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Use of Electrochemical Techniques In metal Conservation

Metal WG

Bibliography
on the use of electrochemical techniques in metal conservation

This bibliography has been compiled by Dr Kilian Anheuser, Conservateur responsable du laboratoire, des ateliers de restauration et de la conservation prventive at the Muse d'art et d'histoire in Geneva (Switzerland). Contributors were: Annemie Adriaens, Kilian Anheuser, Gabriela Cicileo, Virginia Costa, Christian Degrigny, Gerhard Eggert, Marc Gener, Ilonne de Groot, Paola Letardi, Karen Leyssens, Paul Mardikian, Bart Schotte, Karen Stemann Petersen, Hisasi Takenouti and Denise Witschard. Initials after an entry indicate the author of any comment. To avoid a lengthy and confusing list of out-of-date and difficult to obtain papers the following general rules have been applied : Preference was given to recent publications (post 1990) in refereed papers. Student projects and internal reports were not normally included, assuming that the authors and their supervisors would have published any relevant contents. Some reports of particular interest are listed though at the end of the bibliography. The older literature which is today only of historical interest has been largely omitted from this list. It can be easily accessed through references in the publications listed below.

General introduction
Costa, Virginia (2003). "Electrochemistry as a conservation tool: an overview", in: Conservation Science 2002. Ed. Joyce H. Townsend, K. Eremin and A. Adriaens, Archetype, London, 88-95. The application of electrochemical methods to the

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conservation of metallic works of art is reviewed. The two application fields in conservation - treatment and research - are both considered. (KL) Degrigny, Christian (2001). "Du dgagement des canons par lectrolyse la consolidation rductrice des plombs altrs ou lhistoire de loptimisation des techniques de restauration du mtal par voie lectrolytique". Cahier technique de lAraafu 7, 32-35. Degrigny, Christian, et Nol Lacoudre (1999). "Les techniques lectrolytiques", in : A la Recherche du Mtal Perdu,. Ed. H. Roudet-Meyer, Errance, Paris, 114-127. A review of the use of electrochemical techniques in conservation in France (CD) Eggert, Gerhard (1994). "Metallreduktion in Flssigkeiten", in: Peter Heinrich, Ed. Metallrestaurierung, Callwey, Mnchen, 126-137. Introductory, easy to read paper on the theory of electrolytic methods in metals conservation. The references are now rather dated. (KA) Espi, Laurent, Lacoudre, N., Beldjoudi, T. and Dugot J. (2000). "L'lectrochimie au service du patrimoine musical"; Techn 12, 19-27. North, N.A., "Conservation of metals", in: Conservation of marine archaeological objects, Ed. C. Pearson, Butterworth-Heinemann, London, 1987, 207-252. Remains a reference book for iron treated by electrolysis. (PM)

Investigation and treatment of aluminium alloys


Bailey, G. (2004) The stabilization of A wrecked and corroded aluminium aircraft, in the proceedings of the ICOM-CC Metal interim meeting METAL 04, 453-464 Degrigny, Christian (1990). "Mise au point dun traitement cathodique de stabilisation de pices en alliages daluminium dgrades par corrosion en milieu aqueux". Thse de docteur-ingnieur de lUniversit de Paris VI, 169p. Corrosion (pitting) and electrolytic stabilisation of aircraft remains made of aluminium alloys. Study of the sensitivity of aluminium alloys to cathodic corrosion (CD). Degrigny, Christian (1991). "Conservation et stabilisation d'alliages d'aluminium prlevs sur des paves aronautiques immerges en eau douce: les conditions du traitement lectrolytique". Conservation, restauration des biens culturels: revue de l'ARAAFU, 311, 27-39. Degrigny, Christian (1992). "Traitements lectrolytiques de vestiges subaquatiques de grandes dimensions a base d'alliages d'aluminium", in : Conservation et restauration d'objets metalliques. Archologie en Yvelines, Document de travail 5. Versailles: Conseil gnral des Yvelines, 30-49. Degrigny, Christian (1993). "La mise au point d'un traitement cathodique de stabilisation de vestiges aronautiques immergs en alliages d'aluminium", in : Saving the twentieth century: the conservation of modern materials, Ed. D. Grattan, Canadian Conservation Institute, Ottawa, 373-379. Degrigny, Christian (1995). "Stabilisation de moteurs d'avion immergs". Studies in Conservation 40, 10-18. An English translation made by the Canadian Conservation Institute staff can be provided by the author (CD) Hallam, David L., Adams, C.D., Bailey, G. and Heath, Graham, A. (1997). "Redefining the electrochemical treatment of historic aluminium objects", in: Metal 95, Ed. Ian D. Macleod, Stphane L. Pennec and Luc Robbiola, James & James, London, 220-222. The use of electrochemical techniques to redefine the conditions for the electrochemical treatment of aluminium exposed to saline environments is discussed. (KL)

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Bibliography

Investigation and treatment of copper alloys


Al-Kharafi, F. M., and Shalaby, H.M. (1995). "Corrosion behavior of annealed and harddrawn copper in soft tap water". Corrosion 51, 469-481. Ammeloot, F., Fiaud, C. and Sutter, E.M.M. (1997). "Application of photoelectrochemical methods for the characterization of Cu(I) oxide layers modified in the presence of corrosion inhibitors". Electrochimica Acta 42, 3565-3574. The influence of azole-type corrosion inhibitors (benzotriazole, mercaptobenzothiazole or mercaptobenzoxazole) on the photoelectrochemical behaviour of copper electrodes under open-circuit potential was investigated in a 0.5M NaCl solution. A correlation between the inhibition efficiency of an inhibitor, the oxide layer thickness, the polarization resistance and the semiconducting properties of the Cu2O layer more or less stabilized by the inhibitor was proposed. (KL). Angelini, E., Bianco, P., Rosalbino, F. and Zucchi, F. (1995). "A comparative study of methods for the assessment of recovery techniques for aged copper". Science and Technology for Cultural Heritage 4, 1-10. Aucouturier, Marc, Keddam, M., Robbiola, L. and Takenouti, H. "Les patines des alliages de cuivre : processus naturel ou uvre de lhomme". Techn, in press. Bartolini, Marco, Cigna, R., Colombo, B., D'Ercoli, G., Marabelli, M. and Marano, M. (1998), "Misure di elettrocondensazione capillare e controlli elettrochimici per il restauro dei bronzi di Riace", Bollettino d'Arte - Serie speciale. Bartuli, Cecilia, Cigna, R., Colombo, B. and Marabelli, M. (1996). "Valutazione dei fenomeni corrosivi in corso sulla superficie del Marco Aurelio." Materiali e Strutture - problemi di conservazione 6, 127-136. Bartuli, Cecilia, Cigna, R. and Fumei, O (1999). "Prediction of durability for outdoor exposed bronzes: estimation of the corrosivity of the atmospheric environment of the Capitoline Hill in Rome". Studies in Conservation 44, 245-252. Bartuli, Cecilia, Angelucci, S. and Lanuti, S. (1999). "Polarization Resistance measurements for the monitoring of the corrosion rate of protected copper alloy sculptures", in Proceedings of Art 99: 6th international conference on non-destructive testing and microanalysis for the diagnostics and conservation of the cultural and environmental heritage (Rom), Ed. Istituto centrale per il restauro, Associazione italiana prove nondistruttive, Euroma, Rome, 1343-1359. Bastidas, J. M., Alonso, M.P., Mora, E.M. and Chico, B. (1995). "Corrosion of bronze by acetic and formic acid vapours, sulphur dioxide and sodium chloride particles". Werkstoffe und Korrosion 46, 515-519. Bastidas, J. M., Lopez-Delgado, A., Lopez, F.A. and Alonso, M.P. (1997). "Characterization of artificially patinated layers on artistic bronze exposed to laboratory SO2 contamination". Journal of Materials Science 32, 129-133. Bertholon, Rgis, Bell, B., Blengino, J-M. and Lacoudre, N. (1997). "Stabilisation de la corrosion d'un objet archologique en alliage cuivreux par lectrolyse faible pPolarisation dans le sesquicarbonate de sodium", in: Metal 95, Ed. Ian D. Macleod, Stphane L. Pennec and Luc Robbiola, James & James, London, 209-219. Describes the stabilisation of an archeological object of quaternairy bronze (Cu / Sn / Zn / Pb) by means of electrolyse with weak polarization in 1wt% sesquicarbonate. (KL) Bertrand, A. (1999). "Mise en vidence du phnomne de dcuprification dans les bronzes partir dun alliage de synthse 13% en masse dtain. Extension la comprhension du mcanisme des bronzes archologiques". Thse de doctorat de luniversit P. et M.

