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. Z., Zakhachuk, N. F., Sobolev, N. V., & Kozmenko, O. A. (1995). The electrochemical response of radiation defects of non-conducting materials An electrochemical access to age determinations. Journal of Electroanalytical Chemistry, 385(1), 139-142. doi:10.1016/0022-0728(94)03840-yDoménech-Carbó, A., Labuda, J., & Scholz, F. (2012). Electroanalytical chemistry for the analysis of solids: Characterization and classification (IUPAC Technical Report). Pure and Applied Chemistry, 85(3), 609-631. doi:10.1351/pac-rep-11-11-13Doménech-Carbó, A., Doménech-Carbó, M. T., & Costa, V. (Eds.). (2009). Electrochemical Methods in Archaeometry, Conservation and Restoration. Monographs in Electrochemistry. doi:10.1007/978-3-540-92868-3Doménech-Carbó, A., Doménech-Carbó, M. T., & Peiró-Ronda, M. A. (2011). Dating Archeological Lead Artifacts from Measurement of the Corrosion Content Using the Voltammetry of Microparticles. Analytical Chemistry, 83(14), 5639-5644. doi:10.1021/ac200731qDoménech-Carbó, A., Doménech-Carbó, M. T., Capelo, S., Pasíes, T., & Martínez-Lázaro, I. (2014). Dating Archaeological Copper/Bronze Artifacts by Using the Voltammetry of Microparticles. Angewandte Chemie International Edition, 53(35), 9262-9266. doi:10.1002/anie.201404522Benarie, M., & Lipfert, F. L. (1986). A general corrosion function in terms of atmospheric pollutant concentrations and rain pH. Atmospheric Environment (1967), 20(10), 1947-1958. doi:10.1016/0004-6981(86)90336-7Strandberg, H. (1998). Reactions of copper patina compounds—II. influence of sodium chloride in the presence of some air pollutants. Atmospheric Environment, 32(20), 3521-3526. doi:10.1016/s1352-2310(98)00058-2Cano, E., Lafuente, D., & Bastidas, D. M. (2009). Use of EIS for the evaluation of the protective properties of coatings for metallic cultural heritage: a review. Journal of Solid State Electrochemistry, 14(3), 381-391. doi:10.1007/s10008-009-0902-6Hernandez-Escampa, M., Gonzalez, J., & Uruchurtu-Chavarin, J. (2009). Electrochemical assessment of the restoration and conservation of a heavily corroded archaeological iron artifact. Journal of Applied Electrochemistry, 40(2), 345-356. doi:10.1007/s10800-009-0003-3Angelini, E., Grassini, S., Parvis, M., & Zucchi, F. (2011). An in situ investigation of the corrosion behaviour of a weathering steel work of art. Surface and Interface Analysis, 44(8), 942-946. doi:10.1002/sia.3842Grassini, S., Angelini, E., Parvis, M., Bouchar, M., Dillmann, P., & Neff, D. (2013). An in situ corrosion study of Middle Ages wrought iron bar chains in the Amiens Cathedral. Applied Physics A, 113(4), 971-979. doi:10.1007/s00339-013-7724-1Doménech-Carbó, A., Doménech-Carbó, M. T., Peiró-Ronda, M. A., Martínez-Lázaro, I., & Barrio-Martín, J. (2012). Application of the voltammetry of microparticles for dating archaeological lead using polarization curves and electrochemical impedance spectroscopy. Journal of Solid State Electrochemistry, 16(7), 2349-2356. doi:10.1007/s10008-012-1668-9Degrigny, C., Guibert, G., Ramseyer, S., Rapp, G., & Tarchini, A. (2009). Use of E corr vs time plots for the qualitative analysis of metallic elements from scientific and technical objects: the SPAMT Test Project. Journal of Solid State Electrochemistry, 14(3), 425-435. doi:10.1007/s10008-009-0890-6Souissi, N., Bousselmi, L., Khosrof, S., & Triki, E. (2004). Voltammetric behaviour of an archeaological bronze alloy in aqueous chloride media. Materials and Corrosion, 55(4), 284-292. doi:10.1002/maco.200303719Souissi, N., Triki, E., Bousselmi, L., & Khosrof, S. (2006). Comparaison between archaeological and artificially aged bronze interfaces. Materials and Corrosion, 57(10), 794-799. doi:10.1002/maco.200503974Souissi, N., & Triki, E. (2009). Characterization of ethnographic copper corrosion. Materials and Corrosion, 60(4), 262-268. doi:10.1002/maco.200805068Mata, A. L., Salta, M. M. L., Neto, M. M. M., Mendonça, M. H., & Fonseca, I. T. E. (2010). Characterization