Electrochemical analysis of gold embroidery threads from archeological textiles

[EN] A methodology for characterizing archeological gold embroidery threads based on two analytical techniques is described: Field emission scanning electron microscopy (FESEM-EDX) and voltammetry of immobilized microparticle (VIMP) methodologies. After the analysis of the chemical composition of the metallic foil, we analyze specific voltammetric features associated with the oxidation of gold in contact with aqueous H2SO4 and HCl electrolytes. Cyclic and square wave voltammetries (VMP) have been used to get information about the elemental composition and the corrosion products of the samples. AFM, FESEM-EDX, and FESEM-FIB-EDX methodologies complete the study and bring us closer to the composition of the alloys and the embroidery manufacture techniques. This technique actualizes the VIMP data and evidences the morphological and elemental differences between them; in particular, it is confirmed that Au-Ag-Cu alloys, with notably differences in Ag content depending on the provenance, were used.Projects CTQ2014-53736-C3-1-P and CTQ2014-53736-C3-2P, which are supported with Ministerio de Economia, Industria y Competitividad (MINECO), and Fondo Europeo de Desarrollo Regional (ERDF) funds, as well as project CTQ2017-85317-C2-1-P supported with funds from MINECO, ERDF, and Agencia Estatal de Investigacion (AEI), are gratefully acknowledged.Martínez, B.; Piquero-Cilla, J.; Domenech Carbo, MT.; Montoya, N.; Doménech Carbó, A. (2018). Electrochemical analysis of gold embroidery threads from archeological textiles. Journal of Solid State Electrochemistry. 22(7):2205-2215. https://doi.org/10.1007/s10008-018-3927-xS22052215227Járó M (2003). 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Electrochemical analysis of the first Polish coins using voltammetry of immobilized particles

[EN] A series of 20 denarii from Boleslaus the Brave (992-1025) and Mieszko II Lambert (1025-1034), corresponding to the beginning of the Polish state were studied using the voltammetry of immobilized particles (VIMP) methodology. VIMP experiments, applied to nanosamples of the corrosion layers of the coins in contact with aqueous acetate buffer, provided well-defined responses mainly corresponding to the corrosion products of copper and lead. Such voltammetric responses, combined with X-ray fluorescence (XRF) spectroscopy experiments performed on the same set of coins, and complemented by focusing ion beam-field emission scanning electron microscope (FIB-FESEM) on silver coins from the 19th century, supported the hypothesis that two different metal sources were used in the former historical period and suggested that the coins were produced in three different mints. (C) 2016 Elsevier B.V. All rights reserve.Financial support from the MINECO Projects CTQ2014-53736-C3-1-P and CTQ2014-53736-C3-2-P which are supported with ERDF funds is gratefully acknowledged. The authors are very grateful to the Polish Ministry of Science and Higher Education for partly financing the work presented in this paper through a grant within the framework of the National Program for the Development of the Humanities (Decision No. 0100/NPRH3/H12/82/2014) and also wish to thank Dr. Jose Luis Moya Lopez and Mr. Manuel Planes Insausti (Microscopy Service of the Universitat Politecnica de Valencia) for technical support.Doménech Carbó, A.; Del Hoyo Meléndez, JM.; Domenech Carbo, MT.; Piquero-Cilla, J. (2017). Electrochemical analysis of the first Polish coins using voltammetry of immobilized particles. Microchemical Journal. 130:47-55. https://doi.org/10.1016/j.microc.2016.07.020S475513

Dating archaeological copper using electrochemical impedance spectroscopy. Comparison with voltammetry of microparticles dating

[EN] A methodology for dating copper/bronze archaeological objects aged under atmospheric environments using electrochemical impedance spectroscopy (EIS) is described. The method is based on the measurement of resistance associated to the growth of corrosion layers in EIS recorded upon immersion of the pieces in mineral water and applying a bias potential for the reduction of dissolved oxygen. Theoretical expressions for the time variation of such resistance following a potential rate law are presented. Equivalent expressions are derived and applied for estimating the variation of the tenorite/cuprite ratio from their specific voltammetric signals using voltammetry of microparticles data. Calibration curves were constructed from a set of well-documented coins.Financial support from the MEC Projects CTQ2011-28079-CO3-01 and 02 and CTQ2014-53736-C3-2-P which are supported with ERDF funds is gratefully acknowledged.Domenech Carbo, A.; Capelo, S.; Piquero-Cilla, J.; Domenech Carbo, MT.; Barrio, J.; Fuentes, A.; Al Sekhaneh, W. (2016). Dating archaeological copper using electrochemical impedance spectroscopy. Comparison with voltammetry of microparticles dating. Materials and Corrosion. 67(2):120-129. https://doi.org/10.1002/maco.201408048S120129672Friedman, I., & Smith, R. L. (1960). Part I, The Development of the Method. American Antiquity, 25(4), 476-493. doi:10.2307/276634Reich, S., Leitus, G., & Shalev, S. (2003). Measurement of corrosion content of archaeological lead artifacts by their Meissner response in the superconducting state; a new dating method. New Journal of Physics, 5, 99-99. doi:10.1088/1367-2630/5/1/399Scholz, F., Schröder, U., Meyer, S., Brainina, K. 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Dating of Archaeological Gold by Means of Solid State Electrochemistry