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Curie, Paris, 184 p. An essential document for the use of electrochemical techniques to understand the alteration of bronze artefacts (CD). Brostoff, L. (2003). "Coating strategies for the protection of outdoor bronze art and ornamentation", PhD report, University of Amsterdam. Use of Electrochemical Impedance Spectroscopy to assess the protective properties of coatings (CD) Brunoro, G., Zucchi,F., Tommesani, L. and Garagnani, G.L. (1995). "Protection of bronzes by pretreatments with heterocyclic compounds". Science and Technology for Cultural Heritage 4, 1-11. Brunoro, G., Frignani, A., Colledan, A. and Chiavari, C. (2003). "Organic films for protection of copper and bronze against acid rain corrosion". Corrosion Science 45, 2219-2231. Christy, A.G., Lowe, A., Otieno-Alego, V., Stoll, M. and Webster, R.D. (2004). "Voltammetric and raman microspectroscopic studies on artificial copper pits grown in simulated portable water". Journal of Applied Electrochemistry, 34, 225-233. Cicileo, Gabriela P., Cresp, M.A. and Rosales, B.M. (2002). "Patina protectiveness evaluation of bronze monuments exposed to a urban atmosphere", in: Proceedings of the 15th International Corrosion Congress, ICC, Granada, CD-Rom proceedings, n 3411. Cicelio, G.P., Crespo, M.A. and Rosales, B.M. "Comparative study of patinas formed on statuary alloy by means of electrochemical and surface technique analyses". In press in Corrosion Science, Elsevier, UK. Colledan, A., Chiavari, C., Brunoro, G. and Garagnani, G.L. (2001). "Studio del degrado di leghe bronzee: effetto delle piogge acide", in: Proc. La scienza dell'arte, Bressanone. Elsevier. Cortes, J.F. and Rodriguez, F.J. (2002). "Effect of relative humidity on the formation of artificial patina on copper substrate", in: Proceedings of the 15th International Corrosion Congress, ICC, Granada, CD-Rom proceedings, n 6571. Crespo, M.A., Cicelio, G.P. and Rosales, B.M. (2000). "Effect of the acid rain on 3 alloys used for monuments construction", in: Proceedings SIBAE 2000, P097, Oaxaca, Mxico 712 May 2000. Crespo, M.A., Cicelio, G.P. and Rosales, B.M. (2000). "In-situ characterization of patinas formed on statuary alloys in laboratory and Buenos Aires city monuments", in: Proceedings IV NACE Latinamerican Region and Latincorr 2000, Cartagena de Indias, Colombia, 17 - 23 Sep. 2000. Crespo, M.A., Cicelio, G.P. and Rosales B.M. (2002). "Evaluation of the black crusts behaviour in Bronze Monuments exposed to an Urban Atmosphere", in: IV Congreso Internacional de Rehabilitacion del Patrimonio Arquitectnico y Edificacion CICOP, San Bernardino, Paraguay, 8-12 setiembre 2002. D'Ercoli, Giorgio, Marabelli, M. and Santin, V. (1997). "Monumenti bronzei - Valutazione dello stato conservativo mediante la resistenza di polarizzazione", in: Proc. LXIV Riunione SIPS, Roma, 225-233. DErcoli, G. (2004). Polarisation resistance measurement. NdT for patina and coatings characterization on a bronze monument, in Monumenti in Bronzo AllAperto, Esperienze di Conservazione a confronto, Nardini Editore, Florence, 113-117. Es-Salah, K., Rahmouni, K., Ait Chikh, Z., Takenouti, H. and Srhiri, A. (2002). "Effet inhibiteur du amino-triazole a la corrosion de Cu70-Ni30 dans NaCl 3% en prsence dammoniac", in: Acte du 15me Forum sur Impdance Electrochimique, Ed. C. Gabrielli, Paris, 189-198. Es-Salah, K., Keddam, M., Rahmouni, K., Srhiri, A. and Takenouti, H. "Aminotriazole as corrosion inhibitor of Cu-30Ni alloy in 3 % NaCl in presence of ammoniac". Electrochimica Acta, in press.

