock-Forming Minerals. Longman, Great Britain. DiPietro, G., Mahon, P., Creagh, D.C., Newnham, M., 2005. The identication of photographic dyes in cultural materials using Raman spectroscopy. In: Proceedings of the Eighth Conference on Non-Destructive Investigations and the Diagnostics and Conservation of the Cultural and Environmental Heritage. Paper 102. Edwards, H.G.M., Drummond, F., Ross, X., 1991. J. J. Raman Spectrosc. 30, 421428. Edwards, H.G.M., Farwell, D.W., Perez, F.R., Villar, S.J., 1999. Appl. Spectrosc. 53, 14361440. Gatenby, S.L., 1996. The identication of traditional binders used on Australian Aboriginal painted objects prior to 1970. Master of Applied Science in the Conservation of Cultural Materials Thesis, National Centre for Cultural Heritage Science Studies, Faculty of Applied Science, University of Canberra. Heady, R., Roth, K., Smith, N., 2003. Issues in conservation, in press. Larson, A.C., Von Dreele, R.B., 1986. General Structure Analysis System. Report LAUR 86-784. Los Alamos National Laboratory, Los Alamos, NM, USA.

442 D.C. Creagh / Radiation Physics and Chemistry 74 (2005) 426442 Taylor, J.C., 1991. Computer programs for standardless quantitative analysis of minerals using the full powder diffraction prole. Powder Diffract 6, 29. ONeill, P.M., CREAGH, D.C., Sterns, M., 2004. Studies of the composition of pigments used traditionally in Australian Aboriginal Bark paintings. Radiat. Phys. Chem. 71 (3-4), 841842. Rietveld, H.M., 1969. J. Appl. Crystallogr. 2, 6571. Rodriguez-Carvajal, A., 1993. J. Phys. B 192, 5566. Young, R.A. (Ed.), 1993. The Rietveld Method. International Union of Crystallography. Oxford University Press, Oxford, England.

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