This is the peer reviewed version of the following article: Doménech Carbó, Antonio, Scholz, Fritz , Domenech Carbo, Mª Teresa, Piquero-Cilla, Juan , Montoya, Noemí, Pasies -Oviedo, Trinidad, Gozalbes, Manuel , Melchor Montserrat, José Manuel , Oliver, Arturo . (2018). Dating of Archaeological Gold by Means of Solid State Electrochemistry.ChemElectroChem, 5, 15, 2113-2117. DOI: 10.1002/celc.201800435 , which has been published in final form at http://doi.org/10.1002/celc.201800435. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving[EN] In archaeology and history of art, age determination is a fundamental analytical problem. While several techniques for age determination of various materials, like radiocarbon dating, are established, these methods cannot be applied for metals, for which new techniques have to be developed. For the first time a dating method for archaeological gold objects is described which is based on a corrosion clock and electrochemical measurements, using the voltammetry of immobilized particles. Samples are prepared by one touch' with a graphite pencil, only transferring a few nanograms of the archaeological gold. The method has been calibrated with the help of a series of well-documented gold specimen from different prehistory museums covering the last 2600years. Our results prove that this corrosion clock is going on a constant pace, practically independent of the environment, making it most attractive for applications in archaeometry.Projects CTQ2014-53736-C3-1-P and CTQ2014-53736-C3-2-P, which are supported with Ministerio de Economia, Industria y Competitividad (MINECO) and Fondo Europeo de Desarrollo Regional (ERDF) funds, as well as project CTQ2017-85317-C2-1-P supported with funds from, MINECO, ERDF and Agencia Estatal de Investigacion (AEI) are gratefully acknowledged. The authors also wish to thank Dr. Jose Luis Moya Lopez, Mrs. Alicia Nuez Inbernon and Mr. Manuel Planes Insausti (Microscopy Service of the Universitat Politecnica de Valencia) and M. Teresa Minguez and Clara Yebenes (Seccion de Microscopia del SCSIE, Universitat deValencia) for technical support.Doménech Carbó, A.; Scholz, F.; Domenech Carbo, MT.; Piquero-Cilla, J.; Montoya, N.; Pasies -Oviedo, T.; Gozalbes, M.... (2018). Dating of Archaeological Gold by Means of Solid State Electrochemistry. ChemElectroChem. 5(15):2113-2117. https://doi.org/10.1002/celc.201800435S2113211751

Monitoring stabilizing procedures of archaeological iron using electrochemical impedance spectroscopy

A methodology for monitoring washing procedures applied to stabilize archaeological iron is described. It is based on the combination of voltammetry of microparticles (VMP) with electrochemical impedance spectroscopy (EIS). A semiempirical approach is used where the impedances at low and high frequencies were related with the fraction areas of passive and corrosion layers generated during the stabilizing treatment, the thickness, and the porosity of the corrosion layer. The variation of such parameters with the time of washing was determined from EIS data for four types of desalination procedures using concentrated NaOH and/or Na2SO3 aqueous solutions on archaeological iron artifacts. After 2 months of treatment, EIS data indicate that an essentially identical stable state was attained in all cases, as confirmed by the formation of a passive magnetite layer identified in VMP measurements while the rate of variation of corroded surface and porosity at short washing times varied significantly from one stabilization procedure to another.Financial support from the MEC Project CTQ2011-28079-CO3-02 which is supported with ERDF funds is gratefully acknowledged.Domenech Carbo, A.; Lastras Pérez, M.; Rodríguez Calás, F.; Cano, E.; Piquero Cilla, J.; Osete Cortina, L. (2013). Monitoring stabilizing procedures of archaeological iron using electrochemical impedance spectroscopy. Journal of Solid State Electrochemistry. 18(2):399-409. https://doi.org/10.1007/s10008-013-2232-yS399409182Cronyn JM (1990) The elements of archaeological conservation. 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Monitoring stabilizing procedures of archaeological iron using electrochemical impedance spectroscopy

A methodology for monitoring washing procedures applied to stabilize archaeological iron is described. It is based on the combination of voltammetry of microparticles (VMP) with electrochemical impedance spectroscopy (EIS). A semi-empirical approach is used where the impedances at low and high frequencies were related with the fraction areas of passive and corrosion layers generated during the stabilizing treatment, the thickness, and the porosity of the corrosion layer. The variation of such parameters with the time of washing was determined from EIS data for four types of desalination procedures using concentrated NaOH and/or Na2SO3 aqueous solutions on archaeological iron artifacts. After 2 months of treatment, EIS data indicate that an essentially identical “stable” state was attained in all cases, as confirmed by the formation of a passive magnetite layer identified in VMP measurements while the rate of variation of corroded surface and porosity at short washing times varied significantly from one stabilization procedure to another.Peer Reviewe