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Bibliography

Feng, Y., Teo, W-K., Siow, K-S., Tan, K-L. and Hsieh, A-K. (1996). "The corrosion behaviour of copper in neutral tap water". Corrosion Science 38, 369-395. Fischer, W. R., Wagner, D., Siedlarek, H., Finger, B., Hnel, I. and von der Bank, N. (1997). "The influence of chloride ions and light on the corrosion behaviour of copper alloys in aqueous environments with special regard to bronze disease", in: Metal 95, Ed. Ian D. MacLeod, Stphane L. Pennec and Luc Robbiola, James & James, London, 89-94. By anodic polarization of copper in chloride containing electrolytes at neutral pH a twofold reaction layer is formed, copper(I)-chloride underneath copper(I)-oxide. The influence of light and wet-dry cycles are investigated by several electrochemical techniques. (KL) Guilminot, Elodie, Degrigny, C., Hiron, X. and Dalard, F. (1998). "Protection d'un cuivre archologique par le benzotriazole (BTA) en milieu aqueux de polythylne glycol (PEG)", in: Metal 98, Ed. William Mourey and Luc Robbiola, James & James, London, 234-241. Guilminot, Elodie, Rameau, J-J., Dalard, F., Degrigny, C. and Hiron, X. (2000). "Benzotriazole as inhibitor for copper with and without corrosion products in aqueous polyethylene glycol". Journal of Applied Electrochemistry 30, 21-28. Itoh, M., Nishihara, H. and Aramaki, K. (1995). "The protection ability of 11-mercapto-1undecanol self assembled monolayer modified with alkyltrichlorosilanes against corrosion of copper". Journal of the Electrochemical Society 142, 1839-1846. Keddam, Michel, Srhiri, A., Takenouti, H. and Trachli, B. (2000)."Inhibition de la corrosion du cuivre en milieu NaCl 0.5M pH 9.3", in: Acte du 13me Forum sur Impdance Electrochimique, Ed. C. Gabrielli, Paris, 81-90. Keddam, Michel, Srhiri, A., Takenouti, H. and Trachli, B. (2002). "Inhibiting effect of azole derivatives on the corrosion of copper and copper alloys in chloride medium", in: Proceedings of the 15th International Corrosion Congress, ICC, Granada, CD-Rom proceedings, n 701. Kruger, Jerome (1992). "Analytical techniques for the study of corroding bronze", in: The conservation of bronze Sculpture in the outdoor environment: a dialogue among conservators, curators, environmental scientists, and corrosion engineers, Ed.. Terry Drayman-Weisser, National Association of Corrosion Engineers, Houston, USA, 135159. Lago, D., de Miranda, L. and Sathler, L. (2002). "Artificial patina process applied to bronze structures under climate conditions of Rio de Janeiro city", in: Proceedings of the 15th International Corrosion Congress, ICC, Granada, CD-Rom proceedings, n 526. Letardi, P., Beccaria, A., Marabelli, M. and DErcoli, G. (1998). "Application of electrochemical impedance measurements as a tool for the characterization of the conservation and protection state of bronze works of art", in: Metal 98, Ed. William Mourey and Luc Robbiola, James & James, London, 303-308. This paper describes a research project that is developing an in situ application of electro-chemical impedance measurements for field monitoring of the protective behaviour of coatings applied on bronze works of art. (KL) Letardi, P., Beccaria, A.M., Marabelli, M. and D'Ercoli, G. (1999). "Non-destructive electrochemical impedance measurements: application to the corrosion characterisation on bronze works of art", in: Art 99: 6th international conference on non-destructive testing and microanalysis for the diagnostics and conservation of the cultural and environmental heritage (Rome), Ed. Istituto centrale per il restauro, Associazione italiana prove non-distruttive, Euroma, Roma, 313-319. Letardi, P., Beccaria, A.M., Marabelli, M. and D'Ercoli, G. (1999). "Applicazione delle misure di Impedenza Elettrochimica per la Caratterizzazione dei rivestimenti applicati nel

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campo della conservazione di bronzi artistici", in Proc. Giornate Nazionali sulla Corrosione e Protezione dei Materiali Metallici, Genova: AIM 1999, 267-272. Letardi, P., Beccaria, A.M., Marabelli, M. and D'Ercoli, G. (2000). "Development of Electrochemical Impedance Spectroscopy as a tool for outdoors bronze corrosion characterization", in: Proc. 2nd International Congress on Science and Technology for the Safeguard of Cultural Heritage in the Mediterranean Basin (Paris, Amsterdam: Elsevier, 407-411. Letardi, P. (2000). "Electrochemical impedance measurements in the conservation of metals", in Radiation in Art and Archeometry, Ed. D. C. Creagh and D. A. Bradley, Elsevier, Amsterdam, 15-39. Letardi, P.a, and Spiniello, R. "Characterisation of bronze corrosion and protection by contactprobe electrochemical impedance measurements", in: Proc. Metal 2001, Ed. I. MacLeod, J. Theile and C. Degrigny (in press). Letardi, P. (2002). "Outdoor bronze protective coatings: characterisation by a new contactprobe electrochemical impedance measurements technique", in: Proc. La Scienza dell'Arte, Bressanone 2002, 173-178. Letardi, P. (2002). "Contact-probe EIS characterization of protective coating systems for outdoor bronze sculpture: atmospheric weathering behaviour in marine environment", in: Proceedings of the 15th International Corrosion Congress, ICC, Granada, CD-Rom proceedings, n 5381. Letardi, P., Marabelli, M., D'Ercoli, G. and Guida, G. (2002). "Comparative study of protective coating systems for outdoor bronze sculpture", in: Proc. 3nd International Congress on Science and Technology for the Safeguard of Cultural Heritage in the Mediterranean Basin (Alcal, Spain), 272-275. Letardi, P. (2003). "Efficacia dei protettivi per i Bronzi esposti in ambiente marino: analisi di laboratorio e misure in campo", in: Proc. Lo Stato dell'Arte, Torino, 354-363. Letardi, P. (2004) Laboratory and field tests on patinas and protective coating systems for outdoor bronze monuments, in the proceedings of the ICOM-CC Metal WG interim meeting METAL 04, 379-387 Letardi, P. (2004) Electrochemical methods for characterisation and monitoring of patina and coatings corrosion rate: the EIS technique, in Monumenti in Bronzo AllAperto, Esperienze di Conservazione a confronto, Nardini Editore, Florence, 119-126 Leyssens, K., Adriaens, A., Pantos, E. and Degrigny, C. (2004) Study of corrosion potential measurements as a means to monitor the storage and stabilisation processes of archaeological copper artefacts, in the proceedings of the ICOM-CC Metal WG interim meeting METAL 04, 332-343 Lopez-Delgado, A., Bastidas, J.M., Alonso, M.P. and Lopez, F.A. (1997). "Influence of acetic and formic vapours on patinated artistic bronze". Journal of Materials Science Letters 16, 776-779. Lopez-Delgado, A., Cano, E., Bastidas, J.M. and Lopez, F.A. (1998). "A Laboratory Study of the Effect of Acetic Acid Vapour on Atmospheric Copper Corrosion". Journal of the Electrochemical Society 12, 4140-4147. Mabille, I., Bertrand, A., Sutter, E.M.M. and Fiaud, C. (2003). "Mechanism of dissolution of a Cu-13Sn alloy in low aggressive conditions." Corrosion Science 45, 855-866. The corrosion of a synthetic Cu-13Sn alloy was investigated by accelerating the corrosion rate through anodic polarization. The composition of the corrosion layer was followed as a function of the polarization time, using SEM and chronoamperometry. (KL) Millet, B., Fiaud, C., Hinnen, C. and Sutter, E.M.M. (1995). "Correlation between electrochemical behaviour, composition and semiconducting properties of naturally grown oxide films on copper". Corrosion Science 37, 1903-1918.

