METAL2022

SEPTEMBER 5–9, 2022

HELSINKI, FINLAND

PROCEEDINGS OF THE INTERIM MEETING OF THE ICOM-CC METALS WORKING GROUP

EDITED BY PAUL MARDIKIAN, LIISA NÄSÄNEN, AND AKI ARPONEN

METAL2022
PROCEEDINGS OF THE INTERIM MEETING OF THE ICOM-CC METALS WORKING GROUP

SEPTEMBER 5–9, 2022

HELSINKI, FINLAND

EDITED BY PAUL MARDIKIAN, LIISA NÄSÄNEN, AND AKI ARPONEN

© 2022 International Council of Museums – Committee for Conservation (ICOM–CC) and The National Museum
of Finland Collections and Conservation Centre (NMF)

The Metals Working Group is part of the Committee for Conservation (ICOM–CC), a committee of the International
Council of Museums (ICOM) network.

Publishers: International Council of Museums – Committee for Conservation (ICOM–CC) and The National Museum
of Finland

All rights reserved. No part of this book may be reproduced in any form or by any means, whether electronic or
mechanical, including photocopying, recording, or otherwise, without the prior permission in writing from the
copyright holder.

ISBN: 978-2-491997-61-8

Proceedings and user interface design and production: Eduardo Pulido (epulido@sapo.pt)

Copy editing: Carla Nunes (carlarnunes@gmail.com), Per Christopher Foster (chris.foster@netcabo.pt), and Wendy
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Cover image: Viking Age swords found in Finland, now in the Archaeological Collections of the Finnish Heritage
Agency. The hilts in Viking Age swords are true masterworks of metal technology. The mythical animals and palmettes
in the hilt of KM10833:1 (front cover, left) were created with gilt silver and niello; in the pommel of KM9243:1 (back
cover, right), copper and silver wires weave a herringbone motif. © Finnish Heritage Agency
Table of contents
Foreword. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
Preface. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . x
Acknowledgments. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiii
In memoriam David Hallam (1956–2020). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiv

Sustainability in Practice
Natural Conservation of Archaeological Iron
H. Matthiesen, J. Frydendahl, L.B. Andersen, C. Carré, P. Dillmann, D. Neff, T. Wiinblad  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Exploiting Biologically Synthetized Chelators in Conservation: Gel-based Bio-cleaning of Corroded
Iron Heritage Objects
L. Cuvillier, A. Passaretti, A. Raimon, V. Dupuy, E. Guilminot, E. Joseph  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Microbial Stabilization of Archaeological Iron Objects (YCP)
S. James, M. Monachon, S. Ganesan, E. Joseph  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Deterioration Tests Using a Simulated Tumulus to Evaluate In Situ Preservation of Metal Artifacts in a
Stone Chamber
A. Yanagida, S. Wakiya, H. Xie, D. Ogura, N. Takatori, H. Yasui, S. Hokoi, Y. Kohdzuma  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Development of a Sunflower-Oil-based Bio-lubricant for Use in Gear Models at the ISEP Museum (YCP)
M. Gonçalves, B. Campos, E. Vieira, P.R. Moreira  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

Modern Metals
A Review of Treatments of Magnesium Alloy Objects at the National Air and Space Museum
K. Wilcox, M. Sweeney, L. Horelick  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
Mitigating Magnesium Corrosion: Testing the Efficacy of Reapplying Conversion Coatings in
Conservation Treatment (YCP)
A.E. Rodriguez. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
Corrosion and Conservation of Nickel Silver Alloys Recovered from Historic Shipwrecks
I.D. MacLeod. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
First Step in the PROCRAFT Project on WWII Aircraft Heritage: Investigation and Conservation of the
Aluminium Alloys
M. Brunet, L. Robbiola, C. Deshayes, E. Bernardi, C. Martini, C. Chiavari, A. Balbo, C. Monticelli, J. Fišer,
T. Vyhlídal, J. Echinard, E. Guilminot  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
DiscoveryMat: A Freeware Electrochemical Tool for the In Situ Analysis of Aluminum Alloys in the Cooling Systems
of Historical Vehicles (YCP)
E. Granget, B. Chalançon, C. Degrigny  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87

Coatings, Consolidants & Corrosion Inhibitors

A Comparison of the Long-Term Outdoor Performance of Two Modern Paint Coating Systems and a
Traditional Lead-based Paint Applied to Historic Wrought Iron
P. Meehan, N. Emmerson, D. Watkinson  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
iv  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND

Keris Blade Protection – A Comparison of Traditional and Contemporary Coatings (YCP)

Janine Meier  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
Preliminary Investigation of the Use of Chitosan-based Coatings for Outdoor Cultural Heritage Objects (YCP)
C. Carvalho, N. Silva, E. Vieira, P.R. Moreira  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
Testing the Compressive Strength and Reversibility of Consolidants Applied to Marine Archaeological Gray
Cast Iron
E. Farrell, M.K. McGath, J. Echerd  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Calcium Sulfonate: Adsorptive Inhibitors for Metal Conservation?
E. Wentland  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
Investigating a Sustainable Alternative: L-Cysteine as a Non-Toxic Corrosion Inhibitor for Copper Alloy
Conservation (YCP)
E. Tréhu, D. Sully  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132

Technical Studies
Sustainable Growth of Mewari Mail Makers: Traditional to Contemporary Practices
V. Singh  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
Development of Mexican Bell Documentation Tools and Methodologies
J. Contreras Vargas, D. Lira Pacheco, Á.E. García Abajo, F. Llop Álvaro, F. Llop I Bayo, F. Magaña Nieto  . . . . . . . . . . . 146
Corrosion Detection by Color Change Using Crowdsourced Photographs. Preliminary Results of the MIPAC Project
B. Ramírez Barat, M.T. Molina, E. Cano  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
Reflectance Transformation Imaging Feature Maps for Visual Documentation of Metal Objects
A. Siatou, M. Nurit, G. Le Goïc, A. Mansouri, L. Brambilla, C. Degrigny  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
Revealing Degradation Patterns: Imaging Techniques for the Study of Metal Soap Formation on Painted
Metal Objects
S. Russo, L. Brambilla, J.-B. Thomas, E. Joseph  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
Monitoring of Metal Sculptures and Their Environment in Art Museums in Sweden
S. Golfomitsou, E. Canosa, M. Pullano, M. Borin, E. Nygårds, M. Florescu, K. Hermerén  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
Discovery of a 12th-Century Enamelled Reliquary Pendant: Elemental Analysis and Content Visualisation
Using Prompt Gamma Neutron Activation Analysis and Neutron Tomography
M. Heinzel, E. Kluge, D. Kemper, B. Schillinger, C. Stieghorst  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184

Analytical Investigations
Sulfur, the ‘Enemy of Copper’: Replication of Sulfurous Efflorescence on Copper-based Heritage Materials with
Elemental Sulfur
C.F. Kuhn-Wawrzinek, G. Eggert, T. Schleid  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
The Role of Patina on Archaeological Copper Alloy Coins in the Outbreak and Progression of Bronze Disease
J.C. Thunberg, D.E. Watkinson, N.J. Emmerson, Z. Kis, I. Harsányi, Z. Kasztovszky, M. Lewis  . . . . . . . . . . . . . . . . . . . . . . . . 203
Non-Invasive Analysis: The Mirage and the Reality
P. Northover. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
 ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND  v

An Analytical Study of the Corrosion Behavior and Microstructural Properties of a Group of Copper Alloy
Artifacts from the Khirbet Yajuz Archaeological Site, Jordan
A.N. Abu-Baker, L.A. Khalil  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
Corrosion Analysis and Assessment of a Collection of Archaeological Copper Alloy Objects from Sagzabad,
Northern Iran
O. Oudbashi, S.Bahadori, A. Aliyari  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
The Effect of Synthesis Routes on the Ability of Akaganeite to Corrode Iron
N.J. Emmerson, D.E. Watkinson, K. Roche, J.H. Seifert, J.C. Thunberg  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
Analysis of Heterogeneous Tarnish on Silver-based Alloys Using the Pleco for Local, Controlled
Electrolytic Cleaning (YCP)
N. Ricotta, A. Cagnini, C. Degrigny  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
Using Epidemiology to Validate Scientific Results for Complex Situations
D. Thickett  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
Long-Term Provision of Stable Environments for Metals Conservation
P. Lankester, D. Thickett, S. Johnson  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261

Conservation Practices
The Reanimation of a Renaissance Automaton: Diana and Stag at the Museum of Fine Arts, Boston
S. Gänsicke, R. Lang  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
Building an Ironclad System: A Quarter-Century of Innovation in the Conservation of USS Monitor
E. Farrell, E. Sangouard, L. Haines, L. King, M.K. McGath, W. Hoffman  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
Conservation and Technical Study of Ten Objects in the Thiriyaya Collection at the Department of
Archaeology in Sri Lanka
K.A. Anusha Kasthuri, D. Ruckmal Athukorala, A. Fernando  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
Conservation of Copper and Copper Alloy Objects: A Training Programme Conducted at the Mehrangarh Museum
Trust, Jodhpur (YCP)
S. Raja, S. Rathore  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
Keeping it Kosher: The Care and Treatment of the Judaica Collection at the Israel Museum, Jerusalem
J. Lewinsky, H. Seri, M. Delano, I.L. Beyth  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
Commercially Available Vacuum Chambers as an Alternative in the Deoxygenated Desalination Treatment of
Archaeological Iron (YCP)
A. Pienimäki. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317

POSTER SESSION
Subcritical Fluids in the Conservation of Archaeological Iron Objects: From Experiments to Permanent Practice
A. Arponen, A. Hyppönen, P. Kilpeläinen, K. Kaipanen  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
When Corrosion is Useful: Absolute Dating of Metals by the Radiocarbon Method
L. Beck, C. Messager. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
Corrosion, Communication, and Comparison: Collaborative Conservation Approaches Towards Two Medieval
Axes from Norfolk, England
K. Berlewen, R. Hudson  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 326
vi  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND

Atmospheric Particulate Matter: How to Include it in Artificial Ageing?

E. Bernardi, C. Martini, C. Velino, C. Chiavari, I. Vassura  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
Study and Restoration of the Trajan’s Column Electrotypes at the National Museum of Archaeology of
Saint-Germain-en-Laye
I. Bonora Andujar, J. Jouet, A. Amarger, B. Branche, A. Molineri  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
Acoustic Emission Techniques for the Detection and Monitoring of Corrosion Phenomena
L. Brambilla, B. Chalançon, A. Roda-Buch, S. Mischler  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
The Bronze Hand of Prêles: Protecting a Valuable Archaeological Object Using 3D Techniques
S. Brechbühl. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
Corrosion of Strings on Musical Instruments
V. de Bruyn-Ouboter, A. Erbe, E.F. Gustad  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
Do the Lubricating Oils Used in Scientific-Technological Objects Protect Metals Against Corrosion?
E. Cano, B. Ramírez Barat, J. Leal, M.T. Molina  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
The Bluish Green and the Greenish Blue
M. Cardoso  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 333
Heritage Biota and Bronze Patina Composition: A Correlation?
C. Chiavari, A. Timoncini, C. Martini, E. Bernardi, F. Costantini  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 334
Testing Silver Lacquers: What about Agateen #27?
G. Eggert, G.D. Smith, M.J. Samide  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335
Possibilities for Implementing Aesthetic Unity, Reversibility and Distinctiveness: Two Conservation Case Studies
E. Tóth  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
Supercritical Carbon Dioxide: Cleaning and Stabilization Tests for Copper Alloys and Iron Keys from a Scientific
Collection of the Centro Hospitalar Conde de Ferreira (Porto, Portugal)
C. Figueiredo, N. Camarneiro, C. Bottaini, R. Bordalo, I. Silva, M. Duarte, E. Vieira  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
A Simple Treatment System for the Deaerated Desalination of Archaeological Iron
J. Frydendahl, L.B. Andersen, T. Wiinblad, C. Carré, D. Neff, P. Dillmann, H. Matthiesen  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
Metals Conservation Teaching at University Level in Greece and the Cultural Vision of EYDAP S.A.
M. Giannoulaki, C. Panagiotopoulou, S. Tzimopoulou, V. Argyropoulos  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
A Lacquer to Dye For! Exploring a UV Fluorescent Additive for Coating Applications in Silver Conservation
R. Grayburn, L. Fair  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340
Port-Jeanne-d’Arc: Is Conservation of an Isolated Site Possible?
M. Grima  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
Evaluation of the Impact of Dechlorination Treatments on the Organic Parts of Composite Objects
E. Guilminot, C. Pelé-Meziani, S. Labroche  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342
Historical Repairs on Ancient Chinese Bronzes: Identification and Conservation Issues
K.-S. (Tracy) Han  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
Microclimates for Marine Archaeological Iron Artillery: Three Case Studies in Treatment, Storage, and Display
L. King, E. Farrell  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
 ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND  vii

Results of Research on 17th–19th-Century Coffin Portraits in the Collection of the National Museum in Krakow
M. Labut, A. Stępień, J. del Hoyo-Meléndez, M. Obarzanowski, P. Krupska, K. Stefańczyk, M. Goryl  .. . . . . . . . . . . . . . . 345
Examination of an Unusual Apulian-Corinthian Helmet Using X-Ray and Computed Tomography
M. Leroux, E. Lambert  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
Diagnostic, Restoration and Maintenance of Outdoor Bronze Artworks: Investigating Patinas in Marine
Environments and Their Stabilisation with Low Environmental Impact Treatments
P. Letardi, G. Monari  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
The Curious Case of Storage at the Petrie Museum of Egyptian Archaeology
G. McArthur, M. Chow  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
Comparing Simple Portable XRF with PIXE Analysis for Archaeological Metal Objects: Suitability, Advantages
and Drawbacks
E. Menart, Ž. Šmit  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
Methods of Marking Small Museum Objects: A Joint Project of the National Museum in Warsaw and the National
Institute of Cultural Heritage in Poland
A. Mistewicz, J. Kwiatkowska  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 350
Influence of the Application Methodology on the Performance of Coatings for the Protection of Metallic Heritage
Objects
M.T. Molina, B. Ramírez Barat, E. Cano  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
Archaeological Tinned-Copper Objects: A Study on Corrosion and Cleaning Treatments
M. Mortazavi, H.R. Bakhshandehfard, A. Abed-Esfahani  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
Archaeometallurgical Investigations of a Late Iron Age Helmet: An Interdisciplinary Approach
N. Nemeček, T. Lazar, L. Grahek, M. Nečemer, P. Fajfar, B. Žužek  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
The Care and Maintenance of Heritage Sample Collections
P. Northover, V. Cheel  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
Monitoring the Effect of Humidity on the Tarnishing of Silver 0.800 by Means of Electrochemical Noise
J. Ortíz-Corona, E.M. García-Ochoa, F.J. Rodríguez-Gómez  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
Investigating Precious Artefacts Using Non-destructive FIB on FEG-SEM: A Case Study of 10th-Century Hollow
Gilded Copper Alloy Pendants (Gombiky) from Prague Castle
E. Ottenwelter, C. Josse, L. Robbiola  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
The Enemy Within: Dezincification and Cyclic Corrosion on a Brass Patinated Equestrian Sculpture
M.J. Pereira, S. Fragoso, R. Silva, A.P. Rodrigues  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
Standardizing Acid Digestion Methodology to Determine the Chloride Content of Ferrous Corrosion Samples
K. Roche, J. Rivera, L. Arslaner, S. Crette  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
Treatment of Two Fanghu Vessels (1st Century BC): Conservation Issues of Archaeological Painted Bronze
C. Scarrone, D.M. Scalarone, F. Varallo, M. Demmelbauer, T. Poli  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
Investigating Three Types of Dry Cell Battery Deterioration
M. Sweeney  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 360
The Complexity of Developing a Restoration Plan for an 18th-Century Cast Iron Fountain
J. Tauber  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
viii  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND

Testing Gap Fillers for Archaeological Metal

S. Tsvetkov  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362
The ‘Hallmarks on (Dutch) Silver’ Project: Where Are We Now?
E. van Bork, R. Erdmann, T. Davidowitz  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
Metallotheek: A Collaborative Exploration of Bronze Patination
H. van Santen, L. van Santen  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
Author index  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 365
Keyword index  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367

Foreword
The National Museum of Finland and Metropolia
University of Applied Sciences were proud to jointly
host Metal 2022, the 10th Interim Meeting of the Metals
Working Group, part of the International Council of
Museums – Committee for Conservation. This 30-year
milestone event took place for the very first time in
Finland and the Northern European region.
After nearly three years of global uncertainty and
isolation caused by the COVID-19 pandemic, and
considering the Russian attack on Ukraine, we were
very pleased that, despite all the challenges, Metal 2022
went full steam ahead as a hybrid meeting at the
spectacular Suomenlinna Fortress, a UNESCO World
Heritage Site in Helsinki’s harbour. The decision to
offer a hybrid conference format was another first that
greatly expands professional inclusion and outreach of
the Metals Working Group and strongly reflects upon
and promotes the overarching theme of the conference:
‘Sustainability in the Conservation of Cultural Heritage’.
This is a vibrant topic reflecting the professional and
personal priorities of today: eco-friendly treatment
approaches, cross-disciplinary collaborations, social
justice, conservation education, as well as data science,
computational techniques and visualisation.
The Metals Working Group is concerned with all issues
related to preserving and presenting cultural historical
objects made of metals or metallic alloys. These consti-
tute a vast percentage of almost any museum collection.
This is also the case at the National Museum of Finland,
which is why we were delighted to see professionals
in metals conservation and related sciences gather in
Helsinki to bring together the latest developments in
Elina Anttila Eero Ehanti
Director General Keeper, Head of the Conservation Department
The National Museum of Finland The National Museum of Finland
ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND  ix
this field. Another reason for pride is this publication,
in which all the papers and poster abstracts presented at
the conference are featured. The publication adds to the
already vast body of scientific articles disseminated in the
Metals Working Group’s conference publications. These
publications are of huge importance and a remaining
point of reference to all those working in the field of
metals conservation worldwide.
Conservation is at the core of preserving cultural heritage,
transmitting its value, as well as documenting and enabling
its interpretation in various ways. Without conservation,
there would be no tangible heritage displayed in museums
and its preservation, presentation and use for research,
interpretation, learning or enjoyment would not be
possible. Conservation is a key element in the cultural
heritage sector and thanks to it, museums can better
fulfil their function of serving society. Conservation is
also an ever-growing and developing science in its own
right. Because of our role, knowledge, interdisciplinary
expertise and responsibility, the National Museum of
Finland aims to be on the frontline in developing the
field. We have ambitious goals for introducing new
conservation methods and promoting research efforts
and perspectives within the field, as well as embracing
more sustainable practices.
All of this is very much in line with the papers presented
in this publication, which is the result of a tremendous
amount of work from contributors, authors and reviewers
alike from all over the world, the Metals Working Group
coordinating team and the conference organisers in
Helsinki, to whom we are deeply thankful. It was indeed
our great pleasure to welcome you to Helsinki!
x  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND

Preface
This publication contains the proceedings of Metal 2022,
the Interim Meeting of the ICOM-CC Metals Working
Group that was held in Helsinki, Finland, on September
5–9, 2022, hosted by The National Museum of Finland
and Metropolia University of Applied Sciences.
The conference program for Metal 2022 formed a
dynamic ensemble of paper and poster presentations,
as well as invited lectures by leading voices in our field.
Authors from 26 countries, including Young Conserva-
tion Professionals, presented their work in Helsinki. In
addition, two pre-conference workshops on Cleaning
Silver Objects and Oxygen Consumption were offered, as
well as two wonderful post-conference day trips.
We were thrilled to welcome Dr. Caitlin Southwick, who
delivered a passionate keynote address on how to become
better advocates for sustainability in our field. Caitlin
also served as a moderator during an inspirational panel
discussion on sustainability—the theme of the confer-
ence—exploring with our panelists and the audience the
future of cultural heritage conservation.
For the first time in the history of our Working Group,
virtual attendance was offered for those who were not
able to travel to Helsinki. The live-streamed and recorded
virtual component expanded the outreach and access of
the Metals Working Group community worldwide. We
hope that a hybrid conference model can remain an
option for future Interim Meetings.
Metal 2022 also marked the 10th international meeting
of the Metals Working Group and offered numerous
opportunities to celebrate the resilience and many
achievements of our members and friends. Gathering
together in person after a worldwide pandemic felt like
a remarkable achievement and clearly demonstrated
the most important pandemic takeaway—our desire for
community and face-to-face dialogue.
Congratulations to all the authors, who have put so much
of themselves into this conference and worked tirelessly
to have their contributions included in this volume. Their
collective work not only reflects the constant dialogue
between conservation practice and conservation research,
but it also provides an important snapshot of the vitality
and creativity of the metals conservation community
worldwide.

Paul Mardikian
Terra Mare Conservation, LLC
Coordinator, ICOM-CC Metals Working Group

   

Liisa Näsänen, Aki Arponen, and Eero Ehanti

The National Museum of Finland

Heikki Häyhä
Metropolia University of Applied Sciences
 ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND  xi

Acknowledgments
The proceedings were edited by Paul Mardikian, Liisa We thank the Program Committee for volunteering their
Näsänen, and Aki Arponen. time to peer review and discuss abstracts and papers:

The ICOM-CC Coordination Team for 2020–2023 Ahmad N. Abu-Baker

comprised Coordinator Paul Mardikian and Assistant Yarmouk University, Jordan
Coordinators Jerrad Alexander, Valentin Boissonnas,
Jerrad Alexander
Nicola Emmerson, Elodie Guilminot, Vandana Singh,
Smithsonian National Air and Space Museum, USA
and Ellen van Bork.
Vasiliki Argyropoulos
Liisa Näsänen from the National Museum of Finland
Technological Educational Institute of Athens, Greece
served as Program Chair.
Tonny Beentjes
The Steering Committee comprised Liisa Näsänen, Eero The University of Amsterdam, The Netherlands
Ehanti, Heikki Häyhä, and Paul Mardikian.
Valentin Boissonnas
The local organizing committee comprised Liisa Näsänen, Haute Ecole Arc Conservation-restauration,
Eero Ehanti, Heikki Häyhä, Elisa Ahverdov, Aki Arponen, Switzerland
Stina Björklund, Satu Haapakoski, Anna Hyppönen,
Roni Iilomo, Pia Klaavu, Rachel Fay-Leino, Jenniina Emilio Cano Díaz
Laine, Kari Nordfors Ane Orue-Etxebarria, Päivi Paaja- National Center for Metallurgical Research (CENIM),
nen-Salmi, Sanna Paakkanen, Viktor Sohlström, Toni Spain
Spännäri, Tuomas Aatola, and Jussi Linkola. Claudia Chemello
We thank the students and lecturers from the bachelor’s Terra Mare Conservation LLC, USA
degree program in Conservation at the Metropolia Cristina Chiavari
University of Applied Sciences, students of Information University of Bologna, Italy
and Communication Technology at the Metropolia
University of Applied Sciences, the Design and Imple- Jannen Contreras Vargas
mentation services Valovirta at the Helsinki XR Center, National Institute of Anthropology and History,
Avanio Oy, and the Collections and Conservation Centre Mexico
of the Finnish Heritage Agency. Nicola Emmerson
Cardiff University, United Kingdom

Susanne Gänsicke
J. Paul Getty Museum, USA

Stavroula Golfomitsou
University of Gothenburg, Sweden

Elodie Guilminot
Arc’Antique, France

Heikki Häyhä
Metropolia University of Applied Sciences, Finland

Paola Letardi
Institute of Marine Sciences (ISMAR), Italy

Ian D. MacLeod
Heritage Conservation Solutions, Australia
xii  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND

Paul Mardikian We are grateful to Nicola Emmerson, João Cura D’Ars de

Terra Mare Conservation LLC, USA Figueiredo Junior, Henning Matthiesen, David Thickett,
and David Watkinson for presenting pre-conference
Henning Matthiesen
workshops, and to Vasilike Argyropoulos, Valentin
National Museum of Denmark, Denmark
Boissonnas, Lauren Fair, Heikki Häyhä, Vandana Singh,
Liisa Näsänen and David Watkinson for their participation in the panel
The National Museum of Finland, Finland discussion on the future of our profession, moderated by
Caitlin Southwick.
Delphine Neff
The Archaeomaterials and Alteration Prediction Thank you to invited speakers Laura Brambilla, Philippe
Laboratory (LAPA), France de Viviés, Arie Pappot, and Lisa Young for accepting
our invitation to be part of Metal 2022 and contribute
Omid Oudbashi
to the diverse program; to Ahmad N. Abu-Baker, Jerrad
University of Isfahan, Iran
Alexander, Aki Arponen, Emilio Cano Díaz, Nicola
Lyndsie Selwyn Emmerson, Elodie Guilminot, Ian D. MacLeod, Ellen
Canadian Conservation Institute (retired), Canada van Bork, and Cátia Viegas Wesołowska for chairing
Vandana Singh the paper sessions; and to Anna Hyppönen and Ane
Centre for Art Conservation and Research Experts, Orue-Etxebarria for chairing the poster sessions.
India We thank Miguel Mertens, Guy Silva, and the team
Stina Björklund from use.it, Portugal, for their hard work and unwa-
The National Museum of Finland, Finland vering support of Paper-flow, the paper management
platform used for our conferences, and Joan Reifsnyder
David Thickett for assisting with collecting the copyright transfer agree-
English Heritage, United Kingdom ments.
Johanna Thunberg Last but not least, we are thankful for the work of Carla
Cardiff University, United Kingdom Nunes and Eduardo Pulido, Portugal, who were respon-
David Thurrowgood sible for the layout and design of another beautiful Metals
Applied Conservation Science, Australia Working Group volume. Carla Nunes, Per Christopher
Foster, and Wendy Ran also provided copy editing.
Ellen van Bork
Rijksmuseum, The Netherlands

David Watkinson
Cardiff University, United Kingdom

Cátia Viegas Wesołowska

National Museum of Gdansk, Poland

Introduction
For nearly three decades, the Interim Meeting of the
Metals Working Group has served as a network to keep
members of our growing community connected, forming
one of the largest Working Groups within ICOM-CC and
possibly the largest group of metal conservation experts
in the world. This success has only been possible through
the determination, hard work, and stamina of generations
of colleagues and amazing hosting institutions.
I extend my heartfelt thanks to our conference hosts
for taking on the task of organizing an in-person and
virtual meeting, and staying the course, through such a
difficult time. Bringing Metal 2022 to the Nordic Coun-
tries has been a wonderful experience. The National
Museum of Finland and Metropolia University of Applied
Sciences surmounted enormous challenges during an
unprecedented world pandemic and economic downturn.
Navigating through a world of unknowns prompted the
organizing committee to offer a hybrid meeting with both
safe in-person and virtual attendance options—a first in
the history of the Metals Working Group. Organizing
Paul Mardikian
Coordinator, ICOM-CC Metals Working Group
ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND  xiii
the conference on Suomenlinna, a UNESCO World
Heritage Site located at the entrance to Helsinki’s harbor,
added a unique dimension to the whole experience. The
exceptional social program and the post-conference day
trips made the conference a truly memorable event. I
would also like to thank our hosts for their determined
fund-raising efforts, which resulted in 22 travel grants
for presenting authors.
Like previous Metals Working Group conferences,
Metal 2022 is the result of a vast amount of unseen work
and preparation. I am particularly grateful for a great
team of Assistant Coordinators and thank Jerrad Alex-
ander, Valentin Boissonnas, Elodie Guilminot, Nicola
Emmerson, and Vandana Singh for co-leadership and
wisdom at much-needed times.
Finally, I would like to thank the former Coordinator of
the Metals Working Group, Claudia Chemello, for her
guidance during this Triennium. None of this work would
have been possible without her unconditional support.
xiv  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND

In memoriam
David Hallam (1956–2020)

This volume is dedicated to our dear friend, colleague, mentor, and teacher David Leslie Hallam,
who left us for another great journey on February 1, 2020. Probably in one of his old Volvos.