of two Roman coins from an archaeological site in Portugal. Materials and Corrosion, 61(3), 205-210. doi:10.1002/maco.200905284Feliu, S., Morcillo, M., & Feliu, S. (1993). The prediction of atmospheric corrosion from meteorological and pollution parameters—II. Long-term forecasts. Corrosion Science, 34(3), 415-422. doi:10.1016/0010-938x(93)90113-uSpence, J. W., Haynie, F. H., Lipfert, F. W., Cramer, S. D., & McDonald, L. G. (1992). Atmospheric Corrosion Model for Galvanized Steel Structures. CORROSION, 48(12), 1009-1019. doi:10.5006/1.3315903Bhattacharjee, S., Roy, N., Dey, A. K., & Banerjee, M. K. (1993). Statistical appraisal of the atmospheric corrosion of mild steel. Corrosion Science, 34(4), 573-581. doi:10.1016/0010-938x(93)90273-jKobus, J. (2000). Long-term atmospheric corrosion monitoring. Materials and Corrosion, 51(2), 104-108. doi:10.1002/(sici)1521-4176(200002)51:23.0.co;2-vBalasubramaniam, R., Laha, T., & Srivastava, A. (2004). Long term corrosion behaviour of copper in soil: A study of archaeological analogues. Materials and Corrosion, 55(3), 194-202. doi:10.1002/maco.200303723Natesan, M., Venkatachari, G., & Palaniswamy, N. (2006). Kinetics of atmospheric corrosion of mild steel, zinc, galvanized iron and aluminium at 10 exposure stations in India. Corrosion Science, 48(11), 3584-3608. doi:10.1016/j.corsci.2006.02.006Doménech, A., Doménech-Carbó, M. T., Pasies, T., & del Carmen Bouzas, M. (2012). Modeling Corrosion of Archaeological Silver-Copper Coins Using the Voltammetry of Immobilized Particles. Electroanalysis, 24(10), 1945-1955. doi:10.1002/elan.201200252Rosas-Camacho, O., Uquidi-Macdonald, M., & Macdonald, D. D. (2009). Deterministic Modeling of the Corrosion of Low-Carbon Steel by Dissolved Carbon Dioxide and the Effect of Acetic Acid. I-Effect of Carbon Dioxide. doi:10.1149/1.3259806Macdonald, D., & Englehardt, G. (2010). The Point Defect Model for Bi-Layer Passive Films. doi:10.1149/1.3496427Sharifi-Asl, S., Taylor, M. L., Lu, Z., Engelhardt, G. R., Kursten, B., & Macdonald, D. D. (2013). Modeling of the electrochemical impedance spectroscopic behavior of passive iron using a genetic algorithm approach. Electrochimica Acta, 102, 161-173. doi:10.1016/j.electacta.2013.03.143Macdonald, D. D. (2011). The history of the Point Defect Model for the passive state: A brief review of film growth aspects. Electrochimica Acta, 56(4), 1761-1772. doi:10.1016/j.electacta.2010.11.005Doménech-Carbó, A., Lastras, M., Rodríguez, 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. doi:10.1007/s10008-013-2232-yBlum, D., Leyffer, W., & Holze, R. (1996). Pencil-Leads as new electrodes for abrasive stripping voltammetry. Electroanalysis, 8(3), 296-297. doi:10.1002/elan.1140080317Doménech-Carbó, A., Doménech-Carbó, M. T., & Peiró-Ronda, Mªa. (2011). ‘One-Touch’ Voltammetry of Microparticles for the Identification of Corrosion Products in Archaeological Lead. Electroanalysis, 23(6), 1391-1400. doi:10.1002/elan.201000739Nair, M. T. ., Guerrero, L., Arenas, O. L., & Nair, P. . (1999). Chemically deposited copper oxide thin films: structural, optical and electrical characteristics. Applied Surface Science, 150(1-4), 143-151. doi:10.1016/s0169-4332(99)00239-1Scott, D. A. (1997). Copper compounds in metals and colorants: oxides and hydroxides. Studies in Conservation, 42(2), 93-100. doi:10.1179/sic.1997.42.2.93Doménech, A., Doménech-Carbó, M. T., & Martínez-Lázaro, I. (2010). Layer-by-layer identification of copper alteration products in metallic works of art using the voltammetry of microparticles. Analytica Chimica Acta, 680(1-2), 1-9. doi:10.1016/j.aca.2010.09.002Doménech, A., Doménech-Carbó, M. T., Pasies, T., & Bouzas, M. C. (2011). Application of Modified Tafel Analysis to the Identification of Corrosion Products on Archaeological Metals Using Voltammetry of Microparticles. Electroanalysis, 23(12), 