Abstract
Non-destructive investigation, chemically fingerprinting, and authentication of ceramic cultural artifacts is a challenging analytical problem. Electron paramagnetic resonance (EPR) spectroscopy is capable of distinguishing between clays based on the paramagnetic metals present, and firing temperature (TF) based on the complexes of these metals formed at different TF values. Unfortunately, the 9 GHz frequency of conventional X-band EPR restricts sample size to a few mm and limits its applicability to small fragments. Low frequency EPR (LFEPR) is based on an EPR spectrometer operating at a few hundred MHz. LFEPR can utilize larger samples on the order of a few cm, but has a lower sensitivity due to the smaller Boltzmann ratio. Additionally, LFEPR may not be capable of detecting a spectral transition if the LFEPR operating frequency is less then the zero-field splitting of the paramagnetic metal complex. We utilized an LFEPR operating at 300 MHz which scans the applied magnetic field between the local Earth’s magnetic field and 26 mT to determine the feasibility of detecting EPR signals from clays, pigments, and glazes. Various clay samples were studied at 100 < TF < 1200 °C. Spectral differences were seen as a function of both clay type and TF. Differences in the LFEPR spectra of Han, Egyptian, and Ultramarine blue support the ability to distinguish among pigments. Paramagnetic impurities in glass may allow distinction between glaze spectra. We have also explored the utility of LFESR by the use of a radio frequency surface coil rather than an enclosed resonator. Although the active volume of the surface coil is ∼1 cm3, objects as large as 20 cm in diameter might be easily characterized with our spectrometer.
Similar content being viewed by others
References
A.N. Shugar, J. L. Mass (eds.), Handheld XRF for Art and Archaeology (Studies in Archaeological Sciences), Leuven University Press, 2013.
P. Vandenabeele, J. Tate, L. Moens, Non-destructive Analysis of Museum Objects by Fibre-optic Raman Spectroscopy, Anal. Bioanal. Chem., 387, 813 (2007).
D. Capitani, V. Di Tullio, N. Proietti, Nuclear Magnetic Resonance to Characterize and Monitor Cultural Heritage, Progress Nucl. Magn. Reson., 64, 29 (2012).
G.V. Robins, N. J. Seeley, D. A. C. McNeil and M. C. R. Symons, Identification of Ancient Heat Treatment in Flint Artefacts by ESR Spectroscopy, Nature, 276, 703 (1978).
D. Cordischi, D. Monna and A. L. Segre, ESR Analysis of Marble Samples from Mediterranean Quarries of Archaeological Interest, Archaeometry, 25, 68 (1983).
D. Attanasio, D. Capitani, C. Federici, A. L. Segre, Electron Spin Resonance Study of Paper Samples Dating from the Fifteenth to the Eighteenth Century, Archaeometry, 37, 377 (1995).
T. Warashina, T. Higashimura, Y. Maeda, Determinationof the Firing Temperature of Ancient Pottery by Means of ESR Spectroscopy, British Museum Occasional Papers, 19, 117 (1981).
Y. Bensimon, B. Deroide, S. Clavel, J.V. Zanchetta, Electron Spin Resonance and Dilatometric Studies of Ancient Ceramics Applied to Determination of Firing Temperature, Jpn. J. Appl. Phys. 37, 4367 (1998).
F. Presciutti, D. Capitani, A. Sgamellotti, B.G. Brunetti, F. Costantino, S. Viel, A. Segre, Electron Paramagnetic Resonance, Scanning Electron Microscopy with Energy Dispersion X-ray Spectrometry, X-ray Powder Diffraction, and NMR Characterization of Iron-Rich Fired Clays, J. Phys. Chem. B, 109, 22147(2005).
J.P. Hornak, M. Spacher, R.G. Bryant, A Modular Low Frequency ESR Spectrometer, Meas. Sci. Technol. 2, 520 (1991).
G.A. Rinard, R.W. Quine, G.R. Eaton, S.S. Eaton, E.D. Barth, C.A. Pelizzari, H.J. Halpern, Magnet and Gradient Coil System for Low-Field EPR Imaging, Concepts Magn. Reson. (Magnetic Resonance Engineering), 15, 51(2002).