We remember and celebrate David’s curiosity, originality, great sense of humor, cross-disciplinary
thinking, and his diverse work in our field, particularly at the Metals Working Group Interim
Meetings, when we come together to celebrate the field’s many achievements and connect with
our friends and colleagues.

Cheers, mate. We miss you.

“Tell me, I forget. Show me, I remember. Involve me, I understand.”

SUSTAINABILITY IN PRACTICE
Natural Conservation of Archaeological Iron

Henning Matthiesen* Lars Brock Andersen Philippe Dillmann Trine Wiinblad

National Museum of Denmark
Lyngby, Denmark
henning.matthiesen@natmus.dk
Jacob Frydendahl
Royal Danish Academy –
Conservation
Copenhagen, Denmark
jacob-frydendahl@hotmail.com
Centre for Preservation of Cultural
Heritage
Vejle, Denmark
lba@konsvejle.dk
Charlotte Carré
LAPA NIMBE – IRAMAT, CEA/
CNRS/U P Saclay, UMR 3685
Gif-sur-Yvette, France
cha03.carre@gmail.com
LAPA NIMBE – IRAMAT, CEA/ National Museum of Denmark
CNRS/U P Saclay, UMR 3685 Lyngby, Denmark
Gif-sur-Yvette, France trine.wiinblad@natmus.dk
philippe.dillmann@cea.fr
*Author for correspondence
Delphine Neff
LAPA NIMBE – IRAMAT, CEA/
CNRS/U P Saclay, UMR 3685
Gif-sur-Yvette, France
delphine.neff@cea.fr

Abstract
The study aimed to test whether reburial of chloride-
containing iron artefacts in a natural protective environment
can be used for the desalination of these objects. This could
constitute an alternative procedure for bulk treatment of
the large amounts of archaeological iron that is currently
discarded or stored without treatment and/or environmental
control. An anoxic, iron-reducing, pH-neutral waterlogged peat
environment was used that was rich in organic matter and had
low chloride and high carbonate content. Thermodynamics
predict that Cl−-containing Fe(II) compounds (such as ferrous
hydroxychloride) will, over time, transform into carbonates
in this environment, while iron-reducing bacteria in the peat
are expected to reduce reactive Fe(III) compounds (including
akaganeite) in the corrosion layers. In addition, anoxic and
pH-neutral conditions are expected to stop active corrosion
during the reburial period. Newly excavated iron artefacts
from a terrestrial chloride-rich environment were reburied in
waterlogged peat and samples were recovered at intervals
over 1.5 years. Their corrosion products were characterised
and compared to untreated reference samples. Desalination
efficiency was compared to burial in a peat microcosm in
the conservation laboratory, as well as to a more traditional
desalination treatment (deaerated NaOH). Analysis by Raman
spectroscopy showed corrosion products were beginning to
transform into carbonated phases, especially along cracks,
where they also seemed to give the objects increased physical
stability. Scanning electron microscopy revealed that the
spatial distribution of Cl− was heterogeneous in both treated
and untreated samples, while digestion experiments suggested
a lower total Cl− content for the treated samples. The results
indicate that reburial has potential for natural conservation,
but that the process can take a long time.
Keywords
archaeological iron, desalination, reburial, iron-reducing
bacteria, natural conservation, in situ treatment

Introduction
Chloride-containing iron artefacts cause severe problems
in museums. The chloride (Cl−) can be tightly embedded
in the thick corrosion layers of iron objects and cause
the objects to crack and disintegrate upon excavation
(Selwyn et al. 1999). If Cl− is not removed, it is necessary
to store artefacts in either very dry conditions (< 12%
RH; Watkinson and Lewis 2005) or oxygen-free envi-
ronments (Paterakis and Hickey-Friedman 2011), both
of which are expensive and may harm their ability to be
exhibited. Alternatively, attempts may be made to remove
the Cl− using electrochemical techniques, annealing in an
inert atmosphere, hydrogen plasma, subcritical fluid or
extraction in alkaline solutions. None of these methods
have been quantitatively proven to be 100% efficient at
removing Cl− and are often labour intensive, ill-adapted
to mass treatment and may cause irreversible changes
to the objects.
Cl− is mainly found either as a counter ion or within
Cl−-bearing compounds at the interface between the
metal core and the corrosion products. The release of
Cl− is determined by how it is bound. For example, the
mineral akaganeite (β-FeOOH) that is formed under
aerated conditions can contain both lattice-bound and
surface-bound Cl− with different properties (Watkinson
NATURAL CONSERVATION OF ARCHAEOLOGICAL IRON
and Emmerson 2017), while ferrous hydroxychloride
(β-Fe2(OH)3Cl) that is formed under anoxic conditions
can release Cl− upon oxidation or dissolution during
storage and conservation of objects (Reguer et al. 2007,
Kergourlay et al. 2018). Potentially, both phases are able
to release Cl− depending on the conditions and their
stability, and ideally both phases should be transformed
during conservation into other more stable phases that
do not contain Cl−.
It is well established that soil contains a large group of
iron-reducing bacteria that under anoxic conditions
reduce iron(III) minerals to iron(II) in order to oxidise
organic material and obtain energy for their metabolism
(Kirk 2004). During preliminary experiments, archaeo-
logical iron artefacts covered by thick layers of iron(III)
oxide corrosion products were reburied in a waterlogged
peat, and after three years the main phase in the corrosion
layer was iron(II) carbonate (Saheb et al. 2011). Similar
effects using pure strains of iron-reducing bacteria in the
laboratory have been recorded (Comensoli et al. 2017,
Kooli et al. 2018).
This study investigated a new low-tech and low-cost
approach to remove Cl− from corrosion layers in archaeo-
logical iron within a natural protective environment. The
low-tech approach is based on reburying the artefacts
in a waterlogged freshwater peat that is organic-rich,
oxygen-free, pH-neutral, carbonate-rich, low in Cl− and
with a natural content of iron-reducing bacteria. Our
hypothesis was that the artefacts would be preserved
in this environment, that the new thermodynamic
conditions and natural iron-reducing bacteria would,
over time, transform the corrosion products into more
stable compounds and that Cl− would slowly be removed
through diffusion. The results of the experiment were
Table 1. Overview of the number of samples and subsamples used in each treatment and for the different analyses. ‘Total number’ shows how many
samples were treated, ‘Retrieved after 0.5/1/1.5 year(s)’ shows how many were retrieved at the different time intervals and ‘Analyses’ shows how many
samples were analysed by the different methods. The remainder of the samples are either under continued treatment or stored for future analysis
Total Retrieved
Treatment Type
number 0.5 year
NaOH Subsample 8 2
NaOH Whole lance 1 0
Reburied Subsample 9 2
Reburied Whole lance 3 0
Peat, lab Subsample 11 2 2
Peat, lab Whole lance 3 0
Reference Subsample 9 2
Reference Whole lance 2 0
17
compared with state-of-the-art Cl − removal under
oxygen-free, alkaline conditions in the conservation
workshop (Kergourlay et al. 2018).
Samples and methods
The study was carried out on archaeological material from
Stavsager in Western Jutland, Denmark (N 55°21.179’ E
008°56.387’) where the soil is sandy and normally rich in
Cl− due to proximity to the North Sea. A total of 13 lances
measuring 14–20 cm in length and dating from approx-
imately AD 200–500 (Grundvad 2020) were used. Four
of these were divided into ca. 1.5 cm long subsamples
using a diamond saw in order to have sufficient replicate
samples for the study. Both the subsamples and whole
lances were treated for either 0.5, 1 or 1.5 years, and the
results were compared to the untreated reference samples.
The treatments included reburial in a wetland, burial
in waterlogged peat in the laboratory and treatment in
anoxic NaOH (Table 1). Due to space restrictions, only
selected results are presented here that focus on the
samples treated for 1.5 years. Some of the samples (four
of the lances and several subsamples) are still buried for
longer-term examination.
Reburial took place in waterlogged peat at Nydam
Mose in Southern Jutland, Denmark (N 54°57.637’
E 009°43.657’). Nydam is an archaeological site where
large amounts of weapons and personal equipment were
deposited between AD 250–500. Parts of the site were
excavated from 1989 to 1997, and the environmental
conditions were investigated and monitored from 1997
to 2021 to preserve the remaining unexcavated artefacts
in situ (Matthiesen et al. 2004 and 2020). Reburial of
three lances and nine subsamples was carried out in
a backfilled pit from the former excavations. Samples
Retrieved Retrieved
Analyses
1 year 1.5 years
2 4 SEM & Raman (2), or total-Cl (1)
0 1 Cleaning (1)
2 2 SEM & Raman (2), or total-Cl (1)
0 1 Cleaning (1)
2 SEM & Raman (2), or total-Cl (1)
0 1 Cleaning (1)
0 3 SEM & Raman (3), or total-Cl (2)
0 2 Cleaning (2)
18  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
were placed in large-mesh polyester nets that could be
pressed down into pre-drilled holes (3 cm in diameter)
to a depth of 0.8 m below the surface of the soil. The nets
were attached to a polyester string (1.5 mm in diameter)
to the soil surface to allow easy retrieval of the samples
(Figure 1). The pre-drilled holes were backfilled with
peat whose spongy nature created a good seal. On site,
the water level and temperature within the peat were
monitored continuously using a Van Essen TD-Diver and
during site visits oxygen concentration, redox potential
and pH were measured directly in the soil at the depth of
the samples using the methods described in Matthiesen et
al. (2004 and 2013). Samples of soil water were retrieved
and analysed for alkalinity, dissolved iron, sulfate and
Cl− as described in Matthiesen et al. (2004). Buried iron
samples were retrieved with two subsamples after 0.5, 1
and 1.5 years and a whole lance after 1.5 years. They were
pulled up using the attached string so no digging was
required. After retrieval, the samples were transported to
the laboratory in absolute ethanol where they were dried
for a few minutes in warm air and kept under anoxic
and dry conditions (in Escal oxygen barrier film with
nitrogen atmosphere and dried silica gel) until analysed.
Figure 1. Image of net with iron subsample for reburial. The net was
attached by the white string to the surface of the soil to allow easy
retrieval of the sample
Three lances and 11 subsamples were placed in a micro-
cosm constituting a closed system of 100 L of waterlogged
Nydam peat in the laboratory, and the same analyses as
described for Nydam were carried out. The microcosm
was briefly opened for recovery of samples at the same
time intervals as those at Nydam.
SUSTAINABILITY IN PRACTICE
Treatment of one lance and eight subsamples in indi-
vidual baths of 0.5 M NaOH (analytical grade) was
carried out in a nitrogen atmosphere in a custom-made
chamber (Frydendahl et al. 2022). Anoxic conditions
were verified by oxygen sensors (PSt3 from PreSense).
Treatment solutions were changed after 1, 2, 3, 4, 6 and
10 months and analysed for extracted Cl− using ion
chromatography (IC) (Metrohm 881 Compact IC pro
ion chromatograph equipped with a Metrosep A supp
16 250/4.0 column with ion suppression).
Two untreated reference lances and nine untreated
reference subsamples were stored under anoxic and dry
conditions until analysis as described above.
Subsamples from each treatment as well as untreated
reference samples were embedded in epoxy resin, cut
using a diamond saw and ground using 320, 800, 1200
and 4000 grit SiC grinding paper with absolute ethanol
as a coolant and lubricant. They were then polished on
velvet pads using a diamond spray (3 μm and 1 μm).
The cross-sections were analysed by scanning electron
microscopy (SEM) coupled with energy-dispersive x-ray
spectroscopy (EDS) (JEOL 7001F, acceleration voltage of
15 kV, Cl detection limit of ca. 0.5 mass%) and Raman
spectroscopy (inVia Renishaw, 532 nm, 1 µm spot size,
100 µW). Distinction was made between the dense
product layer (DPL, the inner corrosion products that
do not contain markers of the soil such as quartz grains)
and the transformed medium (TM, the outer part of
the corrosion system that is a mix between corrosion
products and markers from the soil), as described in Neff
et al. (2005). Cl content in the DPL was determined by
EDS (Aztec software) for selected zones excluding the
signal from metal, resin and TM. Raman spectroscopy
was used on both DPL and TM. Other subsamples
(both treated and untreated) were dissolved in 4.5 M
sulfuric acid (analytical grade). During dissolution, the
containers were covered with PE film (parafilm) and
lidded, but loosely. After dissolution, the solutions were
neutralised using NaOH (analytical grade), filtered and
the Cl− content was quantified using IC as described
above (modified from Rimmer et al. 2012).
After 1.5 years of treatment, two whole lances (one from
Nydam and one from the peat in the laboratory) were
cleaned to the corrosion layer representing the original
surface by scalpel and air abrasion before being coated
with microcrystalline wax (Mobil Kote 420). The NaOH-
treated lance was impregnated with wax before being
NATURAL CONSERVATION OF ARCHAEOLOGICAL IRON 19

cleaned due to its fragility. Cleaning was carried out

by two conservators working in parallel on each lance,
discussing and noting hardness, tendency to flaking/
spalling and ease of locating the original surface of the
artefacts to compile subjective qualitative assessments
of object condition. Two untreated lances were cleaned
for comparison. The subsamples were too small and
their corrosion products too fragile to test mechanical
cleaning.

Thermodynamic modelling of the stability of different

minerals under the environmental conditions prevailing
at Nydam was carried out using The Geochemist’s Figure 2. Water level and soil temperature variations at Nydam. The
Workbench 2021 software version 15.0.0 (available from samples were buried during spring 2019 at a depth of 80 cm, where the
soil temperature was also monitored
www.gwb.com/, accessed on 3 March 2022). The built-in
thermodynamic database was used and supplemented
with data for ferrous hydroxychloride (Nemer et al.
2011), chukanovite (Kim et al. 2017) and akaganeite
(Rémazeilles et al. 2009).

Results
Environmental conditions varied between the different
treatments. For the reburial site at Nydam, Figure 2
shows limited seasonal variation in temperature and
constant waterlogged conditions at the reburial depth.
Other environmental parameters measured during the
four site visits and the results from the laboratory peat Figure 3. Photomicrograph of a cross-section of an untreated reference
sample with four colour EDS maps, where iron is purple and Cl− is blueish.
microcosm and NaOH treatments are reported in Table 2.
Five areas marked by red boxes (no. 1–5) indicate zones where the Cl−
All parameters except Cl− showed a modest variation content of DPL was quantified and Raman measurements were performed
over time. In the peat microcosm, the Cl− content in the (Figure 4). The green line shows the interface between DPL and TM
water samples increased after burial of the archaeological
iron samples, which was not the case at Nydam. In the
objects (Figure 3). The distribution of Cl− within the
NaOH treatment, the solutions were changed at inter-
corrosion layers was extremely heterogeneous and mostly
vals, and only the first bath showed markedly increased
found in small pockets (blueish colour) near the metal
Cl− concentrations.
surface. Some of the zones (marked by red rectangles)
SEM-EDS analysis of a cross-section from an untreated have been further investigated by Raman point measure-
subsample is shown as an illustrative example of the iron ments to identify corrosion products (Figure 4), and the

Table 2. Comparison between the three treatment environments. Values given as mean ± standard deviation for four site visits (except temperature
at Nydam, which is measured daily). SHE = standard hydrogen electrode; nm = not measured

Reburied Peat, lab NaOH

Temperature (°C) 9.8 ± 1.4 19 ± 1.5 21 ± 1
Oxygen Anoxic Anoxic Anoxic
Redox potential (mV vs SHE) −208 ± 5 −224 ± 7 nm
pH 6.2 ± 0.1 6.5 ± 0.1 13.7
Alkalinity (meq/L) 8.8 ± 0.2 16.3 ± 0.4 nm
Cl− (mg/L) 36 ± 4 62 before sample burial 10–120 in first baths,
89 ± 6 after < 2 in next baths
Fe2+ (mg/L) 6.7 ± 1.0 16 ± 4 nm
20  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND SUSTAINABILITY IN PRACTICE

Figure 4. Backscatter SEM images of zones 1–5 from an untreated

reference sample (red rectangles in Figure 3) with superimposed
identification of corrosion products by Raman spectroscopy. The Figure 5. Backscatter SEM images of a subsample treated for 1.5 years in
different corrosion products are identified in the key, with blue symbols a peat microcosm in the laboratory with superimposed identification of
for iron oxides (magnetite, maghemite and hematite), yellow for iron corrosion products. No. 1–3 show different areas on the sample. Symbols
hydroxy oxides (goethite and ferrihydrite), red for chlorinated phases
and colours as described in Figure 4
(akaganeite and ferrous hydroxychloride) and green for carbonated
phases (chukanovite and siderite). A few analyses showed fayalite (light
blue circle with a cross), which is not a corrosion product but part of the
slag from iron production. The metallic iron is white, while the black part
of the images consists of sand grains and embedding media

average Cl− content was quantified in the DPL within

Figure 6. Photomicrographs of three different areas with carbonated
the same zones by SEM-EDS mapping.
phases from a subsample treated for 1.5 years at Nydam: (1) is from
Raman analysis revealed heterogeneous and highly the inner corrosion products (DPL), (2) shows a crack in the DPL that
is covered with siderite and (3) shows siderite precipitated next to a
complex corrosion layers, with up to nine different corro- sand grain in the outer corrosion products (TM). Symbols and colours
sion products being identified in the untreated sample as described in Figure 4
(Figure 4). At the interface between metal and corrosion
products, large areas of ferrous hydroxychloride and to
The results from the Raman analyses are summarised in
a lesser extent akaganeite were identified in the chlorin-
Figure 7, which shows a relative abundance of different
ated areas (most distinct in Figure 4.2 and 4.4), while
types of corrosion products. Although over 100 meas-
chukanovite and other compounds were identified in the
urements were carried out for each sample, abundance
non-chlorinated areas. The DPL primarily consisted of
measurements cannot offer exact areal distribution of
magnetite, with goethite and maghemite marbling, while
different corrosion products, as this will depend upon
the outer transformed layer (TM) primarily consisted of
where the operator decides to conduct analyses.
goethite (Figure 4, 1–2). Similar analyses were carried out
on samples from all treatments. The results for samples Measurements of total Cl− (as a percentage of the total
treated in peat are similar to the layout of the untreated weight of the sample) for five digested samples (two
sample but with some distinctively different features:
Figure 5 demonstrates how a sample treated for 1.5 years
in the peat microcosm has a distinct presence of siderite
in the outer corrosion layers (TM) as well as siderite layers
in cracks and exposed parts of the DPL. Figure 6 shows
some more detailed investigations of a sample buried
for 1.5 years at Nydam, which confirms the tendencies Figure 7. Relative abundance of phases identified in the corrosion layers
observed from the peat microcosm, and also shows how after 1.5 years of treatment. The total number of analyses for each sample
the surface of cracks is covered by siderite (Figure 6.2). is shown in parenthesis. The phases are grouped as: blue for iron oxides
(magnetite, maghemite and hematite), yellow for iron hydroxy oxides
The results for samples treated in NaOH are markedly
(goethite and ferrihydrite), red for chlorinated phases (akaganeite and
different, showing the presence of magnetite, goethite ferrous hydroxychloride) and green for carbonated phases (chukanovite
and ferrihydrite only (not shown). and siderite)
NATURAL CONSERVATION OF ARCHAEOLOGICAL IRON
untreated reference samples and three treated samples)
are shown in Figure 8a. The results are very uncertain
and recovery tests showed that there may be a loss of
Cl− of up to 56% due to matrix effects and evaporation
during dissolution. Results from mapping Cl− content
by SEM-EDS (as a percentage of the weight of the DPL)
in five zones on each sample (three untreated reference
samples and three treated samples) are compiled in Figure
8b. SEM-EDS focused on the DPL alone, where most Cl
is found; this results in higher Cl content compared to
digestion, as the latter also includes metallic iron and
TM with lower Cl content.
Figure 8. Measurement of Cl− content after 1.5 years of treatment:
(a) total Cl− (as a percentage of total sample weight) measured in five
subsamples after dissolution in acid; (b) mapping of Cl− by SEM-EDS
on six other subsamples. The reference boxplot represents 15 areas on
three untreated reference samples, while the other boxplots represent
five areas on one sample for each treatment. Circles show individual
measurements, crosses show mean value, boxes show 1st, 2nd (line)
and 3rd quartile, and whiskers show minimum and maximum values
Treated lances were cleaned to reveal a corrosion layer
representing the original surface. During this procedure,
it was subjectively noted that the corrosion layers of
objects from reburial and laboratory peat were coherent,
seemed slightly softer than the untreated material and
21
Figure 9. Lance shown before reburial, after reburial for 1.5 years at
Nydam and after final cleaning (with air abrasion)
that the original surface was easily recognised. No loss
of corrosion products had occurred during burial in
peat (Figure 9). In NaOH, the corrosion layer became
extremely porous and fragile, requiring impregnation of
the lance with wax before cleaning, which proved difficult
to control and made the original surface hard to identify.
Discussion
Evidence of change and desalination
The study material was very heterogeneous both in terms
of corrosion products (Figure 4) and Cl distribution
(Figure 3), making it challenging to document changes
unless they were very comprehensive.
NaOH treatment caused significant changes to the
samples: the Cl content was lowered (Figure 8), the corro-
sion products consisted almost exclusively of magnetite
and goethite (Figure 7) and the corrosion layers became
porous and fragile (as reported by Selwyn and Argy-
ropoulos (2005) for heavily degraded objects). Increased
porosity can to some extent be caused by transformation
of chlorinated phases to magnetite, which has a low
volume per iron atom (28–33 cm3/mol Fe for the chlo-
rinated phases and only 15 cm3/mol Fe for magnetite).
While increased porosity may speed up the removal of
Cl− , it may also produce more fragile corrosion layers.
The changes in the samples treated in peat in situ
and in the laboratory were more subtle: Raman anal-
yses identified more carbonated phases and less iron
oxides (Figure 7) and a change in phase distribution
(Figures 5, 6) when compared to the untreated samples,
even if the transformation was by no means complete
after 1.5 years. The transformation from chlorinated
phases (28–33 cm 3/mol Fe) to carbonated phases
22  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND SUSTAINABILITY IN PRACTICE