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Otero, E., and Bastidas, J.M. (1996). "Cleaning of two hundred year-old copper works of art using citric acid with and without benzotriazole and 2-amino-5-mercapto-1,3,4thiadiazole". Werkstoffe und Korrosion 47, 133-138. Otieno-Alego, Vincent, Hallam, D., Viduka, A., Heath, G. and Creagh, D. (1998). "Electrochemical impedance studies of the corrosion resistance of wax coatings on artificially patinated bronze", in: Metal 98, Ed. William Mourey and Luc Robbiola, James & James, London, 315-319. Otieno-Alego, Vincent, Heath, G., Hallam, G. and Creagh, D. (1998). "Electrochemical evaluation of the anti-corrosion performance of waxy coatings for outdoor bronze conservation", in: Metal 98, Ed. William Mourey and Luc Robbiola, James & James, London, 309-314. The corrosion performance of five commercial waxy coatings for long-term protection of outdoor bronze sculptures was investigated by electrochemical impedance spectroscopy. (KL) Pan, Silvia, Bertholon, R. and Lacoudre, N. (1991). "La dchloruration des alliages cuivreux par electrolyse faible polarization dans le sesquicarbonate de sodium". Studies in Conservation 36, 33-43. The electrolytical treatment with weak polarization in sodium sesquicarbonate permits the extraction of the chlorides and the preservation of the stable alteration products. The method has been applied successfully to archaeological objects from both marine and land sites. (KL) Price, C., Hallam, D., Heath, G., Creagh, D. and Ashton, J. (1997). "An electrochemical study of waxes for bronze sculpture", in: Metal 95, Ed. Ian Donald MacLeod, Stphane L. Pennec and Luc Robbiola, James & James, London, 233-241. Artificially and naturally aged wax coatings on bronze were compared to unaged samples using XRD, SEM, FTIR, EIS. (KL) Robbiola, Luc (1990). "Caractrisation de laltration de bronzes archologiques enfouis partir dun corpus dobjets de lge du bronze. Mcanismes de corrosion." Thse de doctorat de lUniversit Paris VI, 207 p. + annexes. Robbiola, Luc, Pereira, N., Thaury, K., Fiaud, C. and Labb, J-P. (1998). "Decuprification phenomenon of Cu-Sn alloys in aqueous solution in nearly neutral pH conditions", in: Metal 98, Ed. William Mourey and Luc Robbiola, James & James, London, 136-144. A recent model to explain the formation of bronze patinas has been developed on the basis of a decuprification phenomenon. In order to check this point, experiments have been carried out on a synthetic single-phase Cu-13Sn alloy (wt %) in a 0.01 M Na2SO4 solution. Both electrochemical (voltametric and chronoamperometric curves) and surface characterization methods (SEM, EDSX, IR) have been utilized. (KL) Rocca, E., Bertrand, G., Rapin, C. and Labrune, J.C. (2001). "Inhibition of copper aqueous corrosion by non-toxic linear sodium heptanoate: mechanism and ECAFM study". Journal of Electroanalytical Chemistry 503, 133-140. Voltamperometry and chronopotentiometry established that sodium heptanoate is a good inhibitor. In situ electrochemical AFM has proved that the inhibition is due to the formation of a layer, mainly constituted by a copper heptanoate. (KL) Rosales, Blanca, Vera, R. and Moriena, G. (1999). "Evaluation of the protective properties of natural and artificial patinas on copper. Part I. Patinas formed by immersion". Corrosion Science 41, 625-651. Rosales, B.M. and Fernandez, A. (2001). "Parameters controlling steel and copper corrosion nucleation and propagation in Antarctica", in: Northern Area Western Region Conference, Shining a Northern Light on Corrosion, Anchorage, Alaska, USA, 2628 Feb. 2001.

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Sequeira, C. A. C. (1995). "Inorganic, physicochemical, and microbial aspects of copper corrosion: literature survey". British Corrosion Journal 30, 137-153. A literature survey on the corrosion of copper in aqueous solutions. (AA, BS, KL) Serghini-Idrissi, M., Bernard, M.C., Harrif, F.Z., Joiret, S., Rahmouni, K., Srhiri, A., Takenouti, H., Vivier, V. et Ziani, M. (2003). "Etude des patines formes sur les pices de monnaie archologiques en bronze", in : Acte du 16me Forum sur Impdance Electrochimique, Ed. C. Gabrielli, 101-112. Shriri, A., Trachli, B., Hajjaji, N., Keddam, M., Takenouti, H., Frignani, A. and Zucchi, F. (2000). "Corrosion inhibition of copper in chloride solution by triazole derivatives", in: 9th European Symposium on Corrosion Inhibitors. Ann. Univ.Ferrara, N.S., Sez:V, Suppl. N. 11, 627 - 637. Siedlarek, H., Fussinger, B., Hanssel, I. and Fischer, W.R. (1994). "Characterization of reaction layers on copper surfaces formed in aqueous chloride and sulphate ion containing electrolytes". Werkstoffe und Korrosion 45, 654-662. Souissi, N., Bousselmi, S., Khosrof, S. and Triki, E. (2002). "Chemical and electrochemical characterization of a Punic bronze", in Proceedings of the 15th International Corrosion Congress, ICC, Granada, CD-Rom proceedings, n 713. Souissi, N., Bousselmi, S., Khosrof, S. and Triki, E. (2003). "Electrochemical behaviour of an archaeological bronze alloy in various aqueous media: new method for understanding artifacts preservation". Materials and Corrosion 54, 318-325. Spencer, H. (2003). "Investigation of a potentiostatic reduction treatment for leaded copper alloys", in: Conservation Science 2002, Ed. Joyce H. Townsend, K. Eremin and A. Adriaens, Archetype, London, 148-154. A series of potentiodynamic experiments were carried out to determine the behaviour of lead-copper mixtures in different electrolytes. Potentiostatic reduction of leaded copper samples showed that the lead corrosion products were reduced successfully. (KL) Sutter, E.M.M., Fiaud, C. and Lincot, D. (1993). "Electrochemical and photoelectrochemical characterization of naturally grown oxide layers on copper in sodium acetate solution with and without benzotriazole". Electrochimica Acta 38, 1471-1479. Virtanen, Jorma, Aromaa, J., Forsen, O. and Korpinen T. (2002). "Durability of artificial patina on copper", in: Proceedings of the 15th International Corrosion Congress, ICC, Granada, CD-Rom proceedings, n 41.