R.W. Quine, G.A. Rinard, S.S. Eaton, G.R. Eaton, A Pulsed and Continuous Wave 250 MHz Electron Paramagnetic Resonance Spectrometer, Concepts Magn. Reson. 15, 84(2002).
H. Nishikawa, H. Fuji, L.J. Berliner, Helices and Surface Coils for Low-Field in vivo ESR and EPR Imaging Applications. J. Magn. Reson. 62, 79 (1969).
A. Sotgiu, H Fuji, G Gualtieri, Toroidal Surface Coil for Topical ESR Spectroscopy. J. Phys. E: Sci. Instrum. 20, 1428 (1987).
M.R. Bendall, Surface Coil Technology. In Magnetic Resonance Imaging, ed. by C.L. Partain, R.R. Price, J.A. Patton, M.V. Kulkarni, A.E. James, Saunders, Philadelphia, 1988.
M. Ono, K. Ito, N. Kawamura, K C Hsieh, H Hirata, N Tsuchihashi, H. Kamada, A Surface-Coil-type Resonator for in vivo ESR Measurements. J. Magn. Reson., 104B, 180 (1994).
Y. Lin, H. Yokoyama, S.-I. Ishida, N. Tsuchihashi, T. Ogata, In vivo Electron Spin Resonance Analysis of Nitroxide Radicals Injected into a Rat by a Flexible Surface-Coil-Type Resonator as an Endoscope- or a Stethoscope-Like Device. MAGMA 5, 99 (1997).
M. Tada, H. Yokoyama, Y. Toyoda, H. Ohya, T. Ito, T. Ogata, Surface-Coil-Type Resonators for in Vivo Temporal ESR Measurements in Different Organs of Nitroxide-Treated Rats. Appl. Magn. Reson. 18, 575 (2000).
H. Yokoyama, M. Tada, T. Sato, H. Ohya, T. Akatsuka, Modified Surface-Coil-Type Resonators for EPR: Measurements of a Thin Membrane Like Sample. Appl Magn Reson 24, 233 (2003).
H. Berke, The Invention of Blue and Purple Pigments in Ancient Times, Chem Soc Rev 36, 15 (2007).
G. Pozza, D. Ajo, G. Chiari, F. De Zuane, M. Favaro, Photoluminescence of the Inorganic Pigments Egyptian Blue, Han Blue, and Han Purple, J. Cult. Herit., 1, 393 (2000).
P. Mirti, L. Appolonia, A. Casoli, Spectrochemical and Structural Studies on a Roman Sample of Egyptian Blue, Spectrochimica Acta (A), 51A, 437 (1995).
R.J.H. Clark, M.L. Curri, C. Laganara, Raman Microscopy: the Identification of Lapis Lazuli on Medieval Pottery Fragments from the South of Italy, Spectrochim. Acta (A) 53, 597 (1997).
P. Colomban, Lapis Lazuli an Unexpected Blue Pigment in Iranian Lajvardina Ceramics, J. Raman Spectr., 34, 420 (2003).
N. Gobeltz, A. Demortier, J.P. Lelieur, C. Duhayon, Correlation between EPR, Raman, and Colorimetric Characteristics of the Blue Ultramarine Pigments. J. Chem. Soc., Faraday Trans., 94, 677 (1998).
J.E. Wertz, J.R. Bolton, Electron Spin Resonance: Elementary Theory and Practical Applications. Chapman and Hall, NY, 1972.
J.P. Hornak, J. Szumowski, R.G. Bryant, Elementary Single Turn Solenoids Used as the Transmitter and Receiver in Magnetic Resonance Imaging, Magn. Res. Imag. 5, 233 (1987).
T. Munsat, W. M. Hooke, S. P. Bozeman, S. Washburnd, Two New Planar Coil Designs for a High Pressure Radio Frequency Plasma Source. Appl. Phys. Lett. 66, 2180 (1995).
E. Szczepaniak, J.P. Hornak, ESR Imaging Based on the Modulation Field Phase, J. Magn. Reson. 104A, 315 (1993).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Ryan, W.J., Zumbulyadis, N. & Hornak, J.P. The Potential of Low Frequency EPR Spectroscopy in Studying Pottery Artifacts and Pigments.. MRS Online Proceedings Library 1656, 309–317 (2014). https://doi.org/10.1557/opl.2014.708
Published:
Issue Date:
DOI: https://doi.org/10.1557/opl.2014.708