(28–29 cm3/mol Fe) is a modest change in volume, so

porosity will not increase as was the case with NaOH
treatment. Local precipitation of carbonates was observed
especially along cracks (Figure 6), which may explain why
the lances treated in peat showed less tendency to flake
than the untreated lances. Total Cl− in samples treated in
peat was lower than in the untreated samples (Figure 8a)
and the Cl− content in the peat microcosm increased after
burial of the samples (Table 2), both indicating some Cl−
removal from the samples. However, desalination was not
complete and there were still zones with high amounts
of Cl− in the DPL in samples both from the microcosm
and from Nydam (Figure 8b). Thus, overall, there were
some indications of changes to the objects and a tendency
towards both desalination and physical stabilisation, but
the changes were slow and it is too early to reach any Figure 10. Pourbaix diagram calculated by The Geochemist’s Workbench
for an environment with 0.12 mM of dissolved iron, alkalinity of
firm conclusions about the removal of Cl− due to the 10 meq/L, 1 mM of Cl− and suppressing hematite. The red dot shows
heterogeneity of the material. the average pH and redox potential measured at Nydam during four
site visits
Burial environment and thermodynamics
ychloride, on the other hand, requires high concentra-
The burial environment at Nydam is very stable with tions of Cl− and Fe2+ to precipitate (Remazeilles et al.
waterlogged, carbonate-rich, Cl −-poor, anoxic and 2009), and thermodynamic modelling indicates that
pH-neutral conditions that are favourable for the pres- it is not stable at the concentrations found in Nydam.
ervation of iron. High carbonate contents in pH-neutral However, the kinetics are slow, which may be explained
conditions indicate high CO2 pressure, and previous
by slow ion transport through compact corrosion layers.
measurements of CO2 pressure have shown up to 0.5 bar
Furthermore, the samples in this study have a relatively
CO2 in the peat (Matthiesen et al. 2004). During this
high content of Fe(II) corrosion products that cannot be
project, the environmental conditions were monitored
utilised by iron-reducing bacteria but have to be trans-
for two years, and the results were similar to values from
formed through abiotic processes such as dissolution and
the last 20 years of monitoring (Matthiesen et al. 2020).
re-precipitation, which can be relatively slow processes.
In the longer term, the presence of very well-preserved
iron objects from AD 200–500 in Nydam show that pres- Safety and accessibility of the objects should also be
ervation conditions for iron have been favourable during considered as far as reburying archaeological iron is
this period. The corrosion products on archaeological concerned, with risk of changes to the environment
objects from Nydam were predominantly siderite, which (such as physical disturbance or changes in water level)
seems to be a long-term stable compound (Matthiesen and risk of theft. At Nydam, these risks are very low, as
et al. 2003). the site is listed. There are strong restrictions with regard
Thermodynamics indicate that corrosion products on the to the water level and use of the site, but this will not be
reburied artefacts will change over time. Figure 10 shows the case everywhere and some monitoring will normally
a Pourbaix diagram for iron adjusted to the environ- be needed. As for accessibility, it is always possible to
mental conditions prevailing at Nydam, and where the pH retrieve the objects, but this is obviously more tedious
and redox potential measured at the site are marked. The than retrieving them from a storage room and therefore
diagram indicates that the system is saturated regarding reburial is not suited for objects that need to be studied
siderite, which means that if Fe2+ is produced during very frequently. Some of these limitations may be solved
transformation or dissolution of corrosion products, it by reburial in peat at the laboratory, where the transfor-
will re-precipitate as siderite, as was indeed observed in mations seem to be slightly faster than in situ (Figure 7),
cracks in the buried artefacts (Figure 6). Ferrous hydrox- but there are also disadvantages to using a closed system,
NATURAL CONSERVATION OF ARCHAEOLOGICAL IRON
as Cl− from artefacts will accumulate in the peat, and it is
not practical for long-term treatment or storage.
Conclusion
Reburial as reported here may offer temporary storage
and/or possible desalination treatment options. As
storage, it can provide a stable and completely anoxic
environment that may be compared to current expensive
museum storage under either very dry or anoxic condi-
tions. In terms of desalination, it is too early to evaluate
the efficiency of reburial – it is certainly significantly
slower than alkaline extraction but may offer other
advantages such as physical stabilisation of the objects,
sustainability (no use of chemicals) and easy upscaling.
Thus, overall, reburial should be considered a supple-
mentary procedure rather than a replacement for existing
methods. It could, for instance, be used for the large
amounts of archaeological iron that is currently discarded
after being recorded due to the high costs of conservation
and storage, or even as a storage solution for some of the
accessioned but unstable iron artefacts that continue to
degrade in museum collections (González and Salvato
2019).
This initial study has only scraped the surface, exam-
ining principles and tendencies rather than quantitative
effects. The results so far have indicated that reburial and
storage in waterlogged peat could be feasible but that
transformation of corrosion products and desalination
is very slow for the studied artefacts. More studies are
needed to reach more firm conclusions. These include
study of iron artefacts from other sites. For instance, it
is likely that artefacts dominated by Fe(III) minerals will
show faster transformation due to iron-reducing bacteria.
Consequently, removal of Cl− from ferric akaganeite could
be faster than from ferrous hydroxychloride. Studies on
the transformation of synthetic corrosion products and
on microbial activity are also needed.
Acknowledgements
We would like to thank Lars Grundvad from Sønder-
skov Museum and Lasse Sørensen from the National
Museum of Denmark for providing the sample material,
the Danish Cultural Ministry for financing the study
and the Ingwersenske Fond, William Demant Fonden,
Augustinus Fonden and Elisabeth Munksgaard Fonden
for supporting Jacob Frydendahl’s research visit to LAPA.
23
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Authors
Henning Matthiesen is senior researcher at the National
Museum of Denmark and an honorary professor at the
Royal Danish Academy – Conservation. He undertakes
research on the preservation of archaeological remains
both in situ and in museum storage.
Jacob Frydendahl has an MSc in conservation from
the Royal Danish Academy – Conservation where he
developed his thesis on the present project. He works
in the field of dechlorination of archaeological iron and
the transformation of corrosion products.
Lars Brock Andersen has a BSc in conservation. He
has been working for many years in the field of method
development and hands-on conservation of chloride-rich
archaeological iron.
Charlotte Carré obtained her master’s from La Rochelle
University (France) and her PhD from New-Caledonia
University. Her current research interests include the
study of the behaviour of metallic materials depending
on their environment.
Philippe Dillmann is director of the Laboratoire
archéomatériaux et prévision de l’altération (LAPA). He
has a PhD in material science and undertakes research
on the long-term alteration of metals and glasses.
Delphine Neff is a research scientist at LAPA. She
undertakes research on understanding the transfor-
mation of ancient corrosion layers during desalination
treatments as well as their interaction with organic
compounds applied as protective coatings.
Trine Wiinblad has an MSc in conservation from the
Royal Danish Academy – Conservation. She has been
working for many years in the field of method devel-
opment and hands-on conservation of composites and
chloride-rich archaeological iron.
Exploiting Biologically Synthetized Chelators in
Conservation: Gel-based Bio-cleaning of Corroded Iron
Heritage Objects
Luana Cuvillier
Haute Ecole Arc Conservation-restauration (HE-Arc CR), HES-SO University of
Applied Sciences and Arts Western Switzerland
Laboratory of Technologies for Heritage Materials (LATHEMA), Institute of
Chemistry, University of Neuchâtel
Neuchâtel, Switzerland
luana.cuvillier@he-arc.ch
Arianna Passaretti
Haute Ecole Arc Conservation-restauration (HE-Arc CR), HES-SO University of
Applied Sciences and Arts Western Switzerland
Laboratory of Technologies for Heritage Materials (LATHEMA), Institute of
Chemistry, University of Neuchâtel
Neuchâtel, Switzerland
arianna.passaretti@he-arc.ch
Aymeric Raimon
Laboratoire Arc’Antique, Grand patrimoine de Loire-Atlantique (GPLA)
Nantes, France
aymeric.raimon@loire-atlantique.fr
Abstract
The complexing agents widely used for the removal of undesired
corrosion products from iron artworks can be difficult to control
and their environmental impact is often overlooked. This paper
compares the efficiency of deferoxamine B (DFO), a siderophore
synthesised by the bacterium Streptomyces pilosus, with that
of disodium ethylenediaminetetraacetic acid (Na2EDTA) in the
removal of iron corrosion phases. Several bio-derived hydrogels
were exploited as carriers and preliminary tests were carried out
on naturally aged samples. The investigated parameters included
siderophore concentration, treatment duration and potential
reapplication, as well as a reliable application protocol. Cleaning
efficacy was evaluated using optical microscopy, colourimetry and
Raman spectroscopy. Iron uptake was monitored in gel matrixes
through colourimetry and atomic absorption spectroscopy. The
Introduction
Like most metals, iron is vulnerable to corrosion. For
iron artworks, this problem requires unique solutions to
ensure their long-term preservation (Kooli et al. 2018).
For artworks stored in museums without appropriate
environmental control (Monnier et al. 2013), the corro-
sion layer that forms is often a combination of several
iron oxyhydroxides, including goethite (α-FeOOH) and
lepidocrocite (γ-FeOOH) (Monnier et al. 2010 and 2013).
In the case of archaeological iron objects, however, the
corrosion layer is more complex and heterogeneous. In
Virginie Dupuy
Laboratoire Arc’Antique, Grand patrimoine de Loire-Atlantique (GPLA)
Nantes, France
virginie.dupuy@loire-atlantique.fr
Elodie Guilminot
Laboratoire Arc’Antique, Grand patrimoine de Loire-Atlantique (GPLA)
Nantes, France
elodie.guilminot@loire-atlantique.fr
Edith Joseph*
Haute Ecole Arc Conservation-restauration (HE-Arc CR), HES-SO University of
Applied Sciences and Arts Western Switzerland
Laboratory of Technologies for Heritage Materials (LATHEMA), Institute of
Chemistry, University of Neuchâtel
Neuchâtel, Switzerland
edith.joseph@he-arc.ch
*Author for correspondence
results showed the comparable cleaning efficiency of DFO and
Na2EDTA at neutral pH. However, the DFO-hydrogel performed
better on iron rust. A frequent renewal of the treatment
formulation ensured more effective cleaning. Among the different
carriers tested, agar gels applied when hot and gellan gum gels
prepared at room temperature were the most effective, and left
few residues on the treated surfaces. The methodology was then
tested on altered steel artefacts belonging to heritage institutions
in Nantes (France). The encouraging outcomes point the way to
a more sustainable approach to treating historical iron artworks.
Keywords
siderophores, iron objects, corrosion, biocleaning, green
chemistry, hydrogels, deferoxamine B
either case, the removal of active or unaesthetic corro-
sion stains is needed to arrest ongoing damage processes
and to facilitate the appreciation, readability and use of
the object. The cleaning agent most commonly used
by conservators is the sodium salt of ethylenediamine-
tetraacetic acid (Na2EDTA), which complexes iron at a
maximum molar ratio of 1:1, according to the pH, and
turns light yellow after iron complexation (Filipsky et al.
2013). However, despite its easy availability and low cost,
EDTA is classified as an irritant and it must be used with
26  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
appropriate caution (Kaurin et al. 2021). In addition,
although the quantities used in cultural heritage are
much smaller than in other industrial applications, EDTA
is not biodegradable and its environmental impact is a
worldwide concern (Gluhar et al. 2020). Thus, in this
study we tested a bio-derived complexing agent in an
effort to develop more sustainable cleaning practices.
Specifically, we examined the efficacy of the siderophore
deferoxamine B (DFO), produced by the bacterium
Streptomyces pilosus. DFO is a natural iron chelator
whose synthesis is stimulated in iron-deficient environ-
ments (Albelda-Berenguer et al. 2019). DFO and other
siderophores are biodegradable and have a pH close to
neutral, which makes them less harmful to the envi-
ronment and in their applications (Fazary et al. 2016).
DFO has been tested on iron-contaminated wood, paper
and textile artworks, due to its high affinity for iron,
as evidenced by its stability constant (logβ), a measure
of the interaction strength between two components
forming a complex: 30.4 for DFO (Farkas et al. 1999)
versus 25 for EDTA (Rapti et al. 2021) (Figure 1). DFO
chelates iron at a 1:1 molar ratio and iron binding causes
it to turn bright orange-red, allowing its activity to be
easily ascertained.
A further consideration in the development of
DFO-based cleaning methods is the delivery system.
Although the use of gels as delivery systems is not as
widespread in metal conservation as in other sectors of
art conservation, their acceptance is rapidly increasing
(Passaretti et al. 2021). The advantages of gels in conser-
vation include: controlled delivery of the embedded
active substances, the need for smaller quantities of
reagents and easy clean-up after treatment, all of which
contribute to the protection of the treated artefact, the
operator and the environment. Several polymers, espe-
cially polysaccharides, can be employed in the design of
DFO-based hydrogels as they are compatible with the
neutral pH (6.8) of the DFO solution and the chelating
Table 1. Overview of the different gel formulations tested
Xanthan gum Agar
Brand, supplier Vanzan©, CTS AgarArt©, CTS
Chelator DFO DFO and Na2EDTA
Preparation 5% w/v in H2O and 3% w/v in H2O, heated to 90°C twice
manual stirring
Application With a spatula at Dripped when still Cooled preformed With a spatula at room
room temperature hot rigid foil
Label in the text A B C
SUSTAINABILITY IN PRACTICE
action of the latter is unaltered even at the relatively high
temperatures (up to 110°C) needed to prepare the gels
(Pawlaczyk and Schroeder 2021). Only naturally derived
gelling agents were considered here, namely gellan and
xanthan gums, which are obtained from bacteria, and
agar, which is extracted from red seaweed.
The application protocol and case studies described
below demonstrate the potential of this ground-breaking
methodology in terms of its greater efficiency and
sustainability compared to Na2EDTA.
Figure 1. Molecular structure or of deferoxamine B (DFO)
Materials and methods
Corroded iron substrates
Naturally corroded mild steel samples (20 × 30 × 2 mm)
were obtained from a private conservation workshop,
where over a period of years they underwent atmos-
pheric corrosion due to uncontrolled indoor conditions.
Prior to their use in the experiments, the steel samples
were degreased with a cotton swab soaked in 70% v/v
ethanol and the corrosion layer was characterised by
Raman spectroscopy, which revealed both goethite and
lepidocrocite, common compounds that develop during
indoor iron corrosion.
Gelling agent selection
The suitability of several naturally derived hydrogels
amended with a solution of DFO mesylate salt (Desferal,
Novartis) was assessed using triplicate steel samples
(Table 1). Each gel formulation was applied to the
corroded surface and removed after 10 min using a cotton
swab soaked in 70% v/v ethanol.
Gellan gum
Phytagel™, Sigma Aldrich
DFO
3% w/v in H2O, manual stirring 3% w/v in H2O, heated to 90°C
Dripped when still hot
temperature
D E
EXPLOITING BIOLOGICALLY SYNTHETIZED CHELATORS IN CONSERVATION: GEL-BASED BIO-CLEANING OF CORRODED IRON HERITAGE OBJECTS 27

Evaluation of the application parameters
Iron chelation was assessed after the immersion of the
corroded steel samples for 10 min, 30 min, 1 h, 5 h and 24
h in a solution of DFO at concentrations of 0, 3·10−4, 3·10−3,
3·10−2 and 6·10−2 M. A 3% w/v agar gel amended with the
same concentrations of DFO was applied to the naturally
corroded iron samples for 10 min. The application was
repeated five more times, for a total application time of 60
min. In addition, a 3% w/v agar DFO-gel at a concentration
of 6·10−2 M was applied to five iron coupons for 10 min,
30 min, 1 h, 5 h and 24 h, respectively. For comparison, a
3% w/v agar gel amended with Na2EDTA (PanReac Appli-
chem) was tested using the same reiterative application
protocol. All tests were carried out on triplicate samples.
Case studies
Four iron-based artefacts were selected: (i) a calyx and
a candle holder from the Diocese of Nantes (France), as
historical objects; (ii) a gorget and a helmet belonging to the
personal collection of Raoul de Rochebrune (1849–1924)
and bequeathed to the Dobrée Museum of Nantes (France)
in 1930, as archaeological objects (Table 2).
The objects were marked by heterogeneous corrosion
phases and conditions, as described in Table 2.
Consequently, the treatment aims for the two sets of
objects differed and had to be specifically defined for
each type (religious artefacts or archaeological objects).
For the diocesan calix and candle holder, a continuous
and homogeneous thin red layer, typical of surface oxida-
tion and probably consisting of goethite, was seen. The
metallic surface was well preserved, and a black patina was
sporadically present. The goal was to reduce the reddish
corrosion layer until the metallic surface by means of gentle
chemical cleaning, in order to limit metal brightness and
preserve the black patina. Based on mock-up results, the
religious artworks received two 15-min applications of 3%

Table 2. Overview of the artefacts treated

Material Description Picture

Calyx Steel

1 – atmospheric corrosion layer

2 – black patina
3 – metallic surface

Candle Holder Cast iron

Gorget Steel
(internal side)

1 – dirt and sediments

2 – corrosion products
3 – original surface
4 – metallic surface
Helmet Steel
(internal side)

1 – external elements (pebbles)

2 – red corrosion products
3 – dense corrosion crust
4 – original surface
5 – metallic surface, visible in the crevices
28  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
w/v agar gels amended either with DFO or EDTA (both
at a concentration of 6·10-2 M); the application of agar gel
to three distinct areas served as a control.
For the gorget and helmet, the lack of conservation of
the original surface can be explained by the fact that,
like most of the collection, these archaeological objects
were probably discovered in a fluvial environment, which
would account for the stripped aspect of both the gorget
and helmet. Heterogeneous crevices or pit corrosion were
seen on the helmet and the strong areas of abrasion on
its outer parts indicated that it had been cleaned in the
past using chemical and/or mechanical means, typical
of the late 19th century. The black patina on the helmet
and gorget was present only sporadically, with its loss
probably the result of uncontrolled cleaning. Further
loss would lead to the undesired exposure of the metallic
surface. As the dense red corrosion layer visible on the
crevices served as historical evidence, its retention was
desirable. Three different areas on the gorget and inte-
rior aspect of the helmet were treated. Due to the thick
corrosion present on both objects, the overall cleaning
consisted of the application of 3% w/v agar gels amended
either with DFO or EDTA (both at a concentration of
6·10−2 M) for 3× 20 min. The control consisted of plain
agar gel applied following the same protocol. In the
case of the gorget, due to the variable thickness of the
corrosion, thinner corrosion areas were cleaned first,
which softened the thicker areas and allowed their later
removal using a scalpel.
Equipment
A Jobin Yvon Horiba T640000 Raman spectrometer
equipped with a microscope (50× magnification) was
used to examine the helmet and gorget. Spectra were
recorded in the spectral range of 100–1500 cm−1 at
0.1 mW using a 633 nm laser, with four accumulations
of 30 s each. The data were collected using Spectragryph
software.
A Minolta CM-508D spectrophotometer was used on the
iron coupons. The setup was as follows: specular compo-
nent excluded (SCE), illuminant D65, d/8° geometry,
10° observer, window size 8 mm, CIELab colour space.
ΔE was calculated using the standard colour variation
formula in CIELab:
SUSTAINABILITY IN PRACTICE
where L*1, a*1 and b*1 are the coordinates in the colouri-
metric space of the first measurement, and L*2, a*2, b*2
those of the second measurement. For each analysed
area, measurements were performed in triplicate.
Optical microscopy images were acquired using a Leica
Digital microscope system (DMS1000) with Leica Appli-
cation Suite software.
A double-beam atomic absorption spectrometer
(iCE 3300, Thermo Fisher) equipped with an acety-
lene-air flame was used to determine the quantity of iron
ions present after treatment. The gels were dissolved in 10
mL of 70% v/v HNO3 and diluted with deionised water to
100 mL. The solutions were not filtered, in order to also
allow a determination of the amount of corrosion that
could be mechanically scraped from the surface during
gel removal. The analyses were performed in triplicate.
Results and discussion
Gelling agent selection
Based on visual observations, DFO-agar hot gel (B)
and DFO-gellan gel prepared at room temperature (D)
showed the best performances in terms of corrosion
removal (Figure 2a, 2b). The DFO-gellan hot gel (E)
achieved mild cleaning following the same protocol
(Figure 2c). The performances of the DFO-xanthan gel
prepared and applied at room temperature (A) and the
rigid DFO-agar gel (C) were poor (Figure 2d, 2e).
The L*a*b* coordinates of the iron substrates before and
after cleaning confirmed the visual observations. After
cleaning with DFO-loaded hot agar (B), room-temper-
ature gellan (D) and to a lesser extent hot gellan (E), the
surface colour became brighter (higher values of L*) and
the hue became blue-green (higher values of a* and b*).
This can be attributed to the removal of the red-orangish
rust compounds. By contrast, few visual modifications
were seen on the samples treated with DFO-amended gels
based on xanthan gum (A) or rigid agar (C). After xanthan
gum treatment, a thin layer of gel remained that could not
be removed by swab rinsing. For the rigid DFO-agar gel
(C), the lack of visible results was due to the failure of the
agar to adhere to or form a close contact with the metal
surface (Guilminot et al. 2019). Due to its good perfor-
mance further tests were carried out using 3% w/v agar gel
amended with DFO and applied when still hot, at ~90°C
(B). Despite its good cleaning potential, DFO-gellan gum
at room temperature was not further tested because its
EXPLOITING BIOLOGICALLY SYNTHETIZED CHELATORS IN CONSERVATION: GEL-BASED BIO-CLEANING OF CORRODED IRON HERITAGE OBJECTS 29

viscous texture implied the need for a thorough rinsing
after removal, especially when applied to carvings.
Evaluation of the application parameters
Tests with the corroded iron samples immersed in
DFO at concentrations of 0, 3·10−4, 3·10−3, 3·10−2 and
6·10 −2 M were performed to better understand the
chelating kinetics of DFO on iron corroded substrates.
The pH of the different DFO solutions was 7.51, 7.68,
7.16, 6.79 and 6.65, respectively. The atomic absorption
spectrometry (AAS) analysis showed that DFO was
effective in the complexation of iron at concentrations
starting from 3·10−2 M (Figure 3a). Some iron ions were
detected in the solution with no siderophore, attributable
to a partial dissolution of the powdery corrosion layer.
After 5 h of immersion, the quantity of iron detected
in solution reached a plateau, indicating that all DFO
molecules had complexed with a ferric ion molecule on
the basis of a 1:1 molar reaction. At a concentration of
6·10−2 M, the best-performing DFO solution was the 3%
w/v hot agar gel (B). The decrease in the reaction rate
after 1 h of treatment (Figure 3b) can be explained by
the drying of the gel matrix, which made it more rigid,
thus hindering interaction of the iron ions with the
chelator (Zaitoun and Lin 1997) as well as contact with
the object’s surface. AAS measurements showed that the
total iron concentration was higher when the formulation
was applied 6× 10 min rather than as a single 60 min
application. According to this result, frequent treatment
reiteration and gel replacement provide a more efficient
cleaning action (Table 3). This finding was consistent
with the decrease in the complexation reaction over
time, as the first 10 min of treatment yielded the highest
complexation rates (Figure 3a).

Figure 2. Iron samples treated for 10 min with

6·10−2 M DFO-amended gels: (a) hot (~90°C)
3% w/v agar gel (B); (b) gellan gum at room
temperature (D); (c) gellan gum at 90°C (E);
(d) rigid agar gel (C); (e) xanthan gum (A).
(f) L* (bright/dark) and colour coordinates a*
(red/green) and b* (yellow/blue) coordinates
of the iron coupons before (circle) and after
(triangles) gel application; the standard errors
are also shown (A-dark blue, B-yellow, C-grey,
  D-light blue, E-orange). Scale bar: 5 mm


Figure 3. (a) Quantity of iron ions (mg/L) measured in solution at different times after the immersion of the corroded iron samples in DFO at
concentrations of 0 (light blue), 3·10−4 (red), 3·10−3 (grey) 3·10−2 (yellow), 6·10−2 (dark blue) M. (b) Quantity of iron ions (mg/L) measured in the gel
after the application of 6·10−2 M DFO-amended gel to the corroded iron coupons for 0 min, 10 min, 30 min, 1 h, 5 h and 24 h
30  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND SUSTAINABILITY IN PRACTICE

After a single 60 min application of 3% w/v agar gel
amended with 6·10−2 M DFO, weathering pits were
still visible whereas a more homogeneous surface was
obtained when the same gel was applied for 6× 10 min.
This was confirmed by colourimetric measurements, in
which multiple treatment reiteration resulted in a higher
colour variation than achieved with the same formulation
applied as continuous treatment (Table 3).
The complexation reaction caused the uncoloured
gel to turn vivid red-orange (Figure 4a). This feature
allows the operator to monitor and assess the cleaning
action. However, no direct correlation could be drawn
between the quantity of extracted iron and the visual
appearance of the gel during treatment. Indeed, the
hues of the agar gel amended with 3·10−2 M and 6·10−2
M DFO were similar despite the greater complexation
action of the higher concentration, as determined by
AAS (Figure 4b).
The results obtained with 3% w/v agar gel amended with
6∙10−2 M Na2EDTA, also applied to the iron corroded
samples for 6× 10 min, were similar to those obtained
with DFO-amended 3% w/v agar gel in terms of the

Table 3. Summary of the colour variation of the treated samples before and after cleaning (ΔE), the amount of iron extracted using 3% w/v agar
gels amended with DFO or EDTA at 6·10−2 M, and micrographs of the samples’ surfaces after the intervention

Extracted [Fe] mg/L

Mean ΔE of triplicates Optical microscope picture (0.75×)
per g of gel
Untreated sample n/a n/a

6·10−2 M - DFO-amended gel; 17.76 ± 3.43 19.26 ± 0.78

1× 60 min

6·10−2 M -DFO-amended gel; 21.22 ± 0.68 37.86 ± 6.68

6× 10 min

6·10−2 M EDTA-amended gel; 16.15 ± 2.97 41.41 ± 2.57

6× 10 min
EXPLOITING BIOLOGICALLY SYNTHETIZED CHELATORS IN CONSERVATION: GEL-BASED BIO-CLEANING OF CORRODED IRON HERITAGE OBJECTS 31

Figure 4. (a) Different concentrations of DFO-amended

3% w/v agar gels applied to the corroded iron
coupons for 10 min. (b) Graphical representation of
ΔE and the extracted iron concentration before and
 after treatment with DFO-amended 3% w/v agar gels

visual appearance of the coupons after cleaning and iron
uptake. However, in the EDTA-amended gel the colour
variation before and after treatment was weaker (Table 3).
Treatment outcome in the case studies
gorget and helmet had been buried. Typical iron indoor
corrosion compounds, such as lepidocrocite and goethite,
were still found in areas after treatment with either DFO-
or EDTA-amended 3% w/v agar gels, but the proportion
in the former was smaller (Criado et al. 2015).

Visual observations of the religious artefacts (calyx AAS of the gels was performed to evaluate the amount
and candle holder) indicated efficient cleaning with of iron extracted using the different formulations.
DFO-amended 3% w/v agar gel (Figure 5a, 5b). The
removal of the corrosion products revealed the under-
lying metal and the objects’ details. On the gorget and
helmet, the gel was less effective in the removal of the
sediment layer but a controlled cleaning was nonetheless
achieved (Figure 5c, 5d, green rectangles). EDTA treat-
ment, however, was aggressive and both the cleaning
process and the achievement of the desired degree of
cleaning were difficult (Figure 5c, 5d, red rectangles). In
both armour pieces, the presence of sediments implied
the presence of calcium-based compounds. Indeed,
unlike EDTA, which readily binds iron and calcium
(logβFe3+-EDTA = 25 versus logβCa2+-EDTA = 10.9) (Rapti et al.
2021), DFO is specific for iron and its affinity for calcium
ions is poor (logβFe3+-DFO = 30.4 versus logβCa2+-DFO ≤ 3.03)
(Farkas et al. 1999). Hence, the use of a DFO-amended
gel resulted in an appropriate surface appearance from
a conservator’s perspective, as the heterogeneous corro-
sion layers were preserved, whereas the use of Na2EDTA
resulted in the removal of the sediment layer, thus
revealing the metallic surface.

Post-treatment Raman analyses confirmed this finding

and detected calcium-based compounds (e.g. CaSO4,
CaCO3) on the zones treated with DFO but not with
EDTA (Figure 6) (Antunes et al. 2014). The calci-
um-based compounds derived from the soil in which the
Figure 5. Photographs of the treated zones of (a) calyx, (b) candle
holder, (c) gorget and (d) helmet before (left) and after (right) cleaning.
Red-delimited zones were treated with EDTA-amended agar gel, green-
delimited zones with DFO-amended agar gel, and blue-delimited zones
with pure water agar gel
32  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
The spectra showed that iron extraction using the
DFO-amended gel was hindered by the presence of an
upper sediment layer of calcium, especially in the case
of the gorget (Table 4). This specific affinity of DFO
for iron supports the use our newly developed DFO
gel formulation as a suitable and reliable agent for the
cleaning of historical iron-based indoor objects. When
the corrosion layer is more complex, such as when it
includes sediments, a preliminary mechanical cleaning
or renewal of the application of DFO-amended gel may
be effective. Although less sustainable, EDTA offers
the benefit of tackling sediments as well as corrosion
products in one step. The choice of DFO versus EDTA
thus depends on the balance between the ease of use
and sustainability.
Table 4. Quantity (mg/L) of iron ions detected in the gels after 20 min
of treatment of the Dobrée Museum objects
Gorget Helmet
DFO 0.16 5.45
EDTA 8.73 9.95
Water-based/plain gels Below limit of detection 0.19
Conclusion
This study demonstrated the potential of a sustainable
alternative to traditional complexing agents for use in
metal conservation, to avoid the health and environ-
mental concerns associated with, for example, the use
of EDTA. Cleaning gels amended with the siderophore
DFO allowed the removal of iron corrosion from natu-
rally altered samples with a performance similar to that
of Na2EDTA. Moreover, the use of DFO at neutral pH
avoids the need for post-treatment rinsing, in contrast to
EDTA solutions, which have an acidic pH. Our innovative
SUSTAINABILITY IN PRACTICE
Figure 6. Raman spectra (633 nm, 0.1 mW,
4 × 30 s, 50×) of the treated objects. The main
Raman signals are reported for each spectrum
displayed: (a) goethite, (b) lepidocrocite,
 (c) anhydrite and (d) calcite
formulation, made from renewable sources, is versatile
in its applications and does not require specific storage
conditions. These features should facilitate its wide
adoption by conservators. Optimal cleaning with the
DFO-amended agar gel was achieved when it was applied
hot, at a concentration not lower than 3∙10−2 M and with
frequent reiteration of the treatment, which also allows
better control of the treatment by the operator.
It is worth mentioning that the application parameters
and protocol will depend on the nature of the objects to
be cleaned, therefore our results should be interpreted as
general guidelines. DFO-amended agar gel may be more
effective when applied to objects with slight corrosion,
such as indoor historical artefacts, rather than archae-
ological items heavily corroded and with the potential
presence of residual sediments. Nonetheless, as an
eco-friendly, water-soluble, agar-based cleaning agent,
DFO is likely to be suitable for a broad range of objects,
with the potential for widespread adoption by conserva-
tors. Further research will be carried out to optimise the
application protocol for different degradation features.
Environmental and economic aspects should also be
considered, from the production of the DFO-agar agent
to its final use (time of application, reiteration, etc.), with
comparisons to Na2EDTA.
Acknowledgements
This research was funded by the Swiss National Science
Foundation (SNSF), grant number 205121_188755,
HELIX (Investigating metal bioremediation for the pres-
ervation of historical metal artworks) project 2020–2024.
The authors would like to acknowledge Jean-Yves
Mevellec from Institut des Matériaux de Nantes and Nath-
EXPLOITING BIOLOGICALLY SYNTHETIZED CHELATORS IN CONSERVATION: GEL-BASED BIO-CLEANING OF CORRODED IRON HERITAGE OBJECTS
alie Guichard from the laboratory Chimie et Interdisci-
plinarité, Synthèse, Analyse, Modélisation (CEISAM)
for their contribution to the Raman spectroscopy and
AAS analyses. We are grateful to Michel Chaillou from
Nantes Diocese for the provision of objects.
References
Albelda-Berenguer, M., M. Monachon, and E. Joseph.
2019. Siderophores: From natural roles to potential
applications. In Advances in applied microbiology, eds. G.
Gadd and S. Sariaslani, 1st ed., vol. 106, ch. 5. Cambridge:
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Carvalho. 2014. Characterization of gypsum and anhy-
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Authors
Edith Joseph is an assistant professor at both the
University of Neuchâtel and the Haute Ecole Arc Conser-
vation-restauration. She holds a PhD in environmental
and heritage chemistry from the University of Bologna,
Italy. Her main research activities are the application
34  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND SUSTAINABILITY IN PRACTICE

of green chemistry for the preservation of artistic and

archaeological objects. The characterisation of hetero-
geneous matrixes and the interaction between organic
substances and inorganic compounds, in particular
microorganisms and metals, are some of her research
interests. She has published around 60 papers on analyt-
ical chemistry and conservation in international journals
and books.