Investigation and treatment of iron


Acquarone, G., Angelini, E., Rosalbino, F. and Spinelli, P. (1997). "Misure d'Impedenza Elettrochimica per la valutazione dell'efficacia dei trattamenti protettivi dello stato di degrado di reperti archeologici in ferro", in: Proc. Materiali: ricerca e prospettive tecnologiche alle soglie del 2000, Milano: Federazione delle Associazioni Scientifiche e Tecniche, 1483-1489. Almeraya Caderon, F., Burunda, T.A., Lugo, C.J., Gaona Tiburcio, C., Orozco, C.V.M. and Martinez Villafane, A. (2002). "Corrosion of the metallic structure of a historical building", in: Proceedings of the 15th International Corrosion Congress, ICC, Granada, CD-Rom proceedings, n 354. Argyropoulos, Vasilike, Rameau, J-J., Dalard, F. and Degrigny, C. (1999). "Testing Hostacor IT as a corrosion inhibitor for iron in polyethylene glycol solutions". Studies in Conservation 44, 49-57. Argyropoulos, Vasilike, Degrigny, C. and Guilminot, E. (2000). "Monitoring treatments of waterlogged iron-wood composite artifacts using Hostacor IT PEG 400". Studies in Conservation 45, 253-264.

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Bibliography

Beaudoin, A., Clerice, M-C., Francoise, J., Labbe, J-P., Loeper-Attia, M-A. and Robbiola, L. (1997). "Corrosion dobjets archologiques en fer aprs dchloruration par la mthode au sulfite alcalin: caractrisation physico-chimique et rtraitement lectrochimique", in: Metal 95. Ed. Ian D. Macleod, Stphane L. Pennec and Luc Robbiola, James & James, London, 170-177. The limits of a first treatment by the alkaline sulphite method are discussed. A testing of re-treatment has been realized using two steps: a simple immersion in a alkaline sodium sulphite solution followed by an electrochemical phase under cathodic polarization. (KL) Bobichon, Carine, Degrigny, C., Dalard, F. and Khi Tran, Q. (2000). "An electrochemical study of iron corrosion inhibitors in aqueous polyethylene glycol solutions". Studies in Conservation 45, 145-153 Carlin, Keith Rodriguez (2001). "Less is more: measure of chloride removal rate from wrought iron artefacts during electrolysis". Studies in Conservation 46, 68-76. A recent useful contribution for the conservation of wrought-iron. Even if this article is talking about marine wrought iron it addresses serious issues of the relationship between current densities and chloride removal. (PM) Carpenter, J., and MacLeod, I. (1993). "Conservation of corroded iron cannons and the influence of degradation on treatment times", in: Proceedings of the 10th ICOM-CC triennial meeting, Washington, 759-766. Dalard, Francis, Gourbeyre, Y. and Degrigny, C. (2002). "Chloride removal from archaeological cast iron by pulsating current". Studies in Conservation 47, 117-121. De Groot, I., Ankersmit, H., van Langh, R. and Wei, W. (2004) Corrosion layers on historic iron artefacts: Cathodic protection of iron artefacts during cleaning in acid solutions, in the proceedings of the ICOM-CC Metal WG interim meeting METAL 04, 307-314 De Groot, I. and Degrigny, C. (2004) Electrolytic stabilisation of a marine composite porthole and its framework, in the proceedings of the ICOM-CC Metal WG interim meeting METAL 04, 427-442 Degrigny, Christian, Morel, O., Morvan, J., Maire, J-M. and Boucard, S. (1995). "Nettoyage et stabilisation de surfaces mtalliques peintes: application la restauration d'une voiture autochenille". Studies in Conservation 40, 227-236. Electrolytic techniques are used to design the best conservation treatments for iron based materials (CD) Degrigny, Christian, and Guilminot, E. (2000). "Dfinition dun traitement de conservationrestauration de composites fer / bois gorgs deau". Cahier technique de lAraafu 5, 510. A review (CD). Degrigny, Christian, Baron, G., Christodoulou, P., Tran, K. and Hiron, X. (2002). "Conservation of a collection of waterlogged composite rifles dating from the 17th century recovered from the Brescou II marine site", in Proceedings of the 8th ICOMCC WOAM conference - Stockholm 2001, Ed. Per Hoffmann and al., Bremerhaven, 399-411. Electrolytic stabilisation and electrochemical monitoring of the PEG impregnation of composite waterlogged composite artefacts (CD). Degrigny, C and Spiteri L (2004). Electrochemical monitoring of marine iron artefacts during their storage / stabilisation in alkaline solutions, in the proceedings of the ICOM-CC Metal WG interim meeting METAL 04, 315-331 Galliano, F., Gerwin, W. and Menzel, K. (1998). "Monitoring of metal corrosion and soil solution at two excavation sites and in the laboratory", in: Metal 98, Ed. William Mourey and Luc Robbiola, James & James, London, 87-91. The use of in situ corrosion potential measurements to monitor the corrosion behaviour of buried iron. (KL) Gregory, David (1999). "Monitoring the effect of sacrificial anodes on the large iron artefacts on the Duart Point wreck, 1997." International Journal of Nautical Archaeology 28,

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164-173. The use of in situ corrosion potential measurements to monitor the corrosion behaviour of marine iron artefacts (CD). Gregory, David (2000). "In situ corrosion studies on the submarine Resurgam a preliminary assessment of her state of preservation." Conservation and management of archaeological sites 4, 95-100. Guilminot, Elodie (2000). "Action dun inhibiteur de corrosion du fer en milieu eaupolyethylene glycol (PEG) 400 lors des traitements des objets archologiques composites de bois gorgs deau / fer". Thse de docteur de lINPG, Grenoble, 170 p. Study of the corrosion mechanism of iron in diluted PEG solutions (CD). Guilminot, Elodie, Dalard, F. and Degrigny, C. (2000). "Electrochemical study of corrosion inhibitors of iron in PEG 400 solutions", in: Proceedings of the 9th European Symposium on Corrosion Inhibitors (9 SEIC), Ann. Univ. Ferrara, Supp. 11, 213-225. Guilminot, Elodie, Dalard, F. and Degrigny, C. (2002). "Mechanism of iron corrosion in water-polyethylene glycol (PEG 400) mixtures". Corrosion Science 44, 2199-2208. Hjelm-Hansen, Nils, van Lanschot, J. Szalkay, C.D. and Turgoose, S. (1992). "Electrochemical monitoring of archaeological iron artefacts during treatment", in: Proceedings of the 3rd International Conference on Non-Destructive Testing, Microanalytical Methods and Environmental Evaluation for Study and Conservation of Works of Art, Instituto Centrale del Restauro, Viterbo, Italy, 4.-8. 10. 1992, 361-373. Hjelm-Hansen, Nils, van Lanschot, J., Szalkay, C.D. and Turgoose, S. (1993). "Electrochemical assessment and monitoring of stabilisation of heavily corroded archaeological iron artifacts". Corrosion Science 35, 767-774. Van Lanschot, Jette, Mathiesen, T., Szalkay, C.D. and Turgoose, S. (1994). "Non-destructive electrochemical measurements of the stability of archaeological iron artifacts", in: Proceedings of the 4th International Conference on Non-Destructive Testing of Works of Art, Berlin 1994, 306-315. MacLeod, I.D., Mardikian, P., Richards, V. (1993). "Observations of the extraction of iron and chloride ions from composite materials", in: Proceedings of the 4th ICOM Group on Wet Organic Archaeological Material Conference, Portland, 199-211. MacLeod, Ian D. (1998). "In situ corrosion studies on iron shipwrecks and cannon: the impact of water depth an archaeological activities on corrosion rates", in: Metal 9, Ed. William Mourey and Luc Robbiola, James & James, London, 116-124. Describes a model to calculate the corrosion rate from in situ corrosion potential measurements. (KL). MacLeod, Ian D. (1998). "In-situ corrosion studies on iron and composite wrecks in South Australian waters: implications for site managers and cultural tourism". Bulletin of the Australian Institute for Maritime Archaeology 22, 81-90. MacLeod, I., Morrison, P., Richards, V. and West, N. (2004) Corrosion monitoring and the environmental impact of decommissioned naval vessels as artificial reefs, in the proceedings of the ICOM-CC Metal WG interim meeting METAL 04, 53-74 MacLeod, I., Heldtberg, M., Richards, V. (2004) Corrosion and cathodic protection of iron in seawater: a case study of the James Matthews (1841), in the proceedings of the ICOM-CC Metal WG interim meeting METAL 04, 75-87 Mardikian, Paul and David, R. (1996). "Conservation of a French pistol from the wreck of Le Cygne (1808)". Studies in Conservation 41, 161-169. Mardikian, Paul (1997). "The Conservation of Two Composite Objects from The Confederate Alabama (1864)", in: Proceedings of the Conference on Historical and Underwater Archaeology. Corpus Christi. Texas, USA, 128-134. Meier, C.K. and Mardikian, P. (2004). "When corrosion science meets an icon of maritime history". Accepted for publication in NACE Conference, New Orleans, LA.