2803-2812. doi:10.1002/elan.201100577Li, W. S., Cai, S. Q., & Luo, J. L. (2004). Chronopotentiometric Responses and Capacitance Behaviors of Passive Film Formed on Iron in Borate Buffer Solution. Journal of The Electrochemical Society, 151(4), B220. doi:10.1149/1.1667521Liu, W., Zhang, H., Qu, Z., Zhang, Y., & Li, J. (2009). Corrosion behavior of the steel used as a huge storage tank in seawater. Journal of Solid State Electrochemistry, 14(6), 965-973. doi:10.1007/s10008-009-0886-2Toledo-Matos, L. A., & Pech-Canul, M. A. (2010). Evolution of an iron passive film in a borate buffer solution (pH 8.4). Journal of Solid State Electrochemistry, 15(9), 1927-1934. doi:10.1007/s10008-010-1213-7Park, J.-J., & Pyun, S.-I. (2003). Analysis of impedance spectra of a pitted Inconel alloy 600 electrode in chloride ion-containing thiosulfate solution at temperatures of 298–573 K. Journal of Solid State Electrochemistry, 7(6), 380-388. doi:10.1007/s10008-002-0346-8Ibrahim, M. A., Pongkao, D., & Yoshimura, M. (2001). The electrochemical behavior and characterization of the anodic oxide film formed on titanium in NaOH solutions. Journal of Solid State Electrochemistry, 6(5), 341-350. doi:10.1007/s100080100229Xia, Z., Nanjo, H., Aizawa, T., Kanakubo, M., Fujimura, M., & Onagawa, J. (2007). Growth process of atomically flat anodic films on titanium under potentiostatical electrochemical treatment in H2SO4 solution. Surface Science, 601(22), 5133-5141. doi:10.1016/j.susc.2007.04.211Acevedo-Peña, P., Vázquez, G., Laverde, D., Pedraza-Rosas, J. E., & González, I. (2009). Influence of structural transformations over the electrochemical behavior of Ti anodic films grown in 0.1 M NaOH. Journal of Solid State Electrochemistry, 14(5), 757-767. doi:10.1007/s10008-009-0838-xFabregat-Santiago, F., Bisquert, J., Garcia-Belmonte, G., Boschloo, G., & Hagfeldt, A. (2005). Influence of electrolyte in transport and recombination in dye-sensitized solar cells studied by impedance spectroscopy. Solar Energy Materials and Solar Cells, 87(1-4), 117-131. doi:10.1016/j.solmat.2004.07.017Rubinstein, I. (1987). Electrochemical Impedance Analysis of Polyaniline Films on Electrodes. Journal of The Electrochemical Society, 134(12), 3078. doi:10.1149/1.2100343Lee, S.-J., & Pyun, S.-I. (2006). Assessment of corrosion resistance of surface-coated galvanized steel by analysis of the AC impedance spectra measured on the salt-spray-tested specimen. Journal of Solid State Electrochemistry, 11(6), 829-839. doi:10.1007/s10008-006-0229-5Doménech, A., Doménech-Carbó, M. T., & Edwards, H. G. M. (2008). Quantitation from Tafel Analysis in Solid-State Voltammetry. Application to the Study of Cobalt and Copper Pigments in Severely Damaged Frescoes. Analytical Chemistry, 80(8), 2704-2716. doi:10.1021/ac7024333Mora, N., Cano, E., Polo, J. L., Puente, J. M., & Bastidas, J. M. (2004). Corrosion protection properties of cerium layers formed on tinplate. Corrosion Science, 46(3), 563-578. doi:10.1016/s0010-938x(03)00171-9Bastidas, J. M., Polo, J. L., Cano, E., Torres, C. L., & Mora, N. (2000). Localised corrosion of highly alloyed stainless steels in an ammonium chloride and diethylamine chloride aqueous solution. Materials and Corrosion, 51(10), 712-718. doi:10.1002/1521-4176(200010)51:103.0.co;2-vXu, J., Huang, W., & McCreery, R. L. (1996). Isotope and surface preparation effects on alkaline dioxygen reduction at carbon electrodes. Journal of Electroanalytical Chemistry, 410(2), 235-242. doi:10.1016/0022-0728(96)04545-7Kuang, F., Zhang, D., Li, Y., Wan, Y., & Hou, B. (2008). Electrochemical impedance spectroscopy analysis for oxygen reduction reaction in 3.5% NaCl solution. Journal of Solid State Electrochemistry, 13(3), 385-390. doi:10.1007/s10008-008-0570-yChen, G., Waraksa, C. C., Cho, H., Macdonald, D. D., & Mallouka, T. E. (2003). EIS Studies of Porous Oxygen Electrodes with Discrete Particles. Journal of The Electrochemical Society, 150(9), E423. doi:10.1149/1.159472