Luana Cuvillier and Arianna Passaretti are PhD

students at Haute Ecole Arc Conservation-restauration,
University of Neuchâtel, Switzerland, working on the
HELIX project.

Elodie Guilminot is a senior conservation scientist at

Arc’Antique, Nantes, France.

Aymeric Raimon and Virginie Dupuy are respectively

conservator and curator at Grand Patrimoine Loire
Atlantique (GPLA) in Nantes, France.

Microbial Stabilization of Archaeological Iron Objects
Sarah James
Laboratory of Technologies for Heritage Materials, University of Neuchâtel
Neuchâtel, Switzerland
sarah.james@unine.ch
Mathilde Monachon
Laboratory of Technologies for Heritage Materials, University of Neuchâtel
Neuchâtel, Switzerland
mathilde.monachon@unine.ch
Sathiyanarayanan Ganesan
Laboratory of Technologies for Heritage Materials, University of Neuchâtel
Neuchâtel, Switzerland
sathiyanarayanan.ganesan@unine.ch
Abstract
Chlorides and sulfides in the archaeological environment react
with iron ions to produce corrosion products such as akaganeite,
goethite, and iron sulfates. Traditional conservation efforts
include chemical and mechanical corrosion removal together
with climate control. The primary chemical treatments for
archaeological iron generally consist of either alkaline baths
for desalination or the application of complexing agents, such
as tannic acid, to transform the corrosion products. However,
green treatments are emerging in the heritage field, including
Introduction
The stability of an archaeological iron object depends
on the specific environment in which it was found and
subsequently stored post-excavation (Groysman 2010).
Both pre- and post-excavation, the object may be exposed
to environmental stresses, such as freeze-thaw cycles
and chemical contamination. The resulting corrosion
crust will differ accordingly with respect to its compo-
sition, thickness, and reactivity (Figure 1). For instance,
depending on pH, burial environments can produce
chloride-containing compounds such as akaganeite
β-ferric oxyhydroxide or combinations of different iron
Young Conservation Professional
Edith Joseph*
Laboratory of Technologies for Heritage Materials, University of Neuchâtel
Haute École Arc Conservation-restauration, HES-SO University of Applied
Sciences and Arts Western Switzerland
Neuchâtel, Switzerland
edith.joseph@he-arc.ch
*Author for correspondence
biomineralization and iron uptake by microorganisms to
remove or stabilize iron corrosion products. In this study, the
iron reduction and dechlorination properties of Pseudomonas
putida mt-2 (KT2440) were examined.
Keywords
archaeology, iron corrosion, green conservation,
biomineralization, iron uptake
oxides (Cornell and Schwertmann 2003, Selwyn 2004).
For objects recovered from freshwater or seawater, the
presence of iron sulfides reflects exposure to sulfur-re-
ducing bacteria (Rémazeilles et al. 2010).
The active corrosion and deterioration of archaeological
iron are primarily caused by contamination with anions
(Cl−, S2−) and the presence of oxygen and moisture, which
together support electrochemical reactions (Thickett
2012; Table 1). As the corrosion products accumulate,
they may cause delamination of the corrosion layers
Figure 1. Formation of iron
 corrosion crust
 36  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND SUSTAINABILITY IN PRACTICE

Table 1. Common chemical equations for iron according to the surrounding environment: aerated soil, acidic soil (pH < 4), with the presence
of chlorides or sulfur-reducing bacteria (SRB). (a) Watkinson 1983; (b) Watkinson 1983, Scott and Eggert 2016; (c) Scott and Eggert 2016; (d)
Groysman 2010

Aerated a Acidic b Chlorides c SRB d

Table 2. Microbial mechanisms and their effect on iron-containing heritage materials

Microbial mechanisms Microorganisms Substrate References

Iron phosphating Rhodococcus sp. C125; Mild steel (industrial process) Volkland et al. 2000a; Volkland et al. 2000b;
Biomineralization

Geobacter sulfurreducens; Volkland et al. 2001; Cote et al. 2015

Pseudomonas putida mt-2

Iron reduction Desulfitobacterium hafniense; Corroded iron (akaganeite, iron Comensoli et al. 2017; Kooli et al. 2018;
Shewanella loihica oxides) Kooli et al. 2019

Iron complexation Siderophore-producing Wood; paper (iron oxides) Rapti et al. 2021
Uptake

bacteria: Pseudomonas sp.

Sulfur oxidation Thiobacillus denitrificans Wood (iron sulfides) Monachon et al. 2020

(Thickett 2012). The increased acidification results in
a loss of mechanical strength, especially in iron-wood
composite objects (Fors et al. 2012).
The treatment of archaeological iron mostly relies on
desalination methods developed in the 1970s (Watkinson
2010). These methods include alkaline baths and
complexing agents (Scott and Eggert 2016). Chemical
treatments have proven to be relatively effective, but
determining the treatment endpoint can be difficult,
thus risking damage to the objects. Accordingly, there is
growing interest in less toxic methods, particularly green
treatments, for long-term stabilization. For example, in a
biologically based approach natural microbial processes
are exploited to convert the corrosion layer into an inert
biomineralized layer or to remove undesired compounds
(iron uptake), as summarized in Table 2. In this study,
the iron reduction and dechlorination properties of
Pseudomonas putida mt-2 (KT2440) were examined.
was synthesized according to Cornell and Schwertmann
(2003). The ground archaeological mixture consisted of
archaeological iron pieces ground with a mortar into a
fine powder. Pyrite was obtained from a geological spec-
imen (Pierre qui Roule, Switzerland) and was ground and
then washed in HCl− acetone before use.
Bacterial treatment
Pseudomonas putida mt-2 (PPmt2, DSM 6125) was
selected for the biological treatment as it was previously
shown to produce a cohesive iron-phosphate layer on
mild steel (Volkland et al. 2000a; Table 2)underwent
a surface reaction leading to the formation of a corro-
sion-inhibiting vivianite layer [Fe3(PO4.
A modified nutrient broth (NBS; peptone 15 g/L, yeast
5 g/L, D±glucose1 g/L) was used to prepare thio1 medium
(thio1; NBS with sodium thioglycolate 250 mg/L)

Materials and methods

Iron sources
Four iron sources were tested in this study: iron powder,
akaganeite, ground archaeological mixture (composed
of iron, iron oxyhydroxides, and traces of quartz from
the soil), and pyrite. The iron powder was sourced from Figure 2. Summary of the design of the biomineralization experiment,
Carl Roth Chemicals (≥ 99.5% p.a., powder). Akaganeite created using biorender.com
MICROBIAL STABILIZATION OF ARCHAEOLOGICAL IRON OBJECTS
according to James and Joseph (2021sulphur species).
MM9 medium was modified from Volkland et al. (2000a)
by the addition of 200 mL of salt solution (NH4NO35 g/L,
NaCl 2.5 g/L, Na2HPO464 g/L, KH2PO415 g/L) to 20 mL
of glucose (20% w/v), 2 mL MgSO4 (1 M), 0.1 mL
Ca(NO3)2 (1 M).
PPmt2 pre-cultures were grown in NBS medium under
180 rpm agitation at 28°C–30°C for 24 h with a bottle
volume ratio of 1:2. The bacterial cells were harvested and
washed via centrifugation (5000 rpm, 15 min), including
two washes with NBS followed by one with either thio1
or MM9 medium.
For each iron source, PPmt2 was inoculated in triplicate
in thio1 or MM9 media. Two abiotic controls were also
included. Growth was monitored from photographs taken
at 1-week intervals for a duration of 6 weeks. The bacteria
were cultured without agitation, to allow for different
application modes (solutions, gels) in future practice.
Results and discussion
In thio1 and MM9 media, there was no bacterial conver-
sion of pyrite and only a partial conversion of akaganeite
(data not shown). These results might be explained by the
Figure 3. Archaeological iron powder treated with Pseudomonas putida mt-2 in the presence of sodium thioglycolate (250 mg/L) as an oxygen
scavenger: (A) day 0 and (B) after a 6-week incubation at 30°C under stationary conditions. The precipitated black particulate material was identified
as a combination of vivianite, quartz, and magnetite
37
fact that some corrosion products are less amenable to
conversion than others due to their particular arrangement
of atoms and their electron charges. However, a conversion
of iron powder and archaeological mixture was observed
(Figure 3). The effective conversion of iron powder over
other oxidized iron species suggests its use as an additive
to boost less favorable reactions. For example, iron powder
could be added to initiate a more uniform phosphating
layer. The conversion of the archaeological mixture,
while significant, cannot be fully attributed to PPmt2 as
the mixture was not sterilized before use and perhaps
because the burial biome was still present. However, a
reactivation of the microorganisms present in the burial
environment during stabilization treatments can also result
in the formation of more stable compounds, resulting in
an object’s preservation (Orr et al. 2021).
An advantage of PPmt2 is that it produces siderophores,
which enhance iron uptake. Thus, PPmt2 treatment
could allow for the removal of thick iron-containing
concretions, while potentially increasing the availability
of iron for conversion (biomineralization). Iron uptake
has been successfully employed in the removal of harmful
iron species from waterlogged wood (Monachon et al.
38  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
2020). Promising iron extraction rates of up to 75% were
obtained with a commercial siderophore, deferoxamine.
Isolation and identification of the natural biome have thus
been initiated by our group to determine the impact of
these microorganisms on the conversion of the treated
iron compounds and their potential relationship with
exogenously added microbes (whole biomes or isolated
strains). In addition, the use of Methylophilus methy-
lotrophus is currently being assessed as an alternative
treatment option, as suggested by Orr et al. (2021).
Conclusion/future prospects
The use of microbial processes to treat corrosion on
archaeological iron requires further studies before this
approach can be applied to recovered or stored objects.
The results will allow versatile methods to be proposed to
end users. For composite objects (i.e., iron parts of water-
logged wood objects), a sequential protocol that includes
iron extraction from the wood substrate and stabilization
of the corroded iron parts may be effective. This would
avoid a lack of compatibility between the microorganisms
used in the treatment of different materials or between
the microorganisms and the object itself.
Acknowledgments
This work was supported by the Swiss National Science
Foundation (grants no. PP00P2_163653/1, 2016–2020,
and PP00P2_190081, 2020–2023).
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Authors
Sarah James has a master’s degree in conservation
science from the University of Cardiff, UK. She is
currently a PhD student at the University of Neuchâtel,
where she investigates biomineralization processes to
stabilize archaeological iron artifacts.

Mathilde Monachon is currently a postdoctoral

researcher at the University of Neuchâtel, where she
studies green extraction methods for iron and sulfur
species to preserve waterlogged archaeological wood.
Her main research area is analytical chemistry with a
focus on conservation science.

Sathiyanarayanan Ganesan is currently a senior

postdoctoral researcher at the University of Neuchâtel
working on green extraction methods for iron and sulfur
species to preserve waterlogged archaeological wood.
His main research area is microbiology with a focus on
conservation science.

Edith Joseph is an assistant professor at the University

of Neuchâtel and the Haute École ARC Conservation-res-
tauration. She has a PhD in chemistry from the University
of Bologna, Italy. Her main research activities are the
application of green chemistry for the preservation of
artistic and archaeological objects.
Deterioration Tests Using a Simulated Tumulus to
Evaluate In Situ Preservation of Metal Artifacts in a Stone
Chamber
Akinobu Yanagida* Huarong Xie Nobumitsu Takatori Shuichi Hokoi
Nara National Research Institute for School of Architecture, Southeast Department of Architecture School of Architecture, Southeast
Cultural Properties University and Architectural Engineering, University
Nara City, Japan Nanjing, China Graduate School of Engineering, Nanjing, China
yanagida8682@gmail.com xie901012@gmail.com Kyoto University hokoi@maia.eonet.ne.jp
Kyoto, Japan
Soichiro Wakiya Daisuke Ogura takatori.nobumitsu.7r@kyoto-u.ac.jp Yohsei Kohdzuma
Nara National Research Institute for Department of Architecture Nara National Research Institute for
Cultural Properties and Architectural Engineering, Hiroyuki Yasui Cultural Properties
Nara City, Japan Graduate School of Engineering, Department of Architecture Nara City, Japan
wakiya-s8s@nich.go.jp Kyoto University and Architectural Engineering, kozuma-y38@nich.go.jp
Kyoto, Japan Graduate School of Engineering, *Author for correspondence
ogurad@archi.kyoto-u.ac.jp Kyoto University
Kyoto, Japan
khx.hiro.yasui.225@gmail.com

Abstract
To verify the possibility of in situ preservation of metal artifacts
inside the stone chamber of a tumulus, the corrosion behavior
of iron and bronze artifacts was studied by conducting a
deterioration test in a simulated tumulus. The corrosion rate
of the suspended carbon steel samples in the stone chamber
was extremely low, at one-tenth that of samples buried in
soil. Malachite formed on the bronze samples because of an
increasing CO2 concentration in the stone chamber after the
emergence of a tin compound corrosion layer. These results were
congruent with genuine artifact corrosion behavior and revealed
the relationship between the corrosion process and the buried
environment within the stone chamber.
Keywords
iron artifact, bronze artifact, tumulus, in situ preservation,
atmospheric corrosion, soil corrosion, buried environment

Introduction
There are approximately 200,000 tumuli1 in Japan with
soil mounds and stone chambers (Figure 1). In most
of the tumuli, significant amounts of iron and bronze
artifacts are buried in the stone chamber (Otsuka 2012).
In a tumulus, the position of artifacts within the stone
chamber relates to their academic value (Tateishi 2020).
Removing significant amounts of artifacts for archeo-
logical investigation would make their conservation in
a storage facility expensive and time-consuming. Conse-
quently, there is a need to preserve the grave contents in
situ. For this purpose, a quantitative investigation of the
relationship between the physical environment of the
artifacts and their corrosion is essential. Furthermore,
by understanding this relationship in the stone chamber,
the artifacts can be actively preserved by adjusting the
environment, such as placing soil on the surface of the
tumulus. This method has benefits in terms of lower
energy consumption and sustainability compared to
controlling the environment using an air conditioner.
Because of the difficulty of investigating the physical
environment and conducting corrosion monitoring of
metal artifacts over time in a genuine stone chamber,
experimental methods need to be adopted.
This study aimed to investigate the initial corrosion of
iron and bronze artifacts in the stone chambers of tumuli
typically found in Japan. A simulated tumulus was used
and environmental investigations (Xie et al. 2020) and
corrosion tests conducted to discover the effect of buried
environments on the corrosion of these metal artifacts.
Experimental methods
Structure of the simulated tumulus
The simulated tumulus was located in a hilly area at
the Katsura Campus of Kyoto University (Figure 1) and
consisted of an antechamber and a stone chamber. The
chamber was 50 × 50 × 100 cm3 in size and its floor was
DETERIORATION TESTS USING A SIMULATED TUMULUS TO EVALUATE IN SITU PRESERVATION OF METAL ARTIFACTS IN A STONE CHAMBER
Table 1. Environmental monitoring of simulated tumulus
Monitoring variables
Stone Temperature
chamber
Relative humidity
Water potential
Oxygen concentration
Carbon dioxide concentration
Outdoor Air temperature, humidity, air pressure, precipitation,
weather solar radiation, wind direction, and speed
1.5 m above the ground. The sides and ceiling of the
chamber were lined with 2 cm-thick granite slabs, while
the floor consisted of earth. The environmental investi-
gations and corrosion tests were conducted in the stone
chamber, whereas the dataloggers for the environmental
measurements and corrosion sensors were placed in the
antechamber (Figure 1a). The inside of the stone chamber
was observed through an acrylic window that separated
it from the antechamber. In the environmental investiga-
tions, in addition to meteorological observations of the
model tumulus, the temperature, water potential,2 and
O2 and CO2 concentrations in the mound were meas-
ured. Inside the stone chamber, the temperature, relative
humidity (RH), and O2 and CO2 concentrations in the
atmosphere were measured according to a previously
described method (Table 1; Xie et al. 2020).
Deterioration test
Samples
Carbon steel (SS400) and two types of bronze—namely,
low-tin (C5191, Sn: 6.69 wt%) and high-tin (CAC502A,
Sn: 9.91 wt%) bronze—were cut to size (50 × 50 × 5 mm3),
polished (final polishing: #400 emery paper), washed in
distilled water, and degreased in acetone using an ultra-
sonic cleaning machine. These samples were installed
on February 14, 2014. One set of samples was suspended
in the stone chamber, and the other was buried in the
ground (Figure 1b-2, 1b-3). Table 3 describes the appa-
ratus.
Analytical methods
The samples were observed from the antechamber
approximately every three months and removed at
regular intervals for analysis. They were observed using
optical microscopy (OM) and scanning electron micros-
copy (SEM). The corrosion products that formed on the
samples were analyzed using energy-dispersive X-ray
41
Position of monitoring sensors Measuring instruments
Ceiling, floor, and air T-type thermocouple
Temperature and relative-humidity sensor
Air
(Onset HOBO U23 Pro v2)
Both sides of the floor soil Dielectric water-potential sensor (METER MPS-2)
Air and soil Soil O2 sensor (EMJ MIJ-03)
Air Carbon dioxide sensor (BARON BEC-CO2SA-A40)
Weather station
(DAVIS)
spectroscopy (EDX) coupled with SEM, micro-X-ray
diffraction (µ-XRD), and micro-Raman (µ-Raman)
spectroscopy. The samples installed for approximately
three years were mounted in epoxy resin, cut, polished—
the final polishing being with a 1 µm polycrystalline
diamond paste—under ethanol, and subjected to the
same analysis.
Calculation of corrosion rate
Table 4 shows the samples used to calculate the corrosion
rate. To remove the corrosion products, carbon steel
samples were soaked in 6 mol/L of hydrochloric acid
containing hexamethylenetetramine (0.35 wt%) for 10 min
(JIS Z 2371; Japanese Standards Association 2015). The
bronze samples were soaked in 6 mol/L of hydrochloric
acid for 3 min. The weight loss in the samples was meas-
ured after washing in distilled water and degreasing in
acetone using an ultrasonic cleaning machine. The weight
loss was determined by subtracting the control weight
loss from the sample weight loss. The corrosion rate was
calculated using the following equation:
(1)

In Equation (1), Rcorr, ΔW, S, Δt, and ρ indicate corrosion
rate (mm/y), weight loss (g), sample area (mm2), and
experimental period (year).
Table 2. Date of stone chamber opening and sample extraction
Opening the stone
Date Sample extraction
chamber
1/9/2014  Sample installation
9/30/2014  
11/24/2015  , Sample installation
11/27/2016  , Sample installation
11/27/2017  
10/10/2018  
42  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND SUSTAINABILITY IN PRACTICE

Table 3. The samples for corrosion rate measurement in the stone chamber and underground increased in
Apparatus Model Manufacturing company winter and decreased in summer (Figure 2b), in contrast
Ultrasonic cleaning US CLEANER AS ONE Co., to the CO2 concentration, which reached approximately
machine 10% in summer. This behavior was attributed to the accel-
Optical microscope Z16 APO A Leica Microsystems Co. Ltd. eration of aerobic microbial respiration in summer owing
Scanning electron JSM-IT200 JEOL Co. Ltd. to the increased temperature. The water potential of the
microscope
soil underground remained high throughout the year.
Micro-X-ray Smart lab Rigaku Co. Ltd.
diffractometer
Micro-Raman LabRAM HR HORIBA Ltd.
spectroscope Evolution

Table 4. The samples for corrosion rate measurement

Installation Removal Experimental Sample

date date period (day) number
1/9/2014 9/30/2014 264 1
1/9/2014 11/24/2015 684 2
1/9/2014 11/27/2017 1418 1
1/9/2014 10/27/2016 1022 2
1/9/2014 10/10/2018 1735 2
11/24/2015 10/27/2016 338 1 Figure 2. Change in the environmental sensors: (a) surface temperature
11/24/2015 10/10/2018 1051 1 of the ceiling and floor; (b) O2 and CO2 concentrations; (c) water potential
10/27/2016 11/27/2017 396 1 in the ground and due to precipitation

Results and discussion Corrosion of carbon steel

Burial environment of the simulated tumulus
The RH in the stone chamber was maintained at 100%
throughout the experiments. The surface temperature at
the ceiling was higher than that at the floor in summer,
whereas in winter it was the opposite (Figure 2a), indi-
cating that condensation occurred near the floor in
summer and the ceiling in winter. The O2 concentration
Figure 3 shows photographs of each sample. On the
carbon steel, a dense rust film formed at the lower edge
of the suspended samples (Figure 4a), causing extensive
corrosion underneath. In contrast, porous rust formation
occurred over the entire surface of the buried samples.
SEM-EDX showed that the samples thinned locally due to
corrosion (indicated by the red ↑ in Figure 4b). Because
Si—attributed to soil particles—was detected in the upper

Figure 1. Illustration of the different

types of ancient tumuli and
schematic diagram of the simulated
tumulus: (a-1) tumulus shape; (a-2)
type of stone chamber; (b-1) the
geometry of the simulated tumulus;
(b-2) location of the metal samples;
 (b-3) setup of the corrosion sensors
DETERIORATION TESTS USING A SIMULATED TUMULUS TO EVALUATE IN SITU PRESERVATION OF METAL ARTIFACTS IN A STONE CHAMBER 43

section of the rust layer, the carbon steel presumably
corroded heavily when in contact with the soil particles.
Goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and
magnetite (Fe3O4) were detected by XRD on the rust on
both suspended and buried samples.
The corrosion rate in the 2–5-year-old suspended samples
was 0.0003–0.0024 mm/y but was slightly higher in the
1-year-old samples (Figure 5a). Because the corrosion rate
was calculated as an average for the entire sample, the
localized corrosion behavior is not presented. Therefore,
in the suspended samples, the actual corrosion rate at the
lower edge is possibly higher than that in Figure 5. In
contrast, the corrosion rate of the buried samples grad-
ually decreased: 0.025–0.038 mm/y after 1 year falling
to 0.015 mm/y after 5 years. The corrosion rate of the
buried samples was approximately 10 times higher than
that of the 4–5-year-old suspended samples.
Corrosion mechanism of iron artifacts
The corrosion rate in the atmosphere depends on the
wetting time and water film thickness on the surface
of the metal (Hœrlé et al. 2004). In the soil, corrosion

Figure 3. Photographs of the

removed samples from the
 simulated tumulus

Figure 4. OM and SEM-EDX

images of the carbon steel
samples: (a) suspended
samples; (b) buried samples.
OM images indicate the surface
corrosion conditions and SEM
images show a cross-section of
 the samples