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Bibliography

Pruckner, F., Theiner, J., Eri, J. and Nauer, G.E. (1996). "In-situ monitoring of efficiency of the cathodic protection of reinforced concrete by Electrochemical Impedance Spectroscopy". Electrochimica Acta 41, 1233-1238. Rosales, B.M. (2002) "Weathering steels", in: Proceedings 14th Rolling Conference and 1st. Conference on Steel Uses, Siderurgy Arg, Institute (IAS), San Nicols, Argentina, 4- 7 Nov 2002. Rosales, B.M., Vera, R. and Tapia, C. (2003). "Effect of the exposition angle in the corrosion rate of plain carbon steel in a marine atmosphere". Corrosion Science. 45, 321-337, (2003).

Investigation and treatment of lead and tin


Abd El Aal, E. E. (2001). "Cyclic voltametric behaviour of the lead electrode in sodium sulphate solutions". Journal of Power Sources 102, 233-241. Boctor, W. H., Zhong, S., Liu, H.K. and Dou, S.X. (1999). "An electrometric method for evaluation of the corrosion of lead alloys". Journal of Power Sources 77, 56-63. Brinic, S., Metikos, M. and Babic, R. (1995). "Characterization of anodic films on lead and lead alloys by impedance spectroscopy". Journal of Power Sources 55, 19-24. Britton, S.C. et Sherlock, J.C. (1974). "Examination of oxides on tin surfaces by cathodic reduction, British Corrosion Journal, 2, 96-102. Carradice, Ian A., and Campbell, Stephen A. (1994). "The conservation of lead communion tokens by potentiostatic reduction". Studies in Conservation 39, 100-106. This paper presents a practical procedure for the electrolytic reduction of lead carbonate corrosion on lead artefacts with dilute sulphuric acid as an electrolyte. (KA). Degrigny, Christian (1998). "Le plomb lpreuve du temps." Revue du Muse des arts et mtiers 23, 55-58. Degrigny, Christian, and Le Gall, Ren (1999). "Conservation of ancient lead artifacts corroded in organic acid environments: electrolytic stabilization / consolidation". Studies in Conservation 44, 157-169. The authors compare sodium hydroxide, sodium carbonate, sodium sulphate and sulphuric acid as electrolytes for the cathodic reduction of lead carbonate corrosion on lead artefacts. (KA) Dickens, J., Smith, N. and Gerritsen, W. (2004) On again, off again - Cathodic protection of a lead and ceramic toilet during desalination, in the proceedings of the ICOM-CC Metal WG interim meeting METAL 04, 465-483 Espinoza-Ramos, L. I., Ramirez, C., Hallen-Lopez, J.M., Arce, E., Palomar-Pardav, M. and Romero-Romo, M. (2002). "Electrochemical study of passive layer formation on leadtin alloys immersed in 5.31 M H2SO4 solution". Journal of the Electrochemical Society 149, B543-B550. Graedel, T. E. (1994). "Chemical mechanisms for the atmospheric corrosion of lead". Journal of the Electrochemical Society 141, 922-927. Guo, Y. (1995). "Kinetics of oxidation processes on lead electrode in H2SO4". Journal of the Electrochemical Society 142, 3643-3648. Guo, Y., Niu, L., Zhang, S. and Chen, S. (2000). "The electrochemical behaviour of PbSO4 with different structures on Pb". Journal of Power Sources 85, 38-43. Hamilton, Donny L. (1999). "Lead, tin and lead tin alloys." http://nautarch.tamu.edu/class/anth605/file14.htm (accessed 27 October 2003). A review of the techniques used to treat lead, tin or tin alloy. (AA, BS, KL) Kelly, D., Niessen, P. and Valeriote, E.M.L. (1985). "The influence of composition and microstructure on the corrosion of Pb-Ca-Sn alloys in sulphuric acid solutions". Journal of the Electrochemical Society 132, 2533-2538.

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Bibliography

MacLeod, Ian Donald, and Wozniak, R. (1996). "Corrosion and conservation of lead in sea water", in: Preprints of the 11th ICOM-CC triennial meeting (Edinburgh). Ed. Janet Bridgland, James & James, London, 884-890. Murugan Vanmathi, G., and Rangarajan, S.K. (1995). "Characterizing the early stages of electrochemical phase formation of lead sulfate films". Journal of the Electrochemical Society 142, 1770-1776. Stein, N., Rocca, E., Klein, R., Lecuire, J.M. and McRoc, E. (1998). "In situ ellipsometric study of lead sulphate film electroformation on lead in a sulphuric acid solution". Electrochimica Acta 44, 445-454. Taguchi, M., and Sugita, H. (2002). "Analysis for electrolytic oxidation and reduction of PbSO4 / Pb electrode by electrochemical QCM technique". Journal of Power Sources 109, 294-300. Takehara, Z. (2000). "Dissolution and precipitation reactions of lead sulphate in positive and negative electrodes in lead acid battery". Journal of Power Sources 85, 29-37. Vilche, J. R., and Varel, F.E. (1997). "Reaction model development for the Pb / PbSO4 system". Journal of Power Sources 64, 39-45.

Investigation and treatment of silver


Bernard, M.C., Dauvergne, E., Evesque, M., Keddam, M. and Takenouti, H. "Reduction of silver tarnishing and the protection against subsequent corrosion". Corrosion Science, accepted Costa, Virginia (2001). "The deterioration of silver alloys and some aspects of their conservation." Reviews in Conservation 2, 18-34. A descriptive review of materials and methods used for cleaning, consolidating and protecting silver artifacts, accompanied by an extensive bibliography. (KL) Degrigny, Christian, and Morel, M. (1992). "Mise au point dun traitement lectrolytique de nettoyage dinstruments de musique vent", in: Conservation et restauration d'objets metalliques. Archologie en Yvelines, Document de travail 5. Versailles: Conseil gnral des Yvelines, 50-61. Degrigny, Christian, Jerme, M. and Lacoudre, N. (1993). "Surface cleaning of silvered brass wind instruments belonging to the Sax collection." Corrosion Australasia 18, 16-18. Definition of a protocol for the electrolytic reduction of silver tarnish on silvered brass artefacts (CD). Degrigny, Christian, and Jerme, M. (1993). "Mise au point dune procdure de traitement dinstruments de musique en laiton argent sulfur". Science et Technologie de la Conservation et de la Restauration des uvres dart et du patrimoine 3, 60-65. Degrigny, Christian, Wry, M., Vescoli, V. et Blengino, J-M. (1996). "Altration et nettoyage de pices en argent dor." Studies in Conservation 41, 170-178. Application of electrolytic reduction to gilt silvered artefacts (CD). Degrigny, Christian, and Witschard, D. "Electrolytic cleaning of silver plates from the shrine of St Sigismonds children of St Maurice Abbey." Paper presented at the Exposure 2001 conference, Hildesheim 2001, submitted for publication. Eggert, Gerhard (1990). "Die Sprdigkeit des Resafasilbers und die Konsequenzen fr seine Restaurierung", in: T. Ulbert, ed. Der kreuzfahrerzeitliche Silberschatz aus ResafaSergiupolis, Resafa III, Ed. T. Ulbert, Mainz: von Zabern, 104-109. Evesque, M., Keddam, M., Klein, L., and Takenouti, H. "The formation of self-assembling membrane of hexadecane-thiol on silver to prevent the tarnishing". Electrochimica Acta, in press.

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Bibliography

.Keddam, Michel, Klein, L., Takenouti, H., Trachli, B. (2002). "Prevention to Tarnishing of Silver and Copper-alloy by a Thin Electropolymerised Coating", in: 15th International Corrosion Congress, Granada, CD-Rom proceedings, n 701 Lacoudre, Nol, Beldjoudi, T. and Dugot, J. (1998). "Influence des conditions dexposition et de protection des surfaces sur laltration de plaquettes en laiton argent au Muse de la Musique Paris", in: Metal 9, Ed.. William Mourey and Luc Robbiola, James & James, London, 265-270. Electrochemical study of small brass plates exposed to different museum environments with and without the application of a corrosion inhibitor. (KL) Morel, Olivier, and Degrigny, C. (1992). "Mise au point d'un traitement lectrolytique de nettoyage d'instruments de musique vent", in : Conservation et restauration d'objets metalliques. Archologie en Yvelines, Document de travail 5. Versailles: Conseil gnral des Yvelines, 50-61. Niemeyer, Barbara (1997). "Early 20th-century restorations and modern conservation treatments on archaeological silver objects", in: Metal 95, Ed. Ian D. MacLeod, Stphane L. Pennec and Luc Robbiola, James & James, London, 190-195. Descriptions of several cleaning operations on archaeological silver objects from the early 20th century until now (case studies). (KL) Stemann-Petersen, Karen, and Taarnskov, B. "Electrolytic cleaning of silver and gilt silver threads in silk textiles." Paper presented at the Exposure 2001 conference, Hildesheim 2001, submitted for publication. Cleaning tarnished silver and gilt silver decorations on silk textiles by electrolysis was examined and compared with earlier used cleaning techniques for silver and gilt silver threads on silk. (KL)

Other and mixed subjects


Aldaz, A., Espana, T., Montiel, V. and Lopez-Segura, M. (1986), "A simple tool for the electrolytic restoration of archaeological metallic objects with localized corrosion". Studies in Conservation 31, 175-176. A plastic cylinder contains the electrolytic solution within which there is a cylindrical bar of carbon that acts as a anode. A porous separator is placed on the end. A drop of solution is placed on the area of the object to be restored and the porous tip is put in contact with this area. Thus, the electrical contact is made and the reduction of the corrosion products proceeds normally. (KL) Amirudin, A., and Thierry, D. (1995). "Electrochemical sensor for monitoring atmospheric corrosion of polymer coated metal". British Corrosion Journal 30, 214-220. Bartolini, Marco, Cigna, R., Colombo, B., D'Ercoli, G., Marabelli, M. and Marano, M. (1999). "Capillary condensation measurements and electrochemical tests for conservation of artistic metals", in: Proceedings of ART 96 - 5th International Conference on NonDestructive testing and Microanalysis for the diagnostics and Conservation of the Cultural and Environmental Heritage (Budapest), 117-130. Bartolini, Marco, Colombo, B., Marabelli, M., Marano, A. and Parisi, C. (1997). "Nondestructive tests for the control of ancient metallic artifacts", in: Metal 95, Ed. Ian Donald MacLeod, Stphane L. Pennec and Luc Robbiola, James & James, London, 43-49. Bernard, M.C., Dauvergne, E., Evesque, M., Keddam, M. and Takenouti, H. . "Reduction of silver tarnishing and the protection against subsequent corrosion". Corrosion Science, in press. Bertholon, Rgis (2001). "Nettoyage et stabilisation de la corrosion par lectrolyse", in: La conservation des mtaux, Ed. Claude Volfovsky. Conservation du patrimoine 5. Paris: ETIC Bibliography

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CNRS, 83-101. Case study of the treatment of cast iron and bronze cannons from marine archaeological sites. (KA) Bonora, P. L., Deflorian, F. and Fedrizzi, L. (1996). "Electrochemical Impedance Spectroscopy as a tool for investigating underpaint corrosion". Electrochimica Acta 41, 1073-1082. Cicileo, Gabriela P., Crespo, M.A. and Rosales, B.M. "Comparative Study of patinas formed on statuary alloys by means of electrochemical and surface techniques". Corrosion Science, in press. De la Baume, S. (1987). "Archaeological wood desalting by electrophoresis", in: Conservation of wet wood and metal. Proceedings of the ICOM-CC Metal and Waterlogged Organic Archaeological Materials, Ed. Ian MacLeod, Fremantle: Western Australia Museum, 153-161. D'Ercoli, Giorgio, Letardi, P., Marabelli, M., Santin, V. (1999). "The resistance of polarization for the testing of corrosion: practice and problems", in: Art 99: 6th international conference on non-destructive testing and microanalysis for the diagnostics and conservation of the cultural and environmental heritage (Rome), Ed. Istituto centrale per il restauro, Associazione italiana prove non-distruttive, Euroma, Roma, 17271738. Hallam, D., Thurrowgood, D., Otieno-Alego, V. and Creagh, D. An EIS Method for assessing thin oil films used in museums, in the proceedings of the ICOM-CC Metal WG interim meeting METAL 04, 388-399 Huet, N., Forrires, C. et Genin, J-M. (1997). "Etude pralable de la pole sel de Salins les Bains: tat physico-chimique de conservation et moyens mettre en oeuvre pour la restauration", in: Metal 95, Ed. Ian D. Macleod, Stphane L. Pennec and Luc Robbiola, James & James, London, 127-130. Description of a stabilisation treatment by electrolysis. (AA, BS, KL) Keddam, Michel, Hugot-Le-Goff, A., Takenouti, H., Thierry, D. and Arevalo, M-C. (1992). "The influence of a thin electrolyte layer on the corrosion process of zinc in chloridecontaining solutions". Corrosion Science 33, 1243-1252. Lee, S., and Staehle, R.W. (1995). "Coulometric reduction of oxides formed on copper, nickel and iron". Journal of the Electrochemical Society 142, 2189-2195. Lins, Andrew, and Malenka, S. (2000). "The use of mercury salts in gold electroplating", in: Gilded metals: history, technology and conservation, Ed. Terry Drayman-Weisser, Archetype, London, 267-282. Mardikian, P. and Lacoudre, N. (1990). "Le Titanic une histoire de corrosion" Neptunia 178, 2-7. Montluon, J. et Lacoudre, N. (1988). "Les objets du Titanic, la mmoire des abmes", Herv, Paris. Nishikata, A., Ichihara, Y. and Tsuru, T. (1995). "An application of electrochemical impedance spectroscopy to atmospheric corrosion study". Corrosion Science 37, 897911. Nishikata, A., Ichihara, Y. and Tsuru, T. (1996). "Electrochemical impedance spectroscopy of metals covered with a thin electrolyte layer". Electrochimica Acta 41, 1057-1062. Pirnt, A., Mszros, A. and Lengyel, B. (1995). "A comparison of electrochemical and analytical chemical methods for the determination of the corrosion rate with very efficient inhibitors". Corrosion Science 37, 963-973. Rammelt, U., and Reinhard, G. (1992). "Application of electrochemical impedance spectroscopy (EIS) for characterizing the corrosion-protective performance of organic coatings on metals". Progress in Organic Coatings 21, 205-226.

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Bibliography

Reedy, Chandra L., Corbett, R.A. and Burke, M. (1998). "Electrochemical tests as alternatives to current methods for assessing effects of exhibition materials on metal artefacts". Studies in Conservation 43, 183-196. Experiments with electrochemical testing are reported here, using typical exhibition and storage materials in conjunction with lead, copper and silver coupons. The polarization resistance test provides a quantitative measure of corrosion rate in milli-inches per year for a specific metal used in conjunction with a particular material. (KL) Scully, J. (2000). "Polarization resistance method for determination of iInstantaneous corrosion rates". Corrosion 56, 199-218. Sembrat Jr., Joseph (1998). "Reliable methods for the measurement and inspection of protective barrier coatings for outdoor monuments", in: Metal 1998, Ed.. William Mourey and Luc Robbiola, James & James, London,. 286-290. A study about equipment and techniques currently used in the protective coatings industry that could be used by the conservators of outdoor monuments. (GC) Zhang, S. H., and Lyon, S.B. (1993). "The electrochemistry of iron, zinc and copper in thin layer electrolytes". Corrosion Science 35, 713-718.

Unpublished reports available from CD


Auger, N. et Carrois, F. (2000) "Validation et optimisation de la ralisation des prouvettes artificielles base fer simulant laltration des objets archologiques", Projet de fin dtudes de lISITEM, Nantes. Use of corrosion potential measurements for the validation of artificially corroded iron based coupons to simulate archaeological iron artefacts (CD). Corbin, S., et Delsaut, C. (1997). "Altration dobjets anciens en tain." Projet de fin dtudes de lISITEM, Nantes. Preliminary electrolytic reductions on oxidized tin artefacts (CD). de Groot, Ilonne (2003). "Corrosion layers on historic iron artefacts, research into the dissolution of iron corrosion layers by acid under cathodic protection." Unpublished dissertation. Amsterdam: Institute for Cultural Heritage. Degrigny, Christian (1991). "Traitements lectrolytiques de vestiges subaquatiques de grandes dimensions base dalliages daluminium au laboratoire de restauration de lAustralian War Memorial." Rapport de mission. Degrigny, Christian (1997). "Etude de la dgradation des objets en plomb dans les collections publiques et des moyens de les stabiliser et de les conserver long terme." Rapport interne ArcAntique, Nantes. 42 p. Electrolytic stabilisation of lead artefacts from public collection with the two steps treatments (cathodic reduction at constant potential in neutral solution followed by anodic oxidation at constant potential in sulphuric acid (CD). Degrigny, Christian (2000), "Protocole de traitement des lments en argent de la chsse des Enfants de St Sigismond". Rapport interne ArcAntique, Nantes, 15p. Use of electrochemical techniques to study the damage on silver plates and specify the parameters of the electrolytic conservation process (CD) Degrigny, Christian (2000), Altration des tuyaux dorgues en tain et alliages tain-plomb de lglise St Sauveur du Petit Andely, Rapport interne ArcAntique, Nantes, 74p. Electrolytic techniques are suggested as a possible conservation process to stabilise organ pipes covered with blisters (CD) Giordana, S. (1998). "Altration des fontes de fer issues du milieu marin et dfinition dun traitement de stabilisation." Mmoire de stage du DEA Mtallurgie et Matriaux, Universit de Paris IX. ETIC Bibliography

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Heldtberg, M. (2002). "Investigations into corrosion and cathodic protection of ferrous metals in the marine environment." Final year dissertation of EVTEK. Kokko, R. E (2002). "Sacrificial anodes: implications to in-situ conservation on the wreck of Kronprins Gustav Adolf (1788)." Final year dissertation of EVTEK. Lamy, C (1997). "Stabilisation dobjets archologiques chlorurs en alliage cuivreux." Rapport interne ArcAntique, Nantes, 50 p + annexes. McLennan, C., and Degrigny (1993), C. "The electrolytic treatment of aluminium alloys: observations on surface appearance." Rapport EDF-Valectra, D.5001/DGY/RA 921169.

EU reports
Criteria for the stability of archaeological and historical artefacts and standards for the assessment of conservation procedures, EU programme report, Contract NSTEPCT90-0115 (1994). Turgoose, S., Hawkins, C., Wrathall, N., Kalsbeek, N., van Lanschot, J., Mathiesen, T. and Sjgren, A., Development and improved conservation procedures for archaeological iron, EU programme report, Contract CT94-0561 (1996)

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Bibliography

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