Isomerization and Redox Tuning: Reorganizing the Maya Blue Puzzle from Synthetic, Spectral, and Electrochemical Issues

[EN] A new approach to describe the composition of Maya blue (MB), an ancient organic- inorganic hybrid material, is presented. It is based on the analysis of attenuated total reflection-Fourier transform infrared (ATR-FTIR), Raman spectroscopy, UV-visible (vis) spectroscopic, and electrochemical data for indigo and dehydroindigo plus palygorskite hybrids, including a novel methodology using electrocatalytic effects on the oxygen reduction reaction. As a result, it is concluded that MB results from the tautomerization of indigo-to-indigo hemienol and the subsequent oxidation of these isomeric forms to dehydroindigo, all associated with the palygorskite clay framework, at temperatures above 100 degrees C. This model is also consistent with C-13 NMR data on indigo plus sepiolite hybrids. A consistent set of thermochemical parameters is obtained from ATR-FTIR, solid-state electrochemistry, and UV-vis diffuse reflectance spectra for the successive isomerization and redox tuning processes experienced by palygorskite-associated indigo.Projects PID2020-113022GB-I00 and RTI2018-100910-BC42, supported by MCIN/AEI/10.13039/501100011033 are gratefully acknowledged for all of the equipment employed. NMR was registered at the U26 facility of ICTS "NANBIOSIS" at the SCSIE of the Universitat of Valencia.Doménech-Carbó, A.; Costero, AM.; Gil Grau, S.; Montoya, N.; López-Carrasco, A.; Sáez, JA.; Arroyo, P.... (2021). Isomerization and Redox Tuning: Reorganizing the Maya Blue Puzzle from Synthetic, Spectral, and Electrochemical Issues. The Journal of Physical Chemistry. 125(47):26188-26200. https://doi.org/10.1021/acs.jpcc.1c0793226188262001254