Figure 5. Change in corrosion

rate: (a) carbon steel samples;
 (b) bronze samples
44  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
proceeds due to Fe2+ removal from the metal surface
and O2 supply from the soil to the metal (Neff et al.
2005). Based on previous studies, three factors cause
intense corrosion in the soil. First, the buried samples
remained wet because of the high water content of the
soil, whereas the wetting area and time on the suspended
samples changed depending on the season. Second, the
conductivity of the pore water in the soil was higher
than that of the water film on the suspended samples,
because the latter was due to condensation. Third, the
pore water on the surface of the samples resulted from
rainfall, stimulating the removal of Fe2+, whereas Fe2+
remained on the surfaces in the stone chamber.
Figure 6a shows a schematic of the corrosion mechanism
on the suspended samples. The water film was thin on
the sides of the samples and thick at the lower edge;
that is, water flowing along the sides accumulated at the
lower edge. In the initial stage of corrosion, dissolved
oxygen in the water film was consumed on both the
sides and lower edges of the samples. The supply of
dissolved oxygen in the water film at the lower edges of
the carbon steel gradually decreased compared to that
at the sides because of its slow diffusion (Figure 6a-I,
6a-II). Consequently, macrocell corrosion proceeded
because of the formation of an oxygen concentration cell
via the fixing of a cathode on the side of the sample and
an anode on the lower edge (Figure 6a-III). Moreover,
by increasing the concentration of Fe2+ via the corrosion
reaction in the water film at the lower edge, a rust film
Figure 6. Schematics of the corrosion mechanism of carbon steel: (a) suspended samples; (b) buried samples. DO = dissolved oxygen
SUSTAINABILITY IN PRACTICE
was formed due to the oxidation of Fe2+ to Fe3+ at the
gas-liquid interface (Figure 6a-IV).
For the buried samples (Figure 6b), thick water films
formed when in contact with large soil particles (He et
al. 2017) (Figure 6b-I). Consequently, localized thinning
presumably occurred in the thick water film in contact
with large soil particles via the fixing of an anode (Figure
6b-II, 6b-IV). Previous studies showed that the supply
of dissolved oxygen to the metal or removal of Fe2+ from
the metal through a rust layer controls the corrosion rate
in soil (Neff et al. 2005, He et al. 2017, Shibata 2019).
The corrosion rate on the buried samples presumably
decreased over time because the growth of the rust
layer suppressed the supply of dissolved oxygen and the
removal of Fe2+.
Corrosion of bronze samples
In the low-tin bronze sample, spots of green corrosion
products, identified using µ-XRD and µ-Raman spec-
troscopy as malachite (Cu2(CO3)(OH)2), were formed on
the dense black corrosion layer (DBCL) (Figure 7a-1).
The distribution of the DBCL—where O and Sn were
detected by EDX—was based on where the water
droplets flowed. Moreover, malachite was generated
at the DBCL cracks (Figure 7a-1). The DBCL was an
aggregate of minute particles, with a corrosion layer of
10–20 µm (Figure 7a-2). Because obvious spectra were
not detected in the DBCL using µ-XRD and µ-Raman
spectroscopy, this corrosion layer was presumably
DETERIORATION TESTS USING A SIMULATED TUMULUS TO EVALUATE IN SITU PRESERVATION OF METAL ARTIFACTS IN A STONE CHAMBER
amorphous. Previous research reported that a DBCL
can occur on the surface of bronze artifacts (Wang
et al. 1995) and that this corrosion layer consists of
amorphous tin oxide or tin hydroxide (Trentelman et
al. 1999, Chiavari et al. 2007). Therefore, the DBCL was
presumably tin oxide or tin hydroxide. The cross-sec-
tional images also indicated that there was substantial
thinning of the alloy under malachite (indicated by the
red △ in Figure 7a-2).
In Figure 7b-1, corrosion of the high-tin bronze sample
was more evident in the upper-left area and less evident
in the lower-right area of the image. The dendrite-shaped
alloy changed to black, and on it formed an acicular of
malachite. In the dendrite-shaped α phase, O and Sn were
detected, while the intensity of Cu decreased. Therefore,
the α phase corroded to leave oxide or tin hydroxide. In
contrast, even in the heavily corroded area, the eutectoid
of the (α+δ) phase showed high luminance in the SEM
image. The eutectoid of the (α+δ) phase does not corrode
easily compared to the α phase. In the cross-section of
the high-tin bronze sample, acicular malachite had also
formed on the DBCL, similar to the low-tin bronze
sample (Figure 7b-2). Furthermore, malachite growth
occurred during summer in both the low-tin and high-tin
bronze samples. Figure 5b shows that the corrosion rate
of the low-tin bronze sample in the stone chamber was
slightly higher than that of the high-tin bronze sample.
In the buried samples, the low-tin and high-tin bronze
samples showed corrosion behaviors similar to that in
the stone chamber. However, acicular malachite was not
observed in the buried samples.
45
Figure 7. OM and SEM images
of the suspended bronze
samples: (a-1) surface of the
low-tin bronze samples; (a-2)
cross-sections of low-tin bronze
samples; (b-1) surface of the
high-tin bronze samples; (a-2)
cross-sections of high-low
 bronze samples
Corrosion mechanism of bronze samples
Figure 8a shows a schematic of the corrosion on bronze
samples suspended in the stone chamber. In the low-tin
bronze sample, the corrosion of the alloy began with
the reduction reaction of dissolved oxygen due to the
formation of the water film (Figure 8a-I). Because of
the low solubility of the tin compound, it was deposited
on the surface of the alloy and became a DBCL. For
copper, cuprite occurs during atmospheric corrosion
(Graedel et al. 1987). In contrast, amorphous tin oxide
or tin hydroxide forms on bronze (Cilvia et al. 2007,
Souissi et al. 2007) and acicular malachite occur on the
tin compound layer (Figure 8a-II, 8a-III). The formation
of malachite is attributed to the reaction between cupric
and carbonate ions by the dissolving of atmospheric CO2
in the water film (Graedel et al. 1987). The concentration
of CO2 decreased to 3% in winter and increased to 10%
in summer in the stone chamber (Figure 3b). When
dependent only on the equilibrium of carbonate (Stumm
and Morgan 1996), the pH of the water film varied from
4.4–4.7, with a total carbon dioxide (Ct) content of
10−3 mol/L in winter and 10−2 mol/L in summer. Figure
9 shows the stable phase change from tenorite in winter
(Ct: 10−2 mol/L) to malachite in summer (Ct: 10−3 mol/L)
depending on the Ct concentration. That is, malachite
formed because of the increasing CO2 concentration in
the stone chamber. In addition, the water film on the
bronze sample decreased because the temperature of the
ceiling in the stone chamber changed, becoming higher
than that of the ground in summer. Acicular malachite
presumably formed because of an increase in the concen-
46  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Figure 8. Schematic of bronze corrosion mechanism in the stone chamber: (a) low-tin bronze sample; (b) high-tin bronze sample
tration of cupric ions (Figure 8a-III). This anode reaction
possibly occurred in a relatively large gap between the
tin compounds (Figure 8a-IV).
In the high-tin bronze sample, Cu was leached from the
center of the dendritic structure where Cu was highly
concentrated, thus increasing the Sn concentration on the
surface (Figure 8b-I). In this process, selective leaching
occurs because the α phase is an anode and the eutectoid
is a cathode. As corrosion proceeds, the α-phase grain
boundary is observed, and the DBCL gradually spreads
(Figure 8b-II). Furthermore, malachite growth was
Figure 9. Effects of Ct concentration on the formation of malachite and
tenorite. This figure shows the copper compound formed by the pH at
each Ct in the water film on the bronze samples
SUSTAINABILITY IN PRACTICE
attributed to an increase in the CO2 concentration in
the stone chamber, similar to the low-tin bronze sample
(Figure 8b-III).
Comparison with the condition of genuine artifacts
Figure 10a shows that the corrosion rate on genuine
iron artifacts buried in the soil was lower than that
of the buried samples. In a buried iron artifact, the
corrosion rate decreases due to the growing corrosion
layer suppressing the diffusion of dissolved oxygen and
Fe2+. In contrast, the corrosion rate of the suspended
samples in the simulated tumulus was identical to that
of the genuine artifacts in the stone chamber of the real
tumulus. This indicates that the corrosion rate in the
stone chamber was suppressed after the initial stages,
because an extremely dense corrosion film was formed.
Figure 10b shows a cuirass excavated from a tumulus,
which was heavily corroded by the soil. In contrast, the
part where the armor was exposed to the atmosphere
presumably corroded very slowly because its original
shape remained intact.
Figure 10c shows bronze artifacts with different Sn
concentrations. The high-tin bronze retained its surface
DETERIORATION TESTS USING A SIMULATED TUMULUS TO EVALUATE IN SITU PRESERVATION OF METAL ARTIFACTS IN A STONE CHAMBER
Figure 10. Comparison of the experimental results and genuine artifacts: (a) relationship between the corrosion depth and time in carbon steel samples
and iron artifacts (Yoshikawa et al. 2008, Yoshikawa et al. 2009, Mitsui et al. 2012, Mitsui 2015a, Mitsui 2015b). The corrosion rate of genuine artifacts
was calculated by dividing the corrosion thickness measured using X-ray computed tomography by the duration of burial; (b) the cuirass excavated
from tumulus; (c) the different Sn content of bronze artifacts
decoration due to protection by the DBCL, whereas the
low-tin bronze corroded heavily. Because the concen-
tration of Sn was 1.71 and 18.77 wt% in the low-tin and
high-tin bronze (Saito et al. 2016), respectively, the metal-
lographic structure of these was presumably the α phase
and eutectoid of the (α+δ) phase. This behavior shows
that the corrosion condition of the bronze samples in the
simulated tumulus corresponded to the bronze artifacts.
Conclusion
In this study, a deterioration test using carbon steel and
two types of bronze samples in a simulated tumulus
was combined with an environmental investigation to
evaluate the corrosion behavior in a stone chamber. The
corrosion rate of the iron artifacts in the stone chamber
was extremely low compared to that of buried iron arti-
facts. In bronze artifacts, the seasonal change in the CO2
concentration affected malachite formation. In addition,
the metallographic structure of bronze strongly affected
the corrosion behavior, bearing in mind that the high-tin
bronze sample was less corrosive. The simulated tumulus
results corresponded to the corrosion conditions of
genuine artifacts.
The study confirmed the initial corrosion behavior
of metal artifacts in a tumulus. In future work, in situ
preservation in a tumulus will be assessed by analyzing
the data from corrosion sensors placed in the simulated
tumulus.
Acknowledgments
This work was supported by a JSPS KAKENHI Grant-
in-Aid for Scientific Research B (Number 26289203) and
47
Scientific Research C (Number 21K00998). We would
like to thank Katsuhiko Aketa (Revive HIKO), Shinji
Yamamoto (Okumura Corporation), Nobuhiro Ichikawa
(Live Architects Office), Nippon Steel Technology, and
Madoka Keshi (Kyoto University).
Notes
1
One tumulus in Japan was constructed in the mid-3rd
century and remained in use until the end of the 7th
century. The size of the soil mound ranged from a few
meters up to 525 m.
2
The decrease and increase in water potential under
the same soil corresponded to a decrease and increase
in moisture in the soil.
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specializes in conservation science.

Materials list
SS400 is ordinary structural carbon steel made by
hot-rolling sheet steel to JIS G 3101 (JAS 2015).

C5191 is a JIS H 3110-standard phosphor bronze (JAS

2018). The samples were α monophase and contained
Cu: 93.32 wt% and Sn: 6.69 wt% according to SEM-EDX.

C502A is a JIS H 5120-standard cast phosphor bronze

(JAS 2015). The samples consisted of an α phase and a
eutectoid in the (α+δ) phase. The chemical composi-
tion of the sample was Cu: 93.32 wt% and Sn: 9.91 wt%
according to SEM-EDX.
 Young Conservation Professional

Development of a Sunflower-Oil-based Bio-lubricant for

Use in Gear Models at the ISEP Museum

Maria Gonçalves Bruno Campos Eduarda Vieira Patrícia R. Moreira*

School of Arts, Universidade
Católica Portuguesa
Porto, Portugal
mcazevedog@gmail.com
Research Centre for Science and
Technology of the Arts (CITAR) and
Centre for Biotechnology and Fine
Chemistry – Associate Laboratory
(CBQF), Universidade Católica
Portuguesa
Porto, Portugal
bchem7@gmail.com
School of Arts and Research Centre
for Science and Technology of the
Arts (CITAR), Universidade Católica
Portuguesa
Porto, Portugal
evieira@ucp.pt
School of Arts, Research Centre
for Science and Technology of
the Arts (CITAR), and Centre for
Biotechnology and Fine Chemistry
– Associate Laboratory (CBQF),
Universidade Católica Portuguesa
Porto, Portugal
prmoreira@ucp.pt
*Author for correspondence

Abstract
In this case study, we describe the development of an eco-
friendly, sunflower-oil-based bio-lubricant for use in the
conservation of exhibited metal gears. The bio-lubricant was
produced from two different sunflower oil bases. In addition to
the methodology used to develop the vegetable-oil lubricant,
we present the results of oxidation and UV resistance tests. In
the FTIR analyses, the bio-lubricant showed good resistance to
oxidation and good UV resistance.
Keywords
antioxidant, Fourier transform infrared (FTIR) spectroscopy,
lubricant, oxidation, sunflower oil, thickener, ultraviolet (UV)

Introduction
Although the importance of industrial and scientific
collections has long been recognized, the conservation
and restoration of scientific and technological objects are
still very much guided by traditional, not entirely effective
methods. Consequently, new approaches adapted to the
requirements of this type of heritage are needed. In this
case, the objects of study were a set of ten scientific-di-
dactic pieces belonging to the Schröder collection of the

Figure 1. The Schröder collection

DEVELOPMENT OF A SUNFLOWER-OIL-BASED BIO-LUBRICANT FOR USE IN GEAR MODELS AT THE ISEP MUSEUM
Museum of Instituto Superior de Engenharia do Porto
(ISEP) (Figure 1). The lubricating oil present in the gears
of the pieces had degraded and was no longer protective,
evidenced by its visible dripping onto undesired areas
of the pieces due to its fluidity. The lubricant had to be
replaced rather than simply removed, to prevent wear
between the gears and to allow their smooth functioning
during use. As this provided the opportunity to take a
“green” approach to conservation, a lubricant of vegeta-
ble-oil origin was developed in our laboratory.
Objective
Commercial lubricants are not biodegradable, since they
are made from mineral oils and other toxic components
that, when discarded, are environmentally damaging
(Woma et al. 2019). Since there are no publications
regarding the adaptation of bio-lubricants for use in
conservation and restoration, including for scientific
and industrial collections, we developed a bio-lubri-
cant from vegetable oil based on previous reports in
other research areas. Sunflower oil was selected due to
its desirable physical characteristics with respect to its
kinematic viscosity, density, and pour and cloud points at
temperatures below 0°C. It also has a high percentage of
unsaturated fatty acids, thus readily allowing the addition
of antioxidants to improve stability and of thickeners
to obtain the appropriate consistency (Karmakar et al.
2017). However, as the gears are exhibited and therefore
mostly static, the performance features of the lubricant
are not further considered herein.
Method
Two formulation bases were selected for the bio-lubri-
cant: a commercial virgin biological sunflower oil from
Naturefoods (purchased in the Portuguese supermarket
chain Celeiro) and a sunflower seed oil from Belianthus
annuus available from Sigma-Aldrich. The bio-lubricants
developed from these two sources were compared to
determine whether a low-cost bio-lubricant could be
developed from an easily available product. As a disad-
vantage of sunflower oil as a base for a lubricant is its poor
resistance to oxidation, three antioxidants were tested:
propyl gallate (PG), 4,4’-methylenebis(2,6-di-tert-butyl-
phenol) (MBP), and tert-butylhydroquinone (TBHQ)
(Merrill et al. 2008), all purchased from Sigma-Aldrich.
Purified beeswax (KahlWax 8105) was selected as the
thickener due to its good compatibility when added to
51
vegetable oils, its biodegradability, and the fact that its
concentration can be easily increased or decreased as
needed (Kreivaitis et al. 2015). For resource management
reasons, the compatibility tests were performed using the
commercial sunflower oil base. After the antioxidant had
been selected, it was added to the high-grade sunflower
oil together with the thickener, and the two bio-lubricants
were then compared.
The miscibility of the selected antioxidants was tested by
adding each one to the commercial sunflower oil base at
a final concentration of 5% (w/w), followed by thorough
mixing using a magnetic stirring and induction plate
first at room temperature and then gradually increasing
both the stirring rate and the temperature to 1000 rpm
and 100°C, respectively. The antioxidant with the best
compatibility with the sunflower oil base was selected.
Next, beeswax at final concentrations of 5%, 7.5%, 10%,
20%, and 30% (w/w) were tested in the commercial
sunflower oil containing the antioxidant.
The resistance to oxidation of the formulation was tested
using a continuous air injection system consisting of an
EHEIM air pump (model Air 400) run at maximum flow
(200 L/h for one air outlet) for 90 consecutive hours. The
test was conducted in the dark to avoid the influence
of light on the results. One hundred mL of sunflower
oil containing the selected antioxidant was added to a
250 mL borosilicate Duran glass bottle. A stainless steel
multiport connector cap with two tubes allowed the
entrance and exit of air from the system. All equipment
was sterilized before use and two Whatman HEPA-VENT
filters were placed in the air inlet and outlet.
To evaluate the commercial-oil-based lubricant’s resist-
ance to photooxidation, it was exposed to direct UV
light at a power of 15 W for 720 consecutive hours. The
lubricant was placed on a ~3 mm thick glass slide, and
light was delivered using an HQ Power device.
The chemical changes to the bio-lubricant that occurred
during the oxidation tests were analyzed by Fourier
transform infrared (FTIR) spectroscopy (Hamed and
Allam 2006), using a PerkinElmer Spectrum 100 FT-IT
instrument. Spectra were obtained between 4000 and
600 cm−1 from formulations with and without air expo-
sure and with and without UV exposure. FTIR was also
used to compare the qualities of the lubricants developed
from the commercial and high-grade oils.
52  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND SUSTAINABILITY IN PRACTICE

Results and discussion

Tests of the three antioxidants showed that optimal
results were obtained with TBHQ, as the solute dissolved
easily in the solvent, forming a homogeneous solution
that remained stable after heating to 100°C followed by
cooling to room temperature and then further storage.
By contrast, in the formulation containing PG, while
at ~100°C the solute was dissolved in the oil base,
after the mixture had cooled to room temperature
the solution became turbid, and 1 h later two distinct
phases, including a precipitate, had formed. Similarly,
while MBP completely dissolved in the oil base and the
mixture remained homogeneous after cooling to room
temperature, after 48 h a precipitate had formed. Thus,
the antioxidant TBHQ was selected for use in the bio-lu-
bricant (Table 1).

Table 1. Antioxidant test results of three antioxidants added to com-

mercial sunflower oil at a final concentration of 5%

Antioxidant During test During cooling After cooling

down to room down to room
temperature temperature
Figure 2. Air injection system used in the oxidation test
PG The solute The solution Two distinct
dissolved in the oil became cloudy phases, with
base, becoming a the solute
crystalline solution deposited at the
bottom
MBP Completely No changes After 48 h, it
dissolved; occurred was possible
crystalline to observe the
appearance formation of
crystals
TBHQ Homogeneous Stable Stable
crystalline solution

Beeswax was initially added to the formulation at a
concentration of 30% (w/w). After heating at 60°C–70°C
with stirring (1000 rpm), the beeswax had completely
melted and a homogeneous mixture was obtained.
However, after cooling, the mixture had a very high hard-
ness, with a texture that was too waxy for the consistency
required for lubricating the gears. Further tests using
the same procedure showed that the best results were
achieved with concentrations of 5%, 7.5%, and 10%, all of
which yielded a homogeneous lubricant with a viscosity
and fluidity appropriate for use with the gears.
During the oxidation tests (Figure 2), no visible changes
were recorded. In the FTIR analysis of the formulations
with and without air exposure (Figure 3), there were no
significant differences in the pattern or intensity of the
peaks, thus demonstrating the antioxidative efficacy
Figure 3. FTIR spectra of the formulation prepared using commercial
sunflower oil and TBHQ, before and after the oxidation test
of TBHQ under the conditions tested. Similarly, in the
UV resistance tests, no changes in color or consistency
were visible to the naked eye and the FTIR spectra of
the samples with and without light exposure did not
significantly differ (Figure 4). Therefore, the developed
lubricant showed good UV resistance under the condi-
tions tested.
The bio-lubricants fabricated from the two oils showed
no significant differences in either peak intensity or peak
location in the FTIR spectra (Figure 5). A comparison
of the two bio-lubricants at a thickener concentration of
10% (Figure 6) showed only a negligible difference in the
intensity of the asymmetric and symmetric stretching of
DEVELOPMENT OF A SUNFLOWER-OIL-BASED BIO-LUBRICANT FOR USE IN GEAR MODELS AT THE ISEP MUSEUM
Figure 4. FTIR spectra of the formulation prepared using commercial
sunflower oil and TBHQ, before and after the UV test
Figure 5. FTIR spectra of the commercial and high-grade sunflower oils
Figure 6. FTIR spectra of the bio-lubricants developed with commercial
and high-grade sunflower oils
-C-H (CH2) peaks at 2925 and 2855 cm−1, respectively.
These results demonstrated that both oils can be used
to formulate the lubricant.
Conclusion
The bio-lubricant developed with commercial or high-
grade sunflower oil, TBHQ as antioxidant, and beeswax
as thickener proved to be a sustainable alternative to
commercial lubricants. The physical and the chemical
stability of the bio-lubricant were demonstrated in air
and UV oxidation tests. As the formulation will be used
to maintain machinery for exhibition purposes, a high
performance is not needed and was therefore not tested.
However, to ensure that our newly developed product
has broader application, further tests in other settings
are needed.
53
References
Hamed, S.F. and M.A. Allam. 2006. Application of
FTIR spectroscopy in the determination of antioxidant
efficiency in sunflower oil. Journal of Applied Sciences
Research 2(1): 27–33.
Karmakar, G., P. Gosh, and B.K. Sharma. 2017. Chemi-
cally modifying vegetable oils to prepare green lubricants.
Lubricants 5(4): 44.
Kreivaitis, R., J. Padgurskas, M. Gumbyte, and A. Kupcin-
skas. 2015. An assessment of beeswax as a thickener for
environmentally friendly lubricating grease production.
Lubrication Science (27): 347–58.
Merrill, L.I, O.A. Pike, L.V. Ogden, and M.L. Dunn.
2008. Oxidative stability of conventional and high-oleic
vegetable oils with added antioxidants. Journal of the
American Oil Chemists’ Society 85(8): 771–76.
Woma, T.Y., S.A. Lawal, A.S. Abdulrahman, M.A. Olutoye,
and M.M. Ojapah. 2019. Vegetable oil based lubricants:
Challenges and prospects. Tribology Online 14(2): 60–70.
Authors
Maria Gonçalves has a bachelor’s degree in art conser-
vation and restoration and is currently a master’s student
in conservation and restoration of cultural heritage at
Universidade Católica Portuguesa (UCP), Porto. She
has a great interest in green conservation focused on the
research of new intervention methodologies, mainly for
inorganic materials.
Bruno Campos holds a PhD in chemistry. He has a vast
experience in analytical methods, research, and devel-
opment of organic molecules and inorganic materials.
Eduarda Vieira holds a PhD in conservation and resto-
ration of historic and artistic heritage. She is currently
an assistant professor at UCP and has been the director
of the UCP Research Centre for Science and Technology
of the Arts (CITAR) since July 2019.
Patrícia R. Moreira holds a PhD in biotechnology, is an
assistant professor at UCP, and coordinates the Heritage,
Conservation and Restoration focus area at CITAR. She
is interested in innovation in the field of cultural heritage
with an emphasis on biodeterioration, sustainability,
circular economy, citizen science, and green conservation.
MODERN METALS
A Review of Treatments of Magnesium Alloy Objects at
the National Air and Space Museum

Karen Wilcox Meredith Sweeney Lauren Horelick*

National Air and Space Museum,
Smithsonian Institution
Chantilly VA, USA
wilcoxkj@si.edu
National Air and Space Museum,
Smithsonian Institution
Chantilly VA, USA
sweeneym3@si.edu
National Air and Space Museum,
Smithsonian Institution
Chantilly VA, USA
horelickl@si.edu
*Author for correspondence

Abstract
This paper assesses the efficacy of treatments used to stabilize
magnesium-containing alloys at the National Air and Space
Museum (NASM) over the course of a grant-funded project from
2012 to the present. Throughout the 20th and 21st centuries,
the desirable physical qualities of magnesium alloys have led to
their extensive use in automotive and aerospace applications,
of which there are numerous examples in NASM’s collection.
The reactivity of these alloys, which is widely acknowledged
as a key limitation for industry, is especially problematic for
historic collections. Yet, there is a paucity of conservation-
specific examples dealing with these alloys, which this survey
sought to remedy. In this study, past treatments performed
at NASM were re-examined, drawing out examples of various
situations a conservator may encounter. It details the methods
used for surface preparation and protection, including
corrosion removal, chemical conversion, and the selection of
protective coatings. The objects under study were treated on a
case-by-case basis, and the methods and levels of intervention
varied, particularly as understanding developed during the
eight years of the project. Following treatment, the objects
were kept in controlled museum storage conditions. Past
documentation was compared to their current condition to
determine the efficacy of the treatments after real-time aging.
The criteria focused on the development of new corrosion or
other signs of deterioration. Most of the objects were found to
have a relatively unchanged appearance, irrespective of the
specific methods used to conserve them. These results factor
into a more nuanced discussion about levels of intervention for
NASM’s complex composite magnesium alloy objects.
Keywords
magnesium, aerospace, corrosion, past treatments

Introduction
The desirable physical qualities of magnesium alloys have
led to their extensive use in automotive and aerospace
applications throughout the 20th and 21st centuries.
However, the reactivity of these alloys is widely acknowl-
edged as a limitation for industry and presents a challenge
for conservators tasked with their stewardship.
This research offers a review of past treatment approaches
by conservators at the National Air and Space Museum
(NASM) to stabilize magnesium alloys. The examples
discussed were compiled from treatment reports prepared
during a Smithsonian Institution Collections Care and
Preservation Fund (CCPF) grant (2012–present), known
in-house as the Triage Project. This initiative supports
documentation and stabilization of artifacts across
NASM’s diverse collection and has included objects with
active magnesium corrosion, a condition for which there
are no established conservation methodologies.
Given the widespread use of magnesium alloys over
the last century, one would expect them to be present
in museum collections. However, as NASM sought to
develop enduring treatment approaches during the Triage
Project, only a short list of conservation-focused literature
was encountered. This is curious given the relative insta-
bility of magnesium alloys. Treatment options and useful
insights into corrosion mitigation methods are discussed
by Dornheim (1999), Worle et al. (2010), Norquest (2013),
Taggart (2016), and Rodriguez and Ravizza (2021). These
publications discuss the balancing act required of conser-
vators, who must walk a fine line between the aggressive
corrosion mitigation measures required for this alloy and
the necessity to preserve integral markings and surface
finishes. Museum professionals are therefore confronted
with the challenge of finding nuanced preservation strat-
egies to balance these two extremes.
A REVIEW OF TREATMENTS OF MAGNESIUM ALLOY OBJECTS AT THE NATIONAL AIR AND SPACE MUSEUM 57

The impetus for this research stems from Riddle et al.

(2019), who highlighted the necessity of reviewing past
treatments on magnesium alloys after observing the
failure of a treatment on NASM’s Surveyor spacecraft.
Corrosion re-formed within only a few years, indicating
that the methods originally used were insufficient. The
current project, therefore, sought to identify what other
treatments might also have been unsuccessful. The Triage
Project is fast paced, with an average of 300 objects
completed annually. A diversity of tools and techniques
have been employed throughout the years, and it was
anticipated that revisiting these treatments would reveal a
variety of results. This paper shares NASM’s approaches,
reflections, and treatment outcomes to discuss the unique Figure 1. (a) Light surface corrosion on a 1960s Satellite Momentum
preservation challenges of magnesium alloys. Wheel; (b) compact crust on an Engine Starter; (c) spiral threads on an
Antenna Drive; (d) voluminous corrosion on the Surveyor 8 battery cell

Magnesium alloy corrosion

Objects in the Triage Project were previously stored in
less-than-ideal conditions, which contributed to the range
and extent of the magnesium corrosion observed. The
high reactivity of magnesium alloys is due to their low
ionization energy, which means they lose electrons easily
in ambient conditions through normal aerobic corrosion
processes (Keronite 2021). A study by Green and Thickett
(1993) characterized corrosion found on museum objects
that included magnesium oxide, magnesium carbonate
hydroxide hydrate, and magnesium acetate. Magnesium
alloys are sensitive to surface contamination, such as
metallic particulates, chlorides, sulfates, and any foreign
material trapping moisture on the surface. As these alloys
do not form a passivating film, and given their sensitivity
to impurities and contamination, manufacturers aggres-
sively clean surfaces before any protective layers can be
applied (Guo 2010). Types of historic corrosion protec-
tion include anodizing, chemical conversion, plating, or
organic coatings (Chen et al. 2011).
Conservators at NASM have observed such protective
surfaces disrupted by magnesium corrosion, which
appears as bright-white-colored, loosely adherent, spher-
ical, acicular, or spiral products that can range from a light
powder on relatively intact original surfaces through to
dramatic, thick crusts (Figure 1). Corrosion has been
found migrating through painted surfaces, conversion
coatings, and, in severe cases, causing blistering, flaking,
and loss to paint layers. Original surface details such as
inscriptions and evidence of casting processes might
be unaffected by the voluminous crust and could be
Figure 2. Boost Control module: (a) corrosion covering the surface before
treatment and (b) after treatment showing retention of the surface
paint. Apollo-era Keyboard Display: (c) dense, spherical corrosion before
treatment and (d) preserved inscriptions after treatment
recovered with thoughtful selection of surface prepara-
tion and protection methods (Figure 2). In other cases,
this crust was associated with severe pitting and surface
loss. Öteyaka et al. (2012) used microscopy to show
that corrosion creates a complex morphology, with pits
ranging from shallow and wide to narrow and deep, and
with subsurface cavities. This creates a complex structure
for treatment.
At NASM, it has also been observed that components
within a single object can be differentially affected.
Figure 3 shows areas of spalling on a machined bezel next
to light superficial corrosion on the same cast exterior.
Portable X-ray fluorescence spectroscopy (pXRF) of
both regions revealed similar elemental compositions,
perhaps reflecting that fabrication methods influence
corrosion (Hu et al. 2014).
58  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND MODERN METALS

products were a multi-elemental reflection of the associ-

ated bulk alloy. However, specific corrosion mechanisms
were not investigated due to this project’s tight scope of
providing stabilizing treatments. From reviewing the 66
reports, two major stages in treatment became evident:
surface preparation and surface protection.

