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The Potential of Low Frequency EPR Spectroscopy in Studying Pottery Artifacts and Pigments.

Published online by Cambridge University Press:  18 July 2014

William J. Ryan ,
Nicholas Zumbulyadis  and
Joseph P. Hornak
William J. Ryan
Affiliation:
RIT Magnetic Resonance Laboratory, RIT Rochester, NY, 14623
Nicholas Zumbulyadis
Affiliation:
Independent Researcher, Rochester, NY
Joseph P. Hornak
Affiliation:
RIT Magnetic Resonance Laboratory, RIT Rochester, NY, 14623
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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.

Keywords

archaeologyelectron spin resonanceceramic
Type
Articles
Information
MRS Online Proceedings Library (OPL) , Volume 1656: Symposium PP – Materials Issues in Art and Archaeology X , 2014 , pp. 371 - 379
Copyright
Copyright © Materials Research Society 2014 

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References

REFERENCES

Shugar, A.N., Mass, J. L. (eds.), Handheld XRF for Art and Archaeology (Studies in Archaeological Sciences), Leuven University Press, 2013.10.11116/9789461660695CrossRefGoogle Scholar
Vandenabeele, P., Tate, J., Moens, L., Non-destructive Analysis of Museum Objects by Fibre-optic Raman Spectroscopy, Anal. Bioanal. Chem. , 387, 813 (2007).10.1007/s00216-006-0758-xCrossRefGoogle ScholarPubMed
Capitani, D., Di Tullio, V., Proietti, N., Nuclear Magnetic Resonance to Characterize and Monitor Cultural Heritage, Progress Nucl. Magn. Reson. , 64, 29 (2012).10.1016/j.pnmrs.2011.11.001CrossRefGoogle ScholarPubMed
Robins, G.V., Seeley, N. J., McNeil, D. A. C. and Symons, M. C. R., Identification of Ancient Heat Treatment in Flint Artefacts by ESR Spectroscopy, Nature , 276, 703 (1978).10.1038/276703a0CrossRefGoogle Scholar
Cordischi, D., Monna, D. and Segre, A. L., ESR Analysis of Marble Samples from Mediterranean Quarries of Archaeological Interest, Archaeometry , 25, 68 (1983).10.1111/j.1475-4754.1983.tb00662.xCrossRefGoogle Scholar
Attanasio, D., Capitani, D., Federici, C., Segre, A. L., Electron Spin Resonance Study of Paper Samples Dating from the Fifteenth to the Eighteenth Century, Archaeometry , 37, 377 (1995).10.1111/j.1475-4754.1995.tb00750.xCrossRefGoogle Scholar
Warashina, T., Higashimura, T., Maeda, Y., Determinationof the Firing Temperature of Ancient Pottery by Means of ESR Spectroscopy, British Museum Occasional Papers , 19, 117 (1981).Google Scholar
Bensimon, Y., Deroide, B., Clavel, S., Zanchetta, J.V., Electron Spin Resonance and Dilatometric Studies of Ancient Ceramics Applied to Determination of Firing Temperature, Jpn. J. Appl. Phys. 37, 4367 (1998).10.1143/JJAP.37.4367CrossRefGoogle Scholar
Presciutti, F., Capitani, D., Sgamellotti, A., Brunetti, B.G., Costantino, F., Viel, S., Segre, A., 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).10.1021/jp0536091CrossRefGoogle Scholar
Hornak, J.P., Spacher, M., Bryant, R.G., A Modular Low Frequency ESR Spectrometer, Meas. Sci. Technol. 2, 520 (1991).10.1088/0957-0233/2/6/005CrossRefGoogle Scholar
Rinard, G.A., Quine, R.W., Eaton, G.R., Eaton, S.S., Barth, E.D., Pelizzari, C.A., Halpern, H.J., Magnet and Gradient Coil System for Low-Field EPR Imaging, Concepts Magn. Reson. (Magnetic Resonance Engineering), 15, 51(2002).10.1002/cmr.10018CrossRefGoogle Scholar
Quine, R.W., Rinard, G.A., Eaton, S.S., Eaton, G.R., Pulsed, A and Wave, Continuous 250 MHz Electron Paramagnetic Resonance Spectrometer, Concepts Magn. Reson. 15, 84(2002).10.1002/cmr.10020CrossRefGoogle Scholar
Nishikawa, H., Fuji, H., Berliner, L.J., Helices and Surface Coils for Low-Field in vivo ESR and EPR Imaging Applications. J. Magn. Reson. 62, 79 (1969).Google Scholar
Sotgiu, A., Fuji, H, Gualtieri, G, Toroidal Surface Coil for Topical ESR Spectroscopy. J. Phys. E: Sci. Instrum. 20, 1428 (1987).10.1088/0022-3735/20/11/030CrossRefGoogle Scholar
Bendall, M.R., Surface Coil Technology. In Magnetic Resonance Imaging , ed. by Partain, C.L., Price, R.R., Patton, J.A., Kulkarni, M.V., James, A.E., Saunders, Philadelphia, 1988.Google Scholar
Ono, M., Ito, K., Kawamura, N., Hsieh, K C, Hirata, H, Tsuchihashi, N, Kamada, H., A Surface-Coil-type Resonator for in vivo ESR Measurements. J. Magn. Reson. , 104B, 180 (1994).10.1006/jmrb.1994.1073CrossRefGoogle ScholarPubMed
Lin, Y., Yokoyama, H., Ishida, S.-I., Tsuchihashi, N., Ogata, T., 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).10.1007/BF02592239CrossRefGoogle ScholarPubMed
Tada, M., Yokoyama, H., Toyoda, Y., Ohya, H., Ito, T., Ogata, T., Surface-Coil-Type Resonators for in Vivo Temporal ESR Measurements in Different Organs of Nitroxide-Treated Rats. Appl. Magn. Reson. 18, 575 (2000).10.1007/BF03162304CrossRefGoogle Scholar
Yokoyama, H., Tada, M., Sato, T., Ohya, H., Akatsuka, T., Modified Surface-Coil-Type Resonators for EPR: Measurements of a Thin Membrane Like Sample. Appl Magn Reson 24, 233 (2003).10.1007/BF03166663CrossRefGoogle Scholar
Berke, H., The Invention of Blue and Purple Pigments in Ancient Times, Chem Soc Rev 36, 15 (2007).10.1039/B606268GCrossRefGoogle ScholarPubMed
Pozza, G., Ajo, D., Chiari, G., De Zuane, F., Favaro, M., Photoluminescence of the Inorganic Pigments Egyptian Blue, Han Blue, and Han Purple, J. Cult. Herit. , 1, 393 (2000).10.1016/S1296-2074(00)01095-5CrossRefGoogle Scholar
Mirti, P., Appolonia, L., Casoli, A., Spectrochemical and Structural Studies on a Roman Sample of Egyptian Blue, Spectrochimica Acta (A) , 51A, 437 (1995).10.1016/0584-8539(94)E0108-MCrossRefGoogle Scholar
Clark, R.J.H., Curri, M.L., Laganara, C., Raman Microscopy: the Identification of Lapis Lazuli on Medieval Pottery Fragments from the South of Italy, Spectrochim. Acta (A) 53, 597 (1997).10.1016/S1386-1425(96)01768-4CrossRefGoogle Scholar
Colomban, P., Lapis Lazuli an Unexpected Blue Pigment in Iranian Lajvardina Ceramics, J. Raman Spectr. , 34, 420 (2003).10.1002/jrs.1014CrossRefGoogle Scholar
Gobeltz, N., Demortier, A., Lelieur, J.P., Duhayon, C., Correlation between EPR, Raman, and Colorimetric Characteristics of the Blue Ultramarine Pigments. J. Chem. Soc., Faraday Trans. , 94, 677 (1998).10.1039/a707619cCrossRefGoogle Scholar
Wertz, J.E., Bolton, J.R., Electron Spin Resonance: Elementary Theory and Practical Applications. Chapman and Hall, NY, 1972.Google Scholar
Hornak, J.P., Szumowski, J., Bryant, R.G., Elementary Single Turn Solenoids Used as the Transmitter and Receiver in Magnetic Resonance Imaging, Magn. Res. Imag. 5, 233 (1987).10.1016/0730-725X(87)90024-5CrossRefGoogle ScholarPubMed
Munsat, T., Hooke, W. M., Bozeman, S. P., Washburnd, S., Two New Planar Coil Designs for a High Pressure Radio Frequency Plasma Source. Appl. Phys. Lett. 66, 2180 (1995).10.1063/1.113939CrossRefGoogle Scholar
Szczepaniak, E., Hornak, J.P., ESR Imaging Based on the Modulation Field Phase, J. Magn. Reson. 104A, 315 (1993).10.1006/jmra.1993.1228CrossRefGoogle Scholar