Multiple-scan voltammetry of immobilized particles of ancient copper/bronze coins

The application of a multiple-scan strategy to study the structure of the corrosion patina of copper/bronze ancient objects using the voltammetry of immobilized microparticles (VIMP) is described. Upon nanosample attachment to graphite electrodes in contact with aqueous acetate buffer, voltammetric signatures characterizing cuprite with variable degree of crystallinity are recorded by means of successive cathodic scans reflecting the composition of the corrosion patina. The reported methodology, complemented with ion beam-field emission scanning electron microscopy (FIB-FESEM) and high-resolution field emission scanning electron microscopy (HRFESM-EDX), is applied to a set of coins fabricated between 1709 and 1962 revealing different corrosion\ua0patterns

Solid-state electrochemical characterization of emissions and authorities producing Roman brass coins

The voltammetry of immobilized particles (VIMP) is applied to describe the solid state electrochemistry of brass. This methodology, which involves sampling at the nanogram level, is applied to discriminate mints/authorities producing different Roman monetary emissions covering since the Republic (88 BCE) to Domitianus (55–96 CE) Upon attachment to graphite electrodes in contact with aqueous acetate buffer at pH 4.75, well defined voltammetric responses were obtained centered on Cu- and Zn-localized signals whose intensity can be correlated to EMP data, being sensitive to the contents of Zn (15–30 wt.%) and Sn (0.01–1.1 wt.%). Voltammetric data, combined with ATR-FTIR and FIB-FESEM/EDS, yield information on the structure of the metal patina and permit to characterize different monetary emissions being able, in the case of Augustus’ sestertii, to discriminate between the productions from different monetary authorities

Hematite as an Electrocatalytic Marker for the Study of Archaeological Ceramic Clay bodies: A VIMP and SECM Study**

The electrocatalytic effect exerted by hematite, a ubiquitous component of clay bodies, on the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) can be used to acquire information on archaeological ceramics. The solid-state voltammetric response of different hematite and ochre specimens, accompanied by SECM analysis in contact with 0.10 M HCl aqueous solution, is described. In air-saturated solutions, catalytic effects on the ORR and OER are accompanied by Fe(III)/Fe(II) and Fe(IV)/Fe(III) redox reactions. Such processes are conditioned by a variety of factors, the hydroxylation degree of the mineral surfaces being particularly influential, and exhibit significant variations upon heating the specimens between 300 and 900 °C. Voltammetric measurements carried out on a set of archaeological samples of Apulian red-figured pottery dated back within 5th and 4th centuries BCE permit to obtain site-characteristic voltammetric profiles

Crossing VIMP and EIS for studying heterogeneous sets of copper/bronze coins

Electrochemical impedance spectroscopy (EIS) and voltammetry of immobilized particles (VIMP) measurements using air-saturated mineral water and 0.10 M NaClO 4 aqueous solution as electrolytes were applied to eurocent coins and a set of copper/bronze coins from the late nineteenth century exhibiting significant heterogeneity in their degree and type of corrosion. The obtained data presented satisfactory repeatability being fitted to relatively simple equivalent circuits which were dependent on the electrolyte and bias potential, the more satisfactory conditions being obtained using the reduction of dissolved oxygen as a redox probe. Consistent data were obtained using VIMP and EIS characterizing different corrosion patterns, and establishing the possibility of discriminating different monetary emissions in favorable cases of high level of corrosion

Experimental and theoretical study of possible correlation between the electrochemistry of canthin-6-one and the anti-proliferative activity against human cancer stem cells

This work presents an approach to study the performance of novel targets able to overcome cancer stem cell chemoresistance, based on the voltammetric data for microparticulate films of natural or synthetic alkaloids from the canthin-6-one series. A comparison of this voltammetric technique with conventional solution phase electrochemistry suggests the differences in the anti-proliferative activity of canthin-6-ones could be tentatively correlated to their different capacity to generate semiquinone radical anions. These data also match theoretical calculations