Figure 3. Satellite camera lens: (a) before treatment overall; (b) detail
of the machined bezel
Surface preparation
All treatments began with cleaning, reportedly aiming for
The variety of corrosion formations, their underlying
an even surface with no evidence of white-colored corro-
surfaces, the composite nature of the objects, and their
sion products and escalating the intervention until this
overall construction greatly influenced conservation
was achieved. However, in some cases, the intervention
decisions, as evidenced by the variety of past treatments
was limited by surface layers (paint, coatings) or phys-
performed during the Triage Project.
ical construction (access to the interior) and proceeded
directly to consolidation or coating. Key materials and
Methods used in the Triage Project
techniques are summarized in Table 1.
In 2020, a search of 1,782 Triage treatment documents
Typically, the removal of corrosion products, dirt, and
commenced, and 66 reports were identified with the term
contamination prepared the surface for a protective
“magnesium” mentioned in the description, condition, or
coating or, less frequently, concluded the treatment.
treatment text. Within these 66 reports, a wide variety of
treatment approaches and methodologies were recorded,
Surface protection
reflecting the experiences of the many contributors to the
project since 2012. All objects examined during the Triage Protective conversion layers are added during the fabrica-
Project underwent before-treatment written and photo- tion of magnesium alloys, but they can become disrupted
graphic documentation with a view to their stabilization by corrosion. The creation of chromate conversion layers
under curatorial guidance. Occasionally objects were was historically performed in industry and at NASM,
characterized with pXRF, revealing that loose corrosion but treatments of this type were discontinued due to

Table 1. Summary of surface preparation techniques used by Triage conservators from 2012–2019

Tool type Specifics Notes

Hand tools Stainless steel scalpels (sharp or dulled), stainless steel micro-tools, wooden Residues cleared by swabbing with solvents
skewers, or fiberglass bristle brushes
Abrasive media Walnut shell Aqueous surface cleaning after application
to remove residues
Not suitable for objects that cannot be
disassembled or have vulnerable areas that
cannot be masked off
Polishes 3M™ Mag and Aluminum Polish Residues cleared by swabbing with mineral
Nuvite™ NuShine II (Grades A, S, or C; fine to finest) spirits
Chemical: Acids o-Phosphoric acid (20% in deionized water) Applied by brushing, swabbing, or
Chemfil™ DX520 Metal Conditioner (phosphoric acid with a detergent) ultrasonic bath if components can be
Cortec™ VpCI-426 disassembled or isolated
(phosphoric acid with corrosion inhibitors) diluted with deionized water Cleared by swabbing with deionized water,
(from 1:1 up to 1:4) followed by ethanol and/or mineral spirits
Sanchem™ 560RTU Mild Acid Cleaner (glycolic acid)
Chemical: Bases Cortec™ VpCI-427 sodium hydroxide with corrosion inhibitors diluted with Same as above
deionized water (1:3 or 1:4)
OTHER METHODS TESTED
Chemical swabbing Cotton swabbing with acetone, ethanol, sodium hydroxide solution (2% w/v Minimally effective
in deionized water)
Electrolytic reduction Electrolytic reduction or softening using a sodium hydroxide electrolyte (10 V) Minimally effective
A REVIEW OF TREATMENTS OF MAGNESIUM ALLOY OBJECTS AT THE NATIONAL AIR AND SPACE MUSEUM
health and safety concerns. Safer formulations have
been developed industrially, and a commercial two-step
system by Sanchem was trialed at NASM using a glycol-
ic-based cleaner (560RTU Mild Acid Cleaner) for surface
preparation followed by a chromate-free conversion
coating (SafeGard CC 13062Mg RTU Rust Preventive
& Conversion Coating). Whilst the cleaner is suitable
for a range of light-metal alloys, the coating was devel-
oped specifically for magnesium alloys. Rodriguez and
Ravizza (2021) reported the use of the Sanchem system
on the Tiros meteorological satellite. They demonstrated
it was possible to retain the original surface layers even
when walnut shell blasting was followed by the Sanchem
products. This treatment was completed with a final
surface coating of microcrystalline wax (Figure 4). The
Sanchem system has been the preferred choice of Triage
conservators since this treatment in 2018.
Figure 4. Tiros meteorological satellite: (a) before treatment and (b) after;
photomicrographs (c) before (40×) and (d) after (100×)
Before this product was identified, the Triage treatments
progressed directly from surface cleaning to a protective
coating. Protective coatings used during the project are
summarized in Table 2.
Collating the treatment reports revealed an array of
materials and methods, as well as the general protocol for
surface preparation and protection. Variations reflected
Table 2. Protective coatings used
Material Specifics
Waxes Renaissance™ microcrystalline wax
Commercial oils and CRC SP-350™ (corrosion inhibitor oil)
waxes containing CRC SP-400™ (a corrosion inhibitor wax)
corrosion inhibitors Cortec™ VpCI®-368 (a petroleum-based film) Cortec™ VpCI®-368, applied and allowed to dry followed by buffing
Acrylics Paraloid B-72 and B48N
Cellulose nitrate Agateen™ lacquer
59
specifics of the object, personal preference, and a devel-
oping understanding of magnesium alloys over time.
In 2020, the authors had the opportunity to review this
topic further by revisiting a selection of case study objects
previously treated and stored at 69°F (±2) (20°C) and
40% RH (±10) in the intervening years.
Evaluation of past treatments
Eight case study objects were purposefully selected
for re-examination to exemplify varied fabrication
methods and types of treatment. Analysis considered:
(a) the efficacy of the treatment methods for the desired
outcome, i.e., achieving a stable surface; (b) the extent
of the treatment intervention; and (c) the longevity of
corrosion protection.
Methodology
The presence of magnesium in each object was confirmed
with pXRF (40 kV, 10 µA, 120 s, vacuum, no filter), and
its appearance was compared with past written and
photographic documentation. One challenge was how
best to parse this documentation to draw meaningful
comparisons.
The evaluation criteria focused on:
a) alterations to the object during treatment, such as to
original surface finishes; and,
b) the post-treatment development of corrosion or other
signs of deterioration after real-time aging, including
changes in NASM-applied coatings.
This was a purely empirical evaluation of treatment
success and “stability” based on appearance before
treatment, combined with the experience that objects
could catastrophically re-corrode with voluminous,
white-colored corrosion product within a few years after
treatment—as in the case of the Surveyor spacecraft—or
even in a matter of hours during a treatment.
Notes
Applied hot or cold, with or without buffing
CRC SP-350™ brushed onto surface, allowing to penetrate and dry for 24
hours up to several days, followed by buffing with CRC SP-400™.
Applied by brush in various concentrations and solvent vehicles
Applied by brush on a gold-plated magnesium alloy
60  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND MODERN METALS

Results purposefully selected to include “worst-case” scenarios

Table 3 organizes the eight selected case study objects.
The table breaks down the relevant factors used to
evaluate the objects. The specific connections between
the objects’ original surface coatings, condition issues,
treatment methods, and the re-emergence of corrosion
are paramount to the discussion of intervention levels,
the success of corrosion removal, and the efficacy of
coatings.
Discussion
Based on the Surveyor experience, it was expected that
some treatments would have also failed. The objects were
where previous corrosion had been very severe or where
treatment was limited by factors of the object or the
conservator’s judgement.
Surprisingly, empirical observations showed that no
new corrosion had formed in the years after treatment,
although a longer time-depth study is warranted. The
review of the objects resulted in three salient trends:
(a) no method completely removed all evidence of corro-
sion; (b) there are multiple suitable treatment pathways
for magnesium alloys kept in controlled storage condi-
tions; and (c) the coatings, in combination with stable
storage conditions, proved to be very effective in the

Table 3. Summary of the case study objects

Year 2020 Corrosion

Object name Original surface Condition Surface preparation Protective coating
treated re-formation
2012 Apollo Chromate Round spheres of Dry brush, scalpel; 3M™ 3 coats of Paraloid B-72 (8% No
Keyboard conversion white corrosion, polish, cleared with MS acetone/ethanol)
Display coating thick
2013 Gemini Gimbal Chromate White Cleaning: vacuum; wooden 3 coats of Paraloid B-72 (5% No
Control conversion layer, efflorescence and skewer; with brush, wooden acetone:ethanol)
white paint pitting skewer; swabbed with Nuvite
polish (grades F9/F10, C)
cleared with MS
2014 German Earth Non extant due White, powdery Scalpel, pointed tools, CRC SP-350, followed by No
Induction to corrosion corrosion cleared with MS; repeated CRC SP-400, dried over 48
Compass immediately prior to coating h, excess removed with soft
Corrosion re-appeared during cloth
treatment
2014 Momentum Conversion White, powdery Dull scalpel, natural rubber No coatings Minor
Wheel coating bloom; conversion eraser, swabbed with MS superficial
layer intact corrosion
2014 ATS 6 Satellite Chromate White corrosion Scalpel, wooden skewer, Several coats of Paraloid No
conversion layer, erupting through swabbed with ethanol and MS B-72 (5% acetone/ethanol),
red primer and surface layers, also used to consolidate
black paint on top minimal white paint
surface, yellow bloom over paint
anti-static film on
bottom surfaces
2014 Northrop P-61C Conversion Extensive Scalpel, wooden skewer, 2 coats of Paraloid B-72 (5% No
Turret Motor coating corrosion fiberglass brush, micro-tools in acetone/ethanol)
cleared with MS; swabbed
with PA (20%) cleared with DI
then MS; swabbed with 3M™
polish cleared with MS
2017 German Chromate Extensive Areas of intact conversion 2 coats of Paraloid B48N (6% No
Aircraft De-icer conversion corrosion, coating masked; walnut shell in xylene); microcrystalline
coating especially at abrasive blasting; swabbed wax around iron-alloy
contact with with acetone fasteners
dissimilar fittings
2018 Intervalometer Chromate Extensive friable Mechanical Sanchem™ products; hot No
Kit Camera conversion with corrosion microcrystalline wax
tope colored
paint
Key: DI = deionized water; MS = mineral spirits; PA = phosphoric acid
A REVIEW OF TREATMENTS OF MAGNESIUM ALLOY OBJECTS AT THE NATIONAL AIR AND SPACE MUSEUM
prevention of corrosion re-emergence, which is critical
given then reactivity of magnesium alloys.
Incomplete corrosion removal
Triage treatments reportedly aimed for surfaces cleared
of corrosion products prior to the surface protection.
Microscopic examination of the case study objects
revealed fine, white-colored material embedded in
the pits. This suggests that no preparation technique
completely removed all corrosion products. Despite the
apparent incomplete removal, the objects did not appear
to worsen while in controlled storage. Even with a tech-
nique as effective overall as walnut shell blasting, used
to treat the German De-icer, some minimal corrosion
product was still observed microscopically in the pits
after treatment (Figure 5). In addition, whilst all metallic
contamination must be cleaned from magnesium alloys
due to their sensitivity to galvanic corrosion, the use of
metallic tools also did not seem to create loci for corro-
sion—likely due to solvent clearance. These observations
have major practical significance for all collections.
Multiple suitable pathways
In the case study objects, both minimal and interventive
treatments were characterized by a trend of increasing
intervention levels as the project progressed. This reflects
a growing vocabulary of tools, techniques, and materials.
Some of the earliest treatments were the most cautious,
as in the example of the Momentum Wheel (Figure 6).
Figure 5. German De-icer: (a) before and (b) after treatment in 2017;
(c) photomicrograph (180×) showing corrosion in the pits with the
wax coating
Figure 6. Momentum Wheel: (a) before and (b) after treatment in 2014;
(c) 2020 condition with location of photomicrographs identified: (d)
65× and (e)178×
61
This object was originally treated in 2014 and did not
have a coating applied. The original, brown-colored
chromate conversion layer appeared relatively intact,
and the conservator recorded their concern that further
intervention might disrupt this thin layer. Of the case
study objects, this was the only one to noticeably re-de-
velop new, bright-white corrosion, albeit minimally over
a seven-year period.
Experimentally, as NASM conservators began to expand
their techniques, they found that some materials could
be used with care over thin-surface conversions layers
with minimal disruption. These included Nuvite metal
polish used on the Gemini-era Gimbal Control (Figure 7)
and the glycolic-based Sanchem system used on the
Intervalometer Kit Camera.
The treatment of the ATS-6 satellite was also limited due
to prioritizing retention of the original black paint film
over stabilizing the corrosion. In 2020, corrosion product
was seen microscopically permeating through the film.
However, there has been no more overt flaking or loss
of the paint due to this underlying instability, suggesting
the value of a good environment, limited handling, and
the protection afforded by the original paint surface.
The most compelling example for an interventive re-treat-
ment is the P-61C Turret Motor, which was minimally
treated in 2014. Surface cleaning ceased when the
conservator noted spalled metal and opted to move to
surface coating with an acrylic resin to limit further
material loss. A visible layer of corrosion remained extant.
Interestingly, when re-examined in 2020, this had not
worsened (Figure 8). At this time a decision was made to
remove more of this corrosion using chemical means. The
bottom portion of the artifact was submerged in Cortec
VpCI-426 (1:4 in deionized water) in an ultrasonic bath
for five minutes, rinsing with deionized water, and then
Figure 7. Gemini Gimbal Control: (a) before and (b) after treatment; (c)
2020 condition with location of photomicrographs identified: (d) 65×
and (e) 178×
62  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND MODERN METALS

Figure 8. Northrop P-61C Black Widow Turret Motor: (a) before and (b) Figure 9. German Earth Induction Compass coated with CRC™ products:
after treatment in 2014; (c) after re-treatment in 2020 (a) before and (b) after treatment in 2012; (c) condition in 2020

with mineral spirits. Whilst more corrosion was removed

and a more even, gray surface appearance was achieved,
etching was noted around the edges. Submersion while in
the ultrasonic bath also resulted in some metal accumu-
lating in the bottom of the bath. Despite this more inter-
ventive re-treatment, minor corrosion product persisted,
and once again the treatment was discontinued out of
concern for further loss. Upon reflection, the immersive
treatment might have been more successful if the glycol- Figure 10. Intervalometer Kit Camera coated with acrylic: (a) before
and (b) after treatment in 2019; (c) condition in 2020 with location of
ic-based Sanchem cleaner had been used rather than
photomicrographs identified: (d) 65× and (e) 180×
Cortec. Both products are identified by manufacturers
as suitable for use on magnesium alloys. This inference is a less-than-ideal micro-climate than the Intervalometer
based on experience from the Intervalometer Kit Camera Kit Camera, both examples highlight the functionality
and TIROS satellite, where the Sanchem product was of commercial wax and corrosion-inhibitor coatings as
observed to be a “gentler” acid cleaner.
distinct from the acrylic coatings used in most of the
This re-treatment spurred discussion about the neces- case study objects.
sity of further intervention. Some conservators felt the
As with other facets of these Triage treatments, there
re-treatment was appropriate due to the amount of extant
corrosion. Others felt it was too interventive given the are multiple suitable pathways for successful coatings to
lack of new corrosion formation from 2012−2020, and adequately prevent corrosion re-formation.
that re-treatment also did not completely remove all Objects must be treated on a case-by-case basis. This
visible corrosion products.
discussion summarized the nuances, variety, and chal-
Utility of coatings lenges encountered with some of the complex, composite
magnesium alloy artifacts found in NASM’s collections.
Where coatings (acrylics, waxes, and commercial formu-
lations with corrosion inhibitors) were applied to objects,
no corrosion re-formed. This was true even for objects Conclusion
stored in less-than-ideal microclimates, specifically This paper details materials and methods used during
wooden enclosures. Two of the objects, the German Earth
NASM’s Triage Project from 2012 to 2019 and reviews
Induction Compass (Figure 9) and the Intervalometer
past treatments. Variations in techniques reflected
Kit Camera (Figure 10), were returned to their original
specifics of the objects, personal preferences, and devel-
wooden enclosures after treatment, and no new corrosion
or alteration of the coating was observed. This is compel- oping approaches. Earlier in the project, approaches were
ling as studies have tied magnesium alloy corrosion to more cautious, drawing from tried-and-true methods
incompatible wooden storage (Green and Thickett 1993, used for other metals and finding their suitability for
Worle et al. 2010). Although the German Earth Induction magnesium alloys, with the added caveat that the relative
Compass, treated in 2014, represents a longer duration in reactivity of these alloys requires a higher level of inter-
A REVIEW OF TREATMENTS OF MAGNESIUM ALLOY OBJECTS AT THE NATIONAL AIR AND SPACE MUSEUM
vention. Since 2018, the preference has been to use the
Sanchem system in concert with wax coatings.
The Triage Project provided a compelling breadth of
examples for evaluation and added surety to previous
conservation methodologies. It was expected that the
review would identify examples of treatment failures
due to the reactivity of magnesium alloys. Surprisingly,
the case study objects mostly remained unchanged up
to seven years after treatment in a controlled environ-
ment. While this is a short timescale for evaluation, it is
warranted due to the experience with Surveyor’s failed
treatment, where corrosion re-formed within five years.
This paper demonstrated the unambiguous need
for protective coatings with examples of corrosion
re-forming when none was applied. The utility of coat-
ings is also evident in the case studies where objects
were kept in their original (acidic) wooden housings
after treatment. The study concluded that no new
corrosion developed in instances where there was still
extant corrosion post-treatment. This suggests that
minor corrosion, if both sealed and maintained in a
controlled environment, can remain stable.
Further work
While this paper examines a small sample size over a
relatively short period of time, the findings have gener-
ated the following areas for future research:
• How much do protective coatings—particularly
waxes—impede future re-treatment if needed?
• Are there other simple methods beyond visual exam-
ination that could be used to qualitatively determine
treatment success and stability?
• To what extent can corrosion protection be proactively
measured in situ, using nondestructive methods?
• Can magnesium and magnesium-containing alloys
(such as in the aluminum series) be differentiated using
simple instrumental analysis? And how does this factor
into necessary levels of intervention, e.g., for purposely
engineered corrosion-resistant formulations?
Through the process of writing this paper, NASM now
has an established baseline survey process based on
visual examination coupled with pXRF and photomi-
croscopy. This will be used for future monitoring of
magnesium alloys, and it is a useful starting point for a
much needed, longer-term study. The authors hope this
63
paper will spur discussion about refining stewardship
practices for these alloys.
Acknowledgments
The authors wish to thank the National Collections Pres-
ervation grant committee, NASM staff, the numerous
CCPF Triage contractors, interns, and fellows.
References
Chen, X., N. Birbilis, and T. Abbott. 2011. Review of
corrosion-resistant conversion coatings for magnesium
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Dornheim, J. 1999. Behandlung korrodierter Oberflächen
von Objekten aus Aluminium- und Magnesiumlegierungen,
257 pp. Beijing: Kexue Chubanshe. https://aata.getty.edu/
permalink/f/1kjitv/GETTY_AATA9934093547401551
(accessed 6 March 2022).
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museum collections. In Saving the Twentieth Century:
The Conservation of Modern Materials. Proceedings
of a Conference Symposium, Ottawa, Canada, 15–20
September 1991, ed. D.W. Grattan, 261–89. Ottawa:
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Guo, K.W. 2010. A review of magnesium/magnesium
alloys corrosion and its protection. Recent Patents on
Corrosion Science 2: 12–21.
Hu, H., X. Nie, and Y. Ma. 2014. Corrosion and surface
treatment of magnesium alloys. In Magnesium alloys:
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chap. 3. London: IntechOpen.
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2022).
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an antenna drive. Posted on the Smithsonian Air and
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take-antenna-drive (accessed 6 March 2022).
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sion behaviour of AZ and ZA magnesium alloys in alka-
line chlorine media. International Journal of Corrosion
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Decision-making in context: Conservation of gold and
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magnesium alloy components on a surveyor spacecraft.

In Objects Specialty Group Postprints, 47th Annual
Meeting in Uncasville, Connecticut, May 12–June 17,
2019, eds. K. Dodson, M. Wilcop, and J. Arista, vol. 26.
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SPNHC 49th Joint Virtual Annual Meeting, May 10–June
24, 2021.
Taggart, C. 2016. Conserving a WWII Black Widow
compressor. Posted on the Smithsonian Air and Space
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pressor (accessed 6 March 2022).
Worle, M., O. Berger, E. Hildbrand, V. Hubert, and K.
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Authors
This work was completed whilst Meredith Sweeney
and Karen Wilcox were Engen Conservation Fellows at
NASM, under the supervision of Conservator Lauren
Horelick.

Mitigating Magnesium Corrosion: Testing the Efficacy
of Reapplying Conversion Coatings in Conservation
Treatment
Abigail Elizabeth Rodriguez
Winterthur/University of Delaware Program in Art Conservation
Winterthur DE, USA
abelizabeth.rod@gmail.com
Abstract
Magnesium and its alloys are highly desirable structural materials
with a propensity to corrode. Used in a variety of industrial
applications since the early 20th century, magnesium alloys
can be found in objects ranging from automobiles to satellites.
Many of these objects have found their way into both museums
and private collections, providing a unique opportunity for
conservators to consider industry standards and proprietary
materials in the mitigation of magnesium corrosion. Placing
the preservation of original material at the forefront, this study
presents a possible treatment methodology for applying a new
conversion coating to replace worn areas of an aged coating on
a magnesium alloy (AZ31). The study examines the effects of the
new coating on the original coating, comparing two application
Introduction
Magnesium and its alloys have a variety of desirable
properties including a high strength to weight ratio and
a low density. For these reasons, they have been used
in many structural applications across a diverse array
of industries. The preferable properties of magnesium
alloys are often offset by the metal’s high reactivity and
susceptibility to corrosion—particularly in the presence
of humidity and contact with dissimilar metals (Figure 1).
The galvanic corrosion of magnesium alloys is a result of
the standard electrode potential of the metal.
Given magnesium’s predisposition to corrode, it can be
difficult to work with as a structural material. However,
Figure 1. Photomicrographs of magnesium corrosion taken at (a) 35×
and (b) 100×
Young Conservation Professional
methods: localized and immersion. The treatment employs two
proprietary materials: (1) Sanchem 560 Cleaner, a glycolic acid-
based solution used to remove surface oxides, followed by (2)
Sanchem SafeGard CC 13062Mg conversion coating, an adherent
protective layer. Analysis was conducted using scanning electron
microscopy and energy-dispersive x-ray spectroscopy, x-ray
diffraction, and digital microscopy. The results of the study
supported the use of immersion treatment as it produces a more
effective coating.
Keywords
conversion coating, magnesium corrosion, modern metal
conservation
advances in corrosion mitigation have prompted the
development of several methods to protect magnesium
alloys (Umehara et al. 2003, Shashikala et al. 2008).
Among these different technologies, chemical conver-
sion has become the least expensive and simplest to
execute (Shashikala et al. 2008, Makhlouf 2011, Frayret
et al. 2017). The conversion coating process changes
the surface of the metal into a more stable non-metallic
compound, providing a barrier between the reactive
surface and the environment.
When considering the efficacy of a coating, it is important
to note that film formation and uniformity play a crucial
role in decreasing corrosion susceptibility. The protective
layer must be uniform, well-adhered, and robust for
applications where physical wear may occur (Gray and
Luan 2002). While many factors contribute to effective
film formation and successful coatings, the number one
cause of coating failure on magnesium is poor adhesion
due to the improper removal of oxide and hydroxide
layers on the metal surface (Mordike and Ebert 2001,
Frayret et al. 2017). Thus, processes including cleaning,
66  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
degreasing, and oxide/hydroxide removal play a critical
role in the application of successful coatings (Gray and
Luan 2002, Umehara et al. 2003). Industry standards
in the application of conversion coatings include the
complete removal of previous coatings. This study aims
to test two application methods for the replacement of
worn areas of aged conversion coatings.
The conversion coating system selected for this study
is Sanchem’s 560 Cleaner (glycolic acid-based) and
SafeGard CC-13062Mg, an acid bath and a conversion
solution, respectively (Sanchem, Inc. 2017, Sanchem,
Inc. 2018). This system was chosen based on its ease of
application and disposal. Sanchem’s SafeGard magnesium
conversion coating and cleaner contain “no toxic mate-
rials;” the spent solution can be diluted and disposed of
in the sewer system. The final coating is a transparent
surface that can readily accept primer or topcoats.
The alloy AZ31, a wrought magnesium alloy with
aluminum and zinc (Table 1), was selected for this study
given its diverse applications (Dziubinska et al. 2015).
Experimental
Materials and sample preparation
Eleven samples were cut into 5E-5 m3 coupons and
die-stamped with sample identification numbers
(Table 2). Five were used as controls and six as test
samples (three for localized treatment and three for
immersion treatment).
Table 1. Chemical composition of magnesium alloy AZ31
Magnesium 94.2%–96.6%
Aluminum 2.5%–3.5%
Zinc 0.7%–1.3%
Manganese 0.2%–1.0%
All 11 samples were polished with 600- to 1200-grit
Micro-Mesh, rinsed with acetone, and dried with
compressed air. The starting mass of each sample was
recorded.
Six conversion-coated samples and their associated
controls were prepared to represent an original coating
(Table 3).
The six samples and associated controls were then
subjected to a controlled corrosion environment. This
corrosion was grown by mechanically abrading areas of
the coating on one side of each sample and placing the
MODERN METALS
Table 2. Sample identification numbers
Sample ID Details
1C control of bare, uncoated magnesium
2C control of conversion coated magnesium,
CONTROLS
pre-corrosion
3C control of corroded magnesium with worn
conversion coating
4C control of immersion-treated samples
5C control of locally treated samples
A Immersion-treated sample
TEST SAMPLES
B Immersion-treated sample
C Immersion-treated sample
D locally treated sample
E locally treated sample
F locally treated sample
Table 3. Sample preparation
1 A 3% v/v (recommended by Sanchem) aqueous solution of the
560 Cleaner was prepared in a small plastic bin
2 The samples were immersed for three minutes each at a pH
of 2.2–2.4 (recommended by Sanchem) to remove oxides and
hydroxides on the metal surface
3 The samples were rinsed with deionized water, dried with
compressed air, and weighed
4 The samples were then immediately immersed in the conversion
coating solution at pH 4.0–4.2 (recommended by Sanchem) for
2 min and set up to air dry
5 Once dry, the samples were weighed and photographed
samples in a commercial humidity chamber for 48 h.
To ensure corrosion growth, an aerosolized 1% aqueous
solution of NaCl was introduced into the chamber at
the 12 h, 24 h, and 36 h marks using a spray bottle. This
corrosion environment was designed based on the cyclic
corrosion standards for automotive and aircraft mate-
rials in VDA 233-102 (Verband der Automobilindustrie
2013). The chamber was kept at 80%–100% RH. After
the samples were removed, they were rinsed, air-dried,
weighed, and photographed.
These corroded samples were then treated using two
application methods of the conversion coating system:
immersion (the industry standard) vs. localized (a
conservative approach) (Table 4).
Analytical techniques
The analytical techniques employed in this study are
detailed in Table 5.
MITIGATING MAGNESIUM CORROSION: TESTING THE EFFICACY OF REAPPLYING CONVERSION COATINGS IN CONSERVATION TREATMENT 67

Table 4. Immersion vs. localized treatment procedure

Immersion Localized
• Loose corrosion products • Loose corrosion products
removed with Scotch-Brite removed with Scotch-Brite
abrasive pads, glass bristle abrasive pads, glass bristle
brushes, and stiff nylon brushes brushes, and stiff nylon
• Samples submerged for 3 min in brushes
a 3% v/v aqueous solution of the • Samples locally treated with a
acid-based 560 Cleaner brush application of a 3% v/v Figure 2. SEM images (25–26×) of (a) a bare polished sample, (b) a
• Samples rinsed, dried, and aqueous solution of the acid- converted sample, and (c) a corroded sample
weighed; weight compared based 560 Cleaner; attempted
to the weight of the samples targeting of areas of extant
before corrosion, applying a oxides and hydroxides highlight the morphological changes that occurred
“weight-loss” method to estimate without damaging the first during the coating and corrosion of the samples. The
an average corrosion rate (see coating
converted surface, as shown in Figure 2b, is smooth
Appendix A) • Samples coated by brush
• Samples coated by immersion in application and glass-like, indicating a cohesive and successful
the conversion solution for 2 min film formation. This successful coating application was
likely influenced by the polishing (the results are shown
Results and discussion in Figure 2a) and acid bath––both of which aided in
removing oxides and hydroxides from the surface.
The sample preparation phase of the study provided the
opportunity to document the conversion coating process X-ray diffraction (XRD) was used to characterize the
using a known alloy (AZ31) and a known set of prod- corrosion products formed during the sample preparation
ucts. The scanning electron microscopy (SEM) images phase. As shown in Figure 3, magnesium oxide (MgO)
in Figure 2 show the contrast between the polished, was the only detected component of the white corrosion
converted, and corroded surfaces of the magnesium collected from sample A. This data is corroborated by
samples. The images, taken at 25–26× magnification, magnesium’s propensity to form oxide and hydroxide

Table 5. Analytical techniques

Instrument Application Sample prep

Hirox digital microscopy Used to capture morphological
changes during the sample preparation
and treatment phase; images were
taken of the etched/polished surfaces,
converted surfaces, corroded surfaces,
areas of coating loss, and morphology
of the new coating
Scanning electron microscopy Used to capture morphological
(SEM) (Zeiss EVO MA15) changes during the sample preparation
and treatment phase; images taken
of the cohesiveness of the coating,
corrosion boundaries, and treatment
effects
Energy-dispersive Used to characterize the changes in the at an accelerating voltage of 20 kV for the electron beam, working
spectroscopy (EDS) chemical composition of the samples
as they were treated with the Sanchem collected with a Bruker Nano X-flash detector 6 | 30 and analyzed with
SafeGard method
X-ray diffraction (XRD) Used to investigate the phase
(Rigaku D/max Rapid II with structures of the polished samples,
a copper anode x-ray tube converted samples, and corrosion
(40 kV, 30 mA) and 0.3 mm
collimator)
N/A
The samples were cut into 1 × 1 cm squares and mounted on SPI Supplies
Zeiss aluminum slot head stubs (12.7 × 3.1 mm) with SPI Supplies
double-sided carbon tabs (12 mm diameter). SPI Supplies conductive
carbon paint (colloidal graphite in isopropanol 20% solids) was applied
on the side and top surfaces of each sample. The samples were examined
using a Zeiss EVO MA15 scanning electron microscope with LaB6 source
distance of approximately 10 mm, and sample tilt of 0°. The EDS data was
Quantax 200/Esprit 1.9 software.
Powdered samples were collected by scraping the surfaces of the
coupons with a diamond blade scalpel. The powdered materials were
adhered to the tip of a silicon loop sample holder and secured to the
sample stage. Each sample was analyzed in spin mode (0°–360° rotation)
at a speed of 10°/sec, and total collection time of 3 h. Rigaku RAPID/XRD
software (v.2.4.2) was used for instrument operation and data collection
and Rigaku 2DP software (v.2.0.1.1) was used to select the portion of
diffraction rings for interpretation. Rigaku PDXL 2 software (v.2.3.1.0) was
used to interpret the diffraction pattern, and the Powder Diffraction File
from the International Center for Diffraction Data (ICDD) was used as a
reference database.
68  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
layers. Subsidiary corrosion products likely included
chlorides and hydroxides, given the conditions of the
corrosion growth.
Figure 3. XRD pattern of magnesium oxide (MgO) compared to corrosion
from sample A
Immersion treatment
Figure 4 shows photomicrographs of the magnesium
sample (B) at various stages of treatment. The immersion
treatment for the corroded samples shows significant
visual contrast before (4b) and after (4c) the acid-bath
treatment step. The sequence of the three photomicro-
graphs illustrates that the corrosion in Figure 4b was
successfully cleared from the surface to reveal areas of the
original coating and extensive pitting. There is damage
to the extant coating where the corrosion pustules were
washed away in the acid bath. While the losses to the
original coating are not ideal for a cultural heritage
setting, the removal of the corrosion from the surface
and pits was necessitated for proper coating formation.
The SEM image and energy-dispersive spectroscopy
(EDS) elemental map in Figure 5 show that the pits on
the magnesium surface (sample 4C) have oxygen and
chloride-containing elements present. Surrounded by a
smooth coated surface, the pits likely have traces of oxides
and chlorides that were not removed during the acid
bath. This finding is important as it indicates a lowered
corrosion resistance for the applied conversion coating.
These areas of pitting are now points of weakness below
the coating that are susceptible to future corrosion.
This can be corrected in future applications of this
methodology. While the samples during this study
were immersed in the acid bath without any agitation
or scrubbing on the surface, abrasive pads can be used
to enhance the cleaning power of the bath (Ravizza and
Rodriguez 2019). Additionally, the mechanical reduction
of the corrosion that was conducted during this mock
MODERN METALS
treatment was conservative, due to the decision not to use
strong abrasives. Industry standards recommend the use
of air abrasives to dislodge corrosion from pits prior to an
acid bath. Walnut shells and plastic beads are preferred
media for reducing corrosion on magnesium-aluminum
alloys (Ravizza and Rodriguez 2019).
Depending on an object’s needs or the treatment inten-
tions, these methods can be adapted to enhance the
cleaning power of the acid bath and the application
technique for the conversion coating.
Figure 4. Photomicrographs (35×) of (a) a polished sample, (b) a corroded
sample, and (c) an immersion-cleaned sample
Figure 5. (a) SEM image and (b) EDS elemental map (25×) of an
immersion-cleaned sample
Localized treatment
In contrast to the immersion treatment discussed above,
the conservative approach of locally treating samples with
the acid-bath solution was unsuccessful in reducing the
white corrosion residues on sample D (Figure 6c). This
lack of clearance was confirmed with EDS (Figure 7b),
showing concentrated areas of oxygen and chloride-con-
taining elements on sample 5C. As stated in the section
above, these are likely oxides and chlorides from the
corrosion environment. The SEM image shown in
Figure 7a depicts layers of corrosion products protruding
from the surface of the sample. Given the extent of
corrosion residues beneath the conversion coating, the
adhesion and effective lifetime of the coating are signif-
icantly compromised.
Within the context of this study, the localized treatment
approach for acid baths was developed as an experimental
alternative to standard industry practice, or immersion
treatment. This method of selectively cleaning a corroded
sample to preserve extant coating elucidates several
MITIGATING MAGNESIUM CORROSION: TESTING THE EFFICACY OF REAPPLYING CONVERSION COATINGS IN CONSERVATION TREATMENT
key issues. The first is the inefficacy of locally treating
corroded magnesium alloys. This method, together
with magnesium’s propensity to corrode, creates areas of
concentrated corrosion development along the bound-
aries of cleaned areas and extant coating. Additionally,
while the localized treatment in this study did not actively
remove the original coating, it also did not produce a
viable new coating to protect the surface.
Figure 6. Photomicrographs (35×) of (a) a polished sample, (b) a corroded
sample, and (c) a locally cleaned sample
Figure 7. (a) SEM image and (b) EDS elemental map (25×) of a locally
cleaned sample
Conclusion
While a conservative approach is traditionally taken
within the context of heritage preservation, this study
explored an interventive option––balancing the preser-
vation of authenticity with the execution of an effective
remedy. For the passivation of modern metal surfaces,
traditional conservation values are often challenged to
provide a successful solution. The importance of acid
baths was explored through two application methods:
localized and immersive. The results of the study support
the use of immersion treatment where possible and the
limited application of localized treatment approaches
to situations where objects cannot be disassembled for
immersion. Future research could include exploration
of additional conversion coating systems as well as the
incorporation of mechanical corrosion reduction prior
to treatment.
While these methods may not be ideal for every treat-
ment, they should be considered an example of the
practical application of “tough love” to magnesium, a
very temperamental metal.
69
References
Dziubinska, A., A. Gontarz, K. Horzelska, and P. Piesko.
2015. The microstructure and mechanical properties of
AZ31 magnesium alloy aircraft brackets produced by
a new forcing technology. Procedia Manufacturing 2:
337–41.
Frayret, J., J.C. Dupin, and S. Pommiers. 2017. Corrosion
protection of magnesium alloys: From chromium VI
process to alternative coatings technologies. In Magne-
sium alloys, ed. M. Aliofkhazraei, 161–87. London:
IntechOpen.
Gray, J.E. and B. Luan. 2002. Protective coatings on
magnesium and its alloys – A critical review. Journal of
Alloys and Compounds 336: 88–113.
Makhlouf, A.S.H. 2011. Current and advanced coating
technologies for industrial applications. In Nanocoat-
ings and ultra-thin films: Technologies and applications,
eds. A.S.H. Makhlouf and I. Tiginyanu, Woodhead
Publishing Series in Metals and Surface Engineering,
3–23. Cambridge: Woodhead Publishing.
Mordike, B.L. and T. Ebert. 2001. Magnesium: Properties,
applications, potential. Materials Science and Engineering
A302: 37–45.
Ravizza, D. and A. Rodriguez. 2019. Tough love for
magnesium. Poster presented at Challenges of the Modern
Object, Science Museum London, 17 October 2019.
Sanchem, Inc. 2017. Sanchem SafeGard CC-13062Mg.
SDS, issued 5 April 2017. Chicago, IL: Sanchem.
Sanchem, Inc. 2018. Sanchem 560 Cleaner. SDS, issued
5 December 2018. Chicago, IL: Sanchem.
Shashikala, A.R., R. Umarani, S.M. Mayanna, and A.K.
Sharma. 2008. Chemical conversion coatings on magne-
sium alloys – A comparative study. International Journal
of Electrochemical Science 3: 993–1004.
Umehara, H., M. Takaya, and S. Terauchi. 2003. Chrome-
free surface treatments for magnesium alloy. Surface and
Coatings Technology 169: 666–69.
Verband der Automobilindustrie. 2013. VDA 233-102
(06/2013): Cyclic corrosion testing of materials and compo-
nents in automotive construction. Berlin: VDA.
Author
Abigail Elizabeth Rodriguez received her BA in art
conservation from Scripps College and is currently in her
70  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND MODERN METALS

third year of the Winterthur/University of Delaware MS

Program in Art Conservation, where she is majoring in
objects and minoring in textiles with a focus on modern
and industrial materials. Her research interests include
the intersection of industrial treatment methods and
conservation practice, alternative approaches to site-
based heritage preservation, and adhesives for plastics.
She is dedicated to promoting community-based pres-
ervation efforts, diversity, equity, and inclusion in the
conservation field.

Materials list
AZ31 – 0.0010-meter sheet from Buy Metal
https://store.buymetal.com/

Sanchem’s SafeGard CC-13062Mg and 560 Cleaner

www.sanchem.com/

Appendix A. Weights of the samples

Polished Coated Corroded Cleaned Final coated Δ after corrosion Average rate over
Sample ID
sample (g) sample (g) sample (g) sample (g) sample (g) (g) 48 h (g/min)
AZ31-A 4.472 4.472 4.475 4.463 4.463 0.009 3.12 × 10−6
AZ31-B 4.429 4.431 4.433 4.421 4.421 0.010 3.47 × 10−6
AZ31-C 4.703 4.704 4.705 4.696 4.697 0.008 2.78 × 10−6
Corrosion and Conservation of Nickel Silver Alloys
Recovered from Historic Shipwrecks
Ian D. MacLeod
Shipwrecks Museum
Fremantle WA, Australia
ian.macleod@museum.wa.gov.au
Abstract
The impact of the corrosion environment on the decay of nickel
silver is illustrated by the contrasts between shallow waters off
the Western Australian coast and those found in the extremely
deep and icy waters at the RMS Titanic (1912) wreck site. A
19th-century nickel silver fob watch and spoon were recovered
from anaerobic sediments on the site of the former Fremantle
Long Jetty at a depth of 2.5 m. The scanning electron microscopy
(SEM) examination of the internal parts of the fob watch revealed
a corrosion matrix with high concentrations of nickel and
lesser amounts of copper and zinc. The anaerobically corroded
watch is contrasted with a set of concreted nickel silver spurs
and chains from the wreck of the Macedon (1883) from the
Shallow aerobic corrosion at the SS Macedon (1883) wreck
A set of nickel silver spurs and chains (stamped with the
sovereign’s initials ‘VR’) from an ill-fated expeditionary
force, which left Fremantle for the Kimberley region of
Western Australia, were recovered from the wreck of a
ship located on a reef off Rottnest Island, only 22 km
from its departure point. The spurs were covered with
an adherent layer of concretion, while parts of the chains
were relatively free of marine deposits (Figure 1). There
was selective corrosion on the chain links corresponding
to corrosion relief from the stress of the drawn metal,
which is seen in the fine striations around the metallic
rings (Figure 2). Chemical analysis of the nickel silver
spurs and chain, reported in Table 1, shows a composition
of 60.2 ± 1.1% Cu, 24.2 ± 2.7% Zn and 13.0 ± 0.1% Ni,
which is typical of nickel silver alloys of that period
(Simons 1969). The concretion was also analysed, and
the normalised results are also reported in Table 1. The
corrosion products trapped in the concretion showed
that there had been selective mobilisation of zinc, along
with impurities such as lead and tin from the single-
phase alloy. The spurs and chains do not conform to
shallow and well-oxygenated wreck site off Rottnest Island. The
corrosion products were identified by X-ray diffraction (XRD)
and revealed significant dezincification and mobilisation of
nickel. Desalination data indicates different chloride release
mechanisms to normal brasses. The heavy silver plate covering
the nickel silver cutlery from the Titanic was re-examined and
a new interpretation of the delamination mechanism has been
developed.
Keywords
shipwrecks, corrosion, conservation, nickel silver alloys,
aerobic, anaerobic
any standard alloy but are similar to a 16% nickel silver
(leaded nickel brass) used in small castings but with more
zinc and less nickel, which would have made for an easier
casting (Simons 1969, 119). Wrought alloys, such as those
used in the chains, are often known as German silver.
They have a white tint, are tough, malleable, ductile and
corrosion-resistant, and their high electrical resistance
is a major factor in affecting corrosion performance
(Simons 1969). A detailed study of the oxide film on
cupronickel alloys in seawater shows substitution of Ni2+
into vacant positions of Cu+ in the Cu2O lattice, which
increases the electrical resistance of the oxide film. The
film changes from straight Cu2O to a mixture of CuxO
and a copper hydroxide/oxide layer, which protects the
underlying alloy (Jin et al. 2019).
Both nickel silver objects from the Macedon wreck come
from the same section of the ternary alloy phase diagram,
which shows that there is only a single α-phase present.
The ratio of copper and nickel in the concretion is the
same at 0.8, which is consistent with the less reactive
72  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND MODERN METALS

found in the concretion are similar to the values for brass

objects found in an aerobic environment with low oxygen
levels (MacLeod 1985). The impact of the concretion on
the corrosion mechanism is to provide an oxygen diffu-
sion barrier to the corroding surfaces. The large amount
of iron in the concretion is due to the incorporation of
iron corrosion products from the adjacent structural steel
of the vessel. The properties of the nickel silver alloys are
sensitive to the relative proportions of zinc and nickel,
since at equal amounts of nickel and zinc the disorder
of the alloys at low concentrations of the third element
Figure 1. Concreted and corroded nickel silver spurs and chains from changes to strong order (Chadwick and Argent 1961).
the Macedon (1883) wreck
The corrosion potentials of the spurs and chains in
seawater were +0.093 and +0.055 V, respectively,
compared to the normal hydrogen electrode. The more
positive Ecorr value of the spurs may be due to a higher zinc
content (Table 1). These voltages are within ± 0.025 V of
the in situ corrosion potentials recorded on the wreck of
the Day Dawn (1886) for dezincified brass bolts which
had been submerged in shallow waters for the same time
as the other wreck. The nature of the zinc-rich corroded
surfaces on the nickel silver objects from the Macedon is
essentially the same as the zinc-rich corroded surfaces
on the brass drifts in the Day Dawn, both vessels being
shipwrecked within three years of each other. Areas of the
objects on the Macedon that were not covered in concre-
tion showed extensive dezincification of the surface. The
corrosion potentials at a pH of 8.2 are equivalent to a
Figure 2. Backscattered secondary electron SEM image of the Macedon surface concentration of 1.1 × 10−9 M Cu+ in equilibrium
chain links showing corrosion along stress lines induced during their
with a cuprite layer, i.e. very low. Infrared analysis of the
fabrication (90×)
corrosion products showed primary Cu2O with CaCO3.
Table 1. Analyses of standard nickel silver alloys and artefacts from the
The X-ray diffraction (XRD) analyses showed that the
Macedon (1883) and Long Jetty sites
principal oxidation product on the spurs was cuprite
Cu Ni Zn Pb Sn Fe (Cu2O), along with major amounts of zincian parata-
Macedon spurs 59.4 13.0 26.1 0.52 0.26 0.31
camite, previously called anarakite (Cu,Zn)2(OH)3Cl)
Macedon chains 60.9 12.9 22.3 0.31 0.10 0.55
(25-325). Areas of the spurs not protected by the concre-
Macedon concretion 17.5 3.5 9.8 0.6 0.09 4.1
concretion to 100% 49.1 9.8 27.5 1.7 0.3 11.6
tion showed extensive mineralisation and scanning
Long Jetty spoon 60.7 21.2 17.1 0.006 n.d. n.d. electron microscopy (SEM) studies indicated that there
Nickel silver 16 60 16 16 5 3 was little mobilisation of nickel but significant loss of zinc
Nickel silver 20 64 20 8 4 4 from the parent metal. Among the corrosion products, the
lemon-green nickel hydroxy chloride (NiClOH) (2-935)
was characterised with the main copper-chloride phase
nature of the parent metals, while the zinc is present in (Cu7Cl4(OH)10.H2O) (23-948). Owing to the ion exchange
the concretion at 1.1 times the alloy composition, which between amorphous FeO.OH corrosion products on the
indicates that there is preferential corrosion of the zinc 532-ton iron-screw steamer, the local surface concentra-
from the alloy, corresponding to its position in the elec- tion of sulfate was increased to the point of precipitating
trochemical series. The relative proportions of the metals mineral species such as Cu19Cl4SO4(OH)32.2H2O (8-135)
CORROSION AND CONSERVATION OF NICKEL SILVER ALLOYS RECOVERED FROM HISTORIC SHIPWRECKS
and the grey, white ZnSO4.3Zn(OH)2.4H2O (9-204), as
evidenced by 0.53% sulfate and 4.4 wt% chloride in the
concretion analyses.
Desalination of the nickel silver spurs was completed after
three months of washing in 2 wt% sodium sesquicarbo-
nate. The desalination of nickel silver objects is different
to binary alloys, owing to the nature of the mixed oxide
coating on the surface of the ternary alloy. The chloride
release rate remains the same after the first plateau has
been reached, as shown in Figure 3, which contrasts
with a marked diminution for second and successive
washes for brass and bronze objects (MacLeod 1987).
The normalised chloride release rate for the Macedon
spurs and chains was 3.5 ± 0.2 μg.cm−2hr−½, which is
significantly lower than the mean rate for brasses of
14.2 ± 5.7 μg.cm−2hr−½. However, the total treatment
times for the Macedon spurs and chains was the same
as most aerobically corroded marine brasses (MacLeod
1987). The similarity of the chloride release slopes in both
the washes and the lower amounts of chlorides being
released into the sesquicarbonate solution are consistent
with decreased permeability of the oxide film covering
the original surface, in which a combination of mixed
oxide and hydroxides of nickel and copper have created
a different chloride diffusion barrier (Jin et al. 2019). A
consequence of the different barrier is that longer wash
times are needed for nickel silver alloy objects compared
to straight brass artefacts. It was noted that under the
standard pH 10 conditions of the sesquicarbonate
wash, the molar ratio of released chloride to copper
was 1.5 ± 0.5; however, the lack of data on the amount
of nickel and zinc ions released into the wash solutions
prevented detailed modelling of the processes.
Aerobic corrosion at depth on the RMS Titanic
(1912)
One of the most comprehensive reports on the corro-
sion of ternary copper-nickel-zinc in deep ocean waters
was written in 1976 by the US Navy when hundreds of
alloys were assessed. The normally good shallow water
performance of copper alloys can fall away as parting
corrosion (dezincification and denickelification) results
in an uneven attack on the solid solution alloys (Reinhart
1976). At depths of 2,500 ft. (762 m), copper corrodes
at the same rate as at the surface, and the addition of
only 8% nickel normally confers protection against
dezincification at 40 wt% of zinc. Ternary alloys created
73
the corrosion products expected at the deepest sites at
6,000 ft. (1,829 m), with minerals such as CuCl2.2 H2O
and Cu2(OH)3Cl being formed. The ratio of sulfate to
chloride in the corrosion products found on nickel silver
corrosion coupons at depth was 11.7, which is much
higher than the 0.12 found in the Macedon corrosion
matrixes. The sulfate levels were 11% by mass and the
chlorides were only 0.9 wt%. Previous reports on the
decay matrixes on the deeper Titanic (1912) site also
showed up a dominance of sulfate-containing corrosion
products due to electrostriction of the sulfate ions in cold
and very deep water, which effectively increases their
surface concentration to the point of bringing about
precipitation of sulfate-containing corrosion products
(MacLeod and Pennec 2004).
The corrosion products on nickel silver alloys reported
by the US Navy at 6,000 ft. are the same as observed on
recovered nickel silver cutlery from the deeper Titanic
wreck site. Coupons of copper-nickel alloys produced
nickel(II) hydroxide {Ni(OH)2} as a significant corrosion
product. It is likely that the hydroxides are precipitated
due to localised increased pH associated with the cathodic
reduction of dissolved oxygen on the non-ferrous metal
alloy surface. This decay product is not unexpected as
surface corrosion of the Macedon nickel silver spurs
produced the nickel hydroxy chloride {NiOHCl} from
corrosion at less than 10 m of turbulent water, which
would decrease the local pH to the point where copre-
cipitation of the mixed hydroxy chloride would be
kinetically favoured. Data on copper coupons showed
a steady decrease in corrosion rate over time, and the
sediment decay rate was 27% lower than the open ocean
rate at 6,000 ft. After three years in the deep dark ocean
waters, the corrosion rate had fallen by 65%, and this is
a common passivation process as the oxide film grows
and slows down the long-term corrosion rate, as shown
in Table 2 (Reinhart 1976).
Table 2. Corrosion rates at 4,000 ft. in the Atlantic Ocean, US Navy
(table 23, pp. 85, 86)
Corrosion rate: Corrosion rate:
Alloy
sea (mm/year) sediment (mm/year)
Copper 0.041 0.030
CA 752 American
0.015 0.010
65% Cu, 18% Ni, 17% Zn
The corrosion products on the tested cupronickel
alloys included tenorite, nickel oxide (NiO) and the
corresponding hydroxide (Ni(OH)2), cupric chloride,
74  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
copper(II) hydroxy chlorides and a trace of nickel sulfide
(NiS). The corrosion on the electroplated nickel silver
cutlery on the wreck of the RMS Titanic (1912) was
much more extensive than on the base metal alloys,
which were exposed for only a few years compared with
65 years at the Titanic wreck site. The nature of the passive
film in seawater changes with pressure, as seen when
the corrosion rate goes through a minimum at around
2,500 ft. (762 m), where the corrosion rate increases from
0.016 mm/year, to reach 0.051 mm/year at the depth of
4,000 ft. (1,828 m) due to changes in the nature of the
passive surface film. If we assume a similar corrosion
rate on the Titanic wreck site, it is not unreasonable to
expect to find significant decay problems with the nickel
silver objects. Recovered artefact treatments were based
on traditional electrolysis in sesquicarbonate solutions
(Montluçon and Lacoudre 1989). Although the results
were initially promising, there were post-treatment issues
with continued internal corrosion which led to surface
exfoliation despite good storage conditions. The products
also indicated continued high concentrations of nantokite
within the objects (Pennec, pers. comm., 1998).
Most of the cutlery on the Titanic was made by Elkington
in the United Kingdom and they typically coated their
nickel silver base metal castings and mouldings with a
35 μm layer of silver, which is readily seen as the surface
material peeling off the dinner plates shown in Figure 4.
Elkington silver plate was the thickest that could be
bought at the time, with most other suppliers happy to
sell their EPNS with coatings of 15–25 μm (MacLeod
and Pennec 2004). For these objects, the deep water has
exacerbated pinhole corrosion in microscopic defects in
the silver plate, which has deformed due to the pressure in
the hollowed-out pits beneath the silver layer (Figure 4).
Chloride ions readily penetrate the plating owing to the
Figure 3. Desalination plot of chloride vs square root of time for Macedon
nickel silver spurs
MODERN METALS
Figure 4. Delamination of the thick electrochemically deposited silver
layer on cutlery from the Titanic. Photo: Chemistry Centre of Western
Australia
electrostriction brought about by the near-freezing water
and high pressure which reduces their size. They also
bring about accelerated pitting corrosion in the under-
lying nickel silver alloy (MacLeod and Pennec 2004).
Even though most of the tableware was recovered from
the debris field between the main structural elements of
the ill-fated wreck, where anoxic sediment layers abound
and create massive differential aeration problems for
brass artefacts, these anaerobic sediments do not appear
to have played a significant role in the decay of the nickel
silver cutlery. The voltage difference between the pure
silver and the underlying nickel silver alloy would have
been sufficient to drive significant internal galvanic
corrosion. The difference in the electrochemical reac-
tivity of the interior of the plated cutlery is like that of
a forged coin recovered from the Batavia (1629) wreck,
where the deeply etched silver-enriched outer layer was
connected by chloride ions to a tin-silver-copper alloy
core (MacLeod 1984). During 350 years in the surf, all the
debased silver-tin-copper core had corroded, with most
decay products being lost through the etching pinholes. It
is not unexpected to have significant amounts of residual
metal left on the Titanic cutlery after only 80 years of
corrosion. It is possible that the microporous surfaces of
the Elkington plate became occluded during their initial
treatment, which left a reactive matrix of copper and
nickel chlorides trapped within the corroded base metals.
Owing to greater solubility, the zinc corrosion products
were expected to have been lost to the Atlantic Ocean.
During the normal cycling of temperature and relative
humidity in non-ideal storage conditions, moisture
would have penetrated the pores and reactivated the pits,
allowing the oxidation products to mobilise and undergo
surface oxidation with concomitant precipitation.
CORROSION AND CONSERVATION OF NICKEL SILVER ALLOYS RECOVERED FROM HISTORIC SHIPWRECKS 75

The impact of the changing nature of the decay products

on the original surface is significant, as indicated by the
molar volumes of corrosion products. The ternary nickel
silver alloys have a density of 7.7 ± 0.5 g.cm−3, so even
the formation of cuprite, with a density of 6 g.cm−3, gives
double the molar volume. Such increases are typical for
decay matrixes that include the corrosion products of
nickel oxide (NiO), which is 50% larger than the parent
alloy. The formation of nickel(II) chloride is associated
with an increase in molar volume by a factor of 3¾, and
the heavy silver plating was readily disbonded under
such pressure. Treatment with a 50% volume aqueous
solution of acetonitrile and water for 48 h in the LP3
laboratories at Semur-en-Auxois stabilised the objects,
since they did not corrode after six months in open
storage with no relative humidity control. During this
process, the acetonitrile complexed and extracted the
copper(I) chlorides, which breaks the cyclic corrosion
process (MacLeod et al. 1981). Apart from the specific
bonding of acetonitrile with Cu+ ions, the formation of
hexacoordinated Ni2+ ions with acetonitrile will also be
effective in removing nickel corrosion products from the Figure 5. Reverse of a nickel silver fob watch from the Long Jetty site
showing the escapement adjustment
degraded matrix (Inada and Funahashi 1997).

Shallow anaerobic corrosion of a nickel silver

pocket watch
The Long Jetty extended 1 km from the shore into
the Indian Ocean from 1873 until 1897 when the new
Fremantle Harbour was opened. Owing to the exposed
nature of the Long Jetty site, localised wave action would
cause the sailing ships to move, and a vast range of
goods, including a pocket watch, were lost by the unco-
ordinated, and often drunk, sailors (Figure 5). During
examination in the conservation laboratory, the inner
workings were assessed and the whole assembly was
examined using backscattered secondary electron SEM
images (Figures 6, 7). Figure 6. Iron screw with (1) lepidocrocite, (2) copper sulfide patina,
(3) redeposited copper, (4) original surface and (5) CaCO3 deposit (90×)
The grey-black corrosion products on the surface of
the fob watch case showed that the parent nickel silver surmounted by a grey-black sulfide layer. This indicates
alloy had been in an anaerobic microenvironment for that the burial position is 180° to the image (Figure 5).
significant periods. This is consistent with the artefacts The details of the image of the cog screw blocked with
being recovered from sediment layers up to 1.8 m deep corrosion products are shown in Figure 6. A detailed
that were rich in decayed sea grass. The patina on the examination of the corrosion products adjacent to the
watch case is a thin mottled layer of chalcocite (Cu2S), outer ring rear locking plate showed that colonies of
and the main flange plate of the watch has a mixed cuprite anaerobic bacteria had penetrated the area and replicated
(Cu2O), in the bottom section, and chalcocite patina, in the as-cast dendritic structure of the watch as an isomor-
the upper section, as indicated by the red-brown patina phous Cu2S layer. A series of corrosion dimples filled with
76  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Figure 7. SEM backscattered second electron image of the copper sulfide
layer at 900×
decay matrixes are indicators that colonies of anaerobic
bacteria had been present inside the back of the watch
(Figure 7). The object was returned to the finder after
six weeks of washing in a 2 wt% sodium sesquicarbonate
solution, which prevented a more detailed examination.
A nickel silver spoon recovered from the same location
as the watch showed a mixed copper sulfide patina
and patches of metal covered with a thin oxide film.
The higher nickel content of the spoon had minimised
segregation attack in the anaerobic microenvironment
(Figure 8; Table 1).
Figure 8. Image of the sulfide-patinated Long Jetty nickel silver spoon
(Table 1)
Conclusion
The deceptively simple microstructure of nickel silver
alloys, in which both the nickel and zinc are completely
soluble in the copper-rich α-phase, can lead to the
false assumption that the problems of internal galvanic
corrosion associated with brass and bronze artefacts
on historic shipwrecks are not going to be present in
such inherently homogeneous materials. Depending on
MODERN METALS
the microenvironment, the main body of the alloys is
subject to selective corrosion of the zinc- or nickel-rich
sections of the alloy. In aerobic corrosion, the greater
solubility of zinc chloride corrosion products means that
zinc corrosion products are often concentrated in the
concretion phases attached to the objects. Underneath
the protective microenvironment of the marine growth,
zinc can accumulate to produce zincian paratacamite
((Cu, Zn)2(OH)3Cl), formerly called anarakite), which
is a strong indicator that the underlying alloy is nickel
silver. The low corrosion rate associated with nickel silver
alloys is due to the changes in the nature of the oxidation
film on top of the original surface, since the copper(I)
oxide incorporates nickel ions in its structure and this
creates a barrier of higher electrical resistance, which
slows down the reduction of dissolved oxygen.
The problems of electroplated nickel silver cutlery
recovered from the wreck of the RMS Titanic have been
compared to the way in which the internal debased
coinage on the Batavia (1629) shipwreck was eaten away
during 350 years of corrosion in the surf. Silver surfaces
function as excellent cathodic sites for the reduction of
dissolved oxygen, and chloride ions readily penetrate
the microscopic pinholes in both the electroplate and
in the depletion-etched surfaces on the forged coins.
This leads to localised pitting corrosion in the vicinity of
the defects. This mechanism became apparent with the
decay of heavily electroplated nickel silver on the wreck
of the RMS Titanic (1912), as sections of the electroplated
layer had depressions around pinholes as the pressure
squashed the noble metal to conform to the shape of the
underlying substrate. During their original electrolysis
treatment, it is possible that the plating pores above the
pits became occluded and sealed the internal structure
from conservation treatment. However, after years of
storage in ambient conditions, moisture was able to
penetrate the pores and reactivate the corrosion cycle.
Owing to the much lower density of the corrosion prod-
ucts, the volume expansion of the decaying metal caused
disbondment of the silver coating. Treatment of these
objects with 50% volume aqueous acetonitrile removed
large volumes of copper(I) and nickel(II) chlorides and
stopped corrosion in its tracks.
Acknowledgements
The authors would like to pay special thanks to Stephane
Pennec, Jon Carpenter and Kalle Kasi for their assistance.
CORROSION AND CONSERVATION OF NICKEL SILVER ALLOYS RECOVERED FROM HISTORIC SHIPWRECKS 77

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Department of Commerce, National Technical Infor-
mation Service, AD-AO21 279, 264 pp.
First Step in the PROCRAFT Project on WWII Aircraft
Heritage: Investigation and Conservation of the
Aluminium Alloys
Magali Brunet*
Centre for Materials Elaboration
and Structural Studies (CEMES-
CNRS), University of Toulouse
Toulouse, France
magali.brunet@cemes.fr
Luc Robbiola
TRACES Laboratory (UT2J-CNRS),
University of Toulouse
Toulouse, France
robbiola@univ-tlse2.fr
Christophe Deshayes
Centre for Materials Elaboration
and Structural Studies (CEMES-
CNRS), University of Toulouse
Toulouse, France
christophe.deshayes@cemes.fr
Elena Bernardi
Department of Industrial
Chemistry, University of Bologna
Bologna, Italy
elena.bernardi@unibo.it
Carla Martini
Department of Industrial
Engineering, University of Bologna
Bologna, Italy
carla.martini@unibo.it
Cristina Chiavari
Department of Cultural Heritage,
University of Bologna
Bologna, Italia
cristina.chiavari@unibo.it
Andrea Balbo
Corrosion and Metallurgy Study
Centre ‘Aldo Daccò’, Department
of Engineering, Technopole of the
University of Ferrara
Ferrara, Italy
andrea.balbo@unife.it
Cecilia Monticelli
Corrosion and Metallurgy Study
Centre ‘Aldo Daccò’, Department
of Engineering, Technopole of the
University of Ferrara
Ferrara, Italy
cecilia.monticelli@unife.it
Jaromír Fišer
Department of Instrumentation
and Control Engineering, Faculty
of Mechanical Engineering, Czech
Technical University in Prague
Prague, Czech Republic
Jaromir.Fiser@fs.cvut.cz
Tomáš Vyhlídal
Department of Instrumentation
and Control Engineering, Faculty
of Mechanical Engineering, Czech
Technical University in Prague
Prague, Czech Republic
Tomas.Vyhlidal@fs.cvut.cz
Jane Echinard
Arc’Antique Laboratory, Grand
patrimoine de Loire-Atlantique
(GPLA)
Nantes, France
Jane.ECHINARD@loire-atlantique.fr
Elodie Guilminot
Arc’Antique Laboratory, Grand
patrimoine de Loire-Atlantique
(GPLA)
Nantes, France
Elodie.GUILMINOT@loire-
atlantique.fr
*Author for correspondence

Abstract
The conservation of excavated wrecks or abandoned aircraft is
of cultural and historical interest. A first step in understanding
the challenges posed by this type of cultural heritage and
in finding solutions for its conservation is to document the
constituent materials and their subsequent alterations.
In the project PROCRAFT, aircraft wrecks from six nations
involved in WWII were collected and then studied. Analysis
of the elemental composition together with archival research
allowed identification of the wrought aluminium alloys used
in the non-structural and structural parts of the aircraft. Three
manufacturing processes were recognised: rolling, extrusion
and forging. The corrosion protection treatments applied during
manufacturing of the aircraft parts were also examined, which
revealed cladding with a thin aluminium foil, anodisation or
the application of primer/paint. Based on typical examples
of the alterations that occurred in the metal components, we
demonstrate the importance of this original protection against
the aggressiveness of the environment.
Keywords
aircraft heritage, aluminium alloys, Al cladding, protective
coatings

Introduction
Although WWII is often considered the golden age of
military aviation, battles in the air resulted in enormous
human and material losses, with the latter including a
large number of wrecks on European soil and in the sea.
Volunteers and associations have long been engaged in
recovering the wrecks, but despite the undeniable histor-
ical and emotional value of WWII aircraft for Europeans,
only recently have these heritage objects come to the
attention of archaeologists and conservators. Nonetheless,
they are still rarely exhibited in museums.
The challenges in the conservation and protection of
aircraft heritage include the documentation of constit-
uent historical materials and their alterations as well as
the need for innovative approaches to the development
of protective coatings and to the monitoring and control
of atmospheric conditions in storage and display areas.
These challenges are addressed in project PROCRAFT
(PROtection and conservation of heritage airCRAFT),1
a joint programming initiative on cultural heritage. The
project also aims at connecting the multiple actors in
FIRST STEP IN THE PROCRAFT PROJECT ON WWII AIRCRAFT HERITAGE: INVESTIGATION AND CONSERVATION OF THE ALUMINIUM ALLOYS
the operational chain, and specifically those in France,
Italy and the Czech Republic, from the recovery to the
exhibition stage.
The present study was based on the work carried out
by several associations (Aérocherche, Aérothèque,
Ailes Anciennes Toulouse, Aéroscope and ABSA 39-45
in France; Volandia and Air Club & Fun in Italy) that
excavated or collected wrecks from various environments
(terrestrial ground, sea, lakes), mainly in France and
Italy, and gathered information/testimonies related to
the crashes. The first task of the project was to identify
and record a significant group of WWII aircraft/wrecks,
most of which are bombers and fighters from Germany,
France, Italy, the USA, the UK and the USSR that crashed
during military operations between 1939 and 1945. Other
aircraft dating from the same historical period, including
civil planes abandoned after the end of their lifetime and
recovered years later (such as the Dewoitine D.338), were
considered as well.
Documentation of the artefacts, parts of wrecks or full
aircraft, and their constituent materials is an important
part of understanding aeronautical heritage, especially
since archival data are difficult to recover. Moreover,
recording the condition of the artefacts (their alteration)
will provide insights into the main parameters driving
corrosion. This knowledge will be used by PROCRAFT
to select restoration treatments, determine the appro-
priate protective coating for these materials and, even-
tually, develop the appropriate preventive conservation
procedures and facilities (large storage hangar, outdoor
storage).
This article focusses on the first task of the PROCRAFT
project, which was to obtain detailed information on a
wide set of WWII aircraft, including the identification of
wrought aluminium alloys, the principal materials used
in the construction of aircraft, and their anti-corrosion
protection. A summary of the conservation state of the
aircraft is provided and the relations between the alloy
manufacturing, the environment and the extent and
morphology of the corrosion are discussed.
Methodology and experimental setup
A methodology was developed to uniformly record
information on each aircraft/wreck. Briefly, in a first
step information is collected on the historical context,
the circumstances of the crash or the abandonment of
79
the aircraft, details about its excavation or recovery, the
global condition of the aircraft (sometimes less than 1%
of the whole aircraft is recovered) and the availability of
any archives linked to the aircraft. All original documents
are clearly very important to correctly classifying the
aircraft, whether historically or technically.
In a second step, the constituent materials (aluminium
alloys and protective coatings) are identified and their
conservation state is assessed. Macro- to micro-scale
observations of the samples coupled with elemental and
structural analyses are performed to extract precise infor-
mation on the elemental composition and microstructure
of the alloys as well as on the nature and composition of
the original protective coatings. Corrosion features are
also examined.
For this study, representative samples were prepared by
cutting the aircraft parts along three spatial directions:
rolling or longitudinal (L), short transverse (i.e. thick-
ness, ST) and long transverse (LT), defining the main
metallurgical planes: rolling (L, LT), transverse (LT, ST)
and normal (L, ST), as shown in the insert of Figure 1.
The sections were then prepared, embedded in epoxy
resin, mechanically polished down to 2400 SiC paper
grade and then polished on diamond paste cloths down
to 1 µm particle size to obtain a mirror-like finish. The
elemental compositions of the alloys were determined
using a scanning electron microscope (SEM) (LaB6 Zeiss
EVO 25) operating at 20 keV (1 nA) equipped with a
Bruker XFLAsh energy dispersive X-ray spectroscopy
(EDS) detector. Three measurements of 5 million counts
on ~0.2 mm2 areas were averaged. Quantitative determi-
nation was carried out with a Quantax system (Bruker
Esprit 2.1 software), applying the phi-rho-z method.
The results were normalised to 100 wt% after carbon
deconvolution. Images in backscattering electron (BE)
mode completed with EDS maps were acquired for the
detection of protective coatings and the observation of
corrosion features.
Results and discussion
Identification of alloys and their anti-corrosion
protection
The 34 aircraft obtained thus far are from Germany (6),
France (7), Italy (5), USA (7), UK (2) and USSR (1). Five
artefacts have yet to be attributed to a specific aircraft
and thus to a country. As invasive analyses could not
80  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
be performed on some aircraft, 16 artefacts for which
sampling could be performed are presented below.
Wrought aluminium alloys are used in three manu-
facturing processes (Davis and Semiatin 1989): rolled
products (plates or sheets, mainly fuselage skin), extruded
products (stiffeners, stringers, both with a structural
role; Alderliesten 2018) and forged products (parts with
complex shapes). In addition, some stiffeners riveted to
plates are fabricated by rolling and folding.
Identification of alloys
Since corrosion is directly linked to microalloying
elements and microstructure, identification of the alloy
type in relation to the manufacturing processes is critical
for establishing a diagnosis and, subsequently, conser-
vation protocols.
In most of the collected and analysed samples (Table 1),
the wrought alloys were exclusively Al-Cu-Mg (Si), corre-
sponding to the Duralumin family, nowadays referred
to as Al alloys of the 2000 series. The nominal composi-
tion of these alloys is Cu (3–5 wt%), Mn (0.4–1.5 wt%),
Mg (0.5–1.7 wt%) and Si (0.5 wt%). Si is either not
controlled or it is added in small quantities whereas
Fe, also present in the alloy composition, is always an
impurity. Trace amounts of other elements (< 0.1 wt%)
may occur as well: Zn, Ti, Ni, Pb.
As reported in Table 1, two specific sub-families of alloys
can be classified. Their denomination differs according
to country (Ouissi et al. 2019, Ouissi 2020):
• Duralumin, with a Mg content < 1 wt%: the forerunner
of the modern 2017A alloy, called Duralumin or
A-U4G in France (Chevigny 1954), AlCuMg1 or 3115
in Germany (Böhle 1956), Hiduminium DU Brand in
the UK (High Duty Alloys 1948) and 17S in the USA
(ALCOA aluminum and its alloys 1935);
• Super Duralumin, with a Mg content of 1–1.5 wt%:
the forerunner of 2024 alloy, called Duralumin FR or
A-U4G1 in France, AlCuMg2 or 3125 in Germany,
Hiduminium 72 in the UK and 24S in the USA. This
alloy has a high yield, a high ultimate strength and a
high degree of hardness.
For German aircraft, both Duralumin (AlCuMg1) and
Super Duralumin (AlCuMg2) were used in the manu-
facture of rolled and extruded products. The choice of
alloy for the different parts of the aircraft was left to the
manufacturers. It should be noted that on some parts, e.g.
MODERN METALS
the stringer of DO 217 and plate 2 of the Junkers 88, the
measured Mg content was at the border of Duralumin and
Super Duralumin. In these cases, the alloy was classified
according to the content of other elements, Mn and Si
in particular.
Duralumin (low Mg rate < 1 wt%) was used in most
French aircraft for structural and non-structural parts.
However, contemporary studies have shown that Super
Duralumin was used in France only after WWII (Guil-
lemin 1946). For example, the Espadon, an aircraft
from 1948, was fabricated with Duralumin, which was
selected for both the structural and non-structural parts
(stiffeners).
In American aircraft, Super Duralumin (24S alloy) was
used for non-structural (skin) and structural parts.
The alloy was employed in aeronautical construction
already in 1937, first in the DC-3 and then more widely
(ALCOA 1935).
Among British and Italian aircraft, only Duralumin has
been identified so far in the collected parts.
The two forged products in the collection are propeller
blades, one from a Lockheed P38 and the other from
an unidentified aircraft. The P38 alloy, which does not
contain any Mg, is a 25S alloy. As noted in ALCOA’s
archives (ALCOA 1935), the 25S was specifically devel-
oped for forged products, with its advantage consisting
of a higher resistance to high temperatures. The alloy of
the blade from the non-identified aircraft is Duralumin.
Identification of the protection type
The corrosion of aluminium alloys was an early concern
for aluminium manufacturers. Although paint was
initially applied mainly as colouring/camouflage, it also
ensured corrosion protection. Primers with anti-corro-
sion pigments (chromates) were applied underneath.
Other types of protection in the 1920s included anodi-
sation. However, due to cost issues and difficulties in
treating large areas with this process, it was replaced in
the late 1920s by a method in which the alloy was cladded
between two thin sheets of pure Al, called Alclad in the
USA (Dix 1927) and Vedal in France (Pubellier 1929).
Most of the recovered WWII aircraft in the collection
(Table 1) were originally painted but the paint has been
retained on only a few of them. In cases of severe corro-
sion, the original protection is missing and cannot be
inferred (ND).
FIRST STEP IN THE PROCRAFT PROJECT ON WWII AIRCRAFT HERITAGE: INVESTIGATION AND CONSERVATION OF THE ALUMINIUM ALLOYS 81

Table 1. Elemental composition (wt%) of wrought aluminium alloys and the protective coatings for aircraft from five countries

Elemental composition (wt%) Protection*/

Manufacturer / Aircraft Product / Manufacturing Identified
Thickness
(year of manufacture) / Thickness (mm) Al Cu Mg Mn Fe Si alloys
(µm)
Sheet / Rolled / 1 93.65 4.04 0.83 0.50 0.40 0.35 AlCuMg1 C / 50
Dornier / Do 217 (1943)
Stringer / Extruded / 3.5–5 92.71 4.20 1.14 0.81 0.33 0.51 AlCuMg2 ND
Heinkel / He 111 (1937) Stringer / Extruded / 2 93.21 4.29 0.61 0.75 0.34 0.46 AlCuMg1 O
Germany

Heinkel / He 177 (1943) Plate / Rolled / 1–1.4 93.39 4.43 0.71 0.55 0.29 0.41 AlCuMg1 C / 50
Messerschmitt / Bf 109 (1944) Plate / Rolled / 1.1–1.2 93.59 4.13 1.52 0.49 0.15 0.02 AlCuMg2 C / 50
Engine plate 1 / Rolled / 1.1 93.21 4.64 1.34 0.45 0.15 0.07 AlCuMg2 C / 75
Engine plate 2 / Rolled / 1.5 93.67 4.15 0.97 0.39 0.24 0.40 AlCuMg1 C / 75
Junkers / Ju 88 (1943)
Stiffener / Rolled and A
92.84 4.75 0.80 0.51 0.32 0.59 AlCuMg1
folded / 0.8
Dewoitine / D.520 O
Plate / Rolled / 0.7–2 93.20 4.35 0.50 0.56 0.31 0.46 Duralumin
(1940)
Dewoitine / D.338 Stiffener / Extruded / 2.5 94.05 3.58 0.59 0.52 0.34 0.64 Duralumin A
France

(1937) Skin / Rolled / 0.5 93.13 4.45 0.79 0.62 0.31 0.50 Duralumin C
SNCASO / C
Skin / Rolled / 2.0 93.68 4.32 0.65 0.47 0.36 0.34 Duralumin
Espadon (1948)
Latécoère / Laté 298 (1940) Plate / Rolled / 1.5 93.69 4.16 0.69 0.58 0.24 0.56 Duralumin C / 95
Plate / Rolled / 1–1.2 93.26 4.19 0.94 0.65 0.43 0.49 Hidu DU Brand ND
UK

Supermarine / Spitfire (1942) Stiffener / Rolled and ND

94.06 3.68 0.91 0.63 0.38 0.28 Hidu DU Brand
folded / 1.8
Republic Aviation / P47D Plate / Rolled / 1 92.72 4.78 1.45 0.54 0.27 0.15 24S/ C / 50
Thunder (1943) Stiffener / Extruded / 1 93.15 4.33 1.32 0.55 0.31 0.18 24S ND
USA

Lockheed / P-38 Lightning Skin / Rolled / 1 91.63 5.44 1.55 0.57 0.39 0.42 24S C / 30
(1943) Stiffener / Extruded / 1 91.63 5.64 1.51 0.62 0.31 0.30 24S A
Lockheed / P38 (< 1944) Blade / Forged / 2–112 93.58 4.57 0.05 0.70 0.44 0.53 25S A
IMAM / RO37 (1936) Plate / Rolled / 0.7 94.35 3.86 0.53 0.55 0.42 0.21 Duralumin ND
Italy

Macchi / MC202 (1942) Sheet / Rolled / 0.9 91.87 4.64 0.94 1.43 0.39 0.66 Duralumin ND
Unknown Blade / Forged / 3–66 93.70 4.05 0.59 0.64 0.40 0.24 Duralumin A
* C = Al cladding; A = anodisation; O = organic (primer/paint); ND = not determined

Nonetheless, Al cladding was largely found on rolled
products, especially fuselage skin and plates. Figure 1
shows an example of an Al-cladded plate in cross-sec-
tion. For plates of ~1 mm thickness, the cladding layer
is typically between 50 and 100 µm. Al cladding was
systematically employed in German and American
aircraft parts, but not always in French aircraft parts.
Several plates of the Dewoitine D.520 (1940) had not been
cladded whereas plates of the D.338, an earlier aircraft
(1937) from the same manufacturer, had Vedal. It may
have been the case that corrosion protection was chosen
according to the expected durability of the aircraft. Thus,
Vedal was used to protect civil aircraft (such as D.338),
expected to be in use for many years, while short-life

Figure 1. SEM-BE images of a

plate from a Messerschmitt
Bf109, evidencing Al cladding:
(a) full view, (b) close-up view.
Insert: main spatial directions
and defined planes of the rolled
 products
82  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
fighters (such as D.520) had no cladding at all. Among
the plates recovered on British and Italian aircraft, no
cladding was found but they were also strongly altered
and difficult to assess.
Some of the extruded profiles and forged products (blades)
had been anodised but the thin layer of aluminium oxide
(few microns) is sometimes difficult to distinguish from
a corrosion layer.
In summary, only a few of the aircraft parts had primer
and paint as the sole protection against corrosion. Those
samples evidence the early awareness of aircraft manufac-
turers about the low corrosion resistance of Duralumin.
General observation of the conservation state of
the artefacts
Most of the artefacts suffered from corrosion due to their
long burial in the ground or sea or their prolonged aban-
donment in the open air. Figure 2 shows representative
artefacts and the typically encountered alterations. Gener-
ally, Al-cladded products were more robust to burial or
environmental conditions. This was demonstrated by
MODERN METALS
the Dornier 217 fuselage (Figure 2a), which was left for
decades in a chasm in the Pyrenees. However, as shown
for the Junkers 88 (Figure 2b), the remnants of which had
been used on a farm as the roof of a poultry house, the
loss of material provided observable evidence that the Al
cladding was no longer effective. On extruded profiles
exposed to atmospheric conditions such as those of the
Dewoitine D.338 (Figure 2c), the anodisation and paints
originally present had significantly degraded. Pitting
and intergranular corrosion could have quickly led to
exfoliation corrosion, as previously reported (Brunet
et al. 2019). In forged products, once the protection is
lost, intergranular corrosion occurs, as has been observed
in other wrought products. On artefacts recovered
from the sea (Figure 2d), corrosion can be severe and
the corrosion products often develop a blue colouring
(Rocca et al. 2021).
An understanding of the degradation processes requires
the examination of corrosion in relation to the manu-
facturing process and the original means of protection.
The environment and the history of the aircraft are key
parameters that have to be considered. Depending on
Figure 2. (left) Photographs of
the artefacts. (right) Optical
microscopy images of the
alterations in the aircraft:
(a) Dornier 217 fuselage
(Al cladded), (b) Junkers 88
engine cowl (Al cladded),
(c) Dewoitine D338 stringer
(anodised), (d) propeller blade
recovered from the sea near
 Brest (Britany)
FIRST STEP IN THE PROCRAFT PROJECT ON WWII AIRCRAFT HERITAGE: INVESTIGATION AND CONSERVATION OF THE ALUMINIUM ALLOYS
the burial environment and the cause of the crash (e.g.
fire), the condition of the original corrosion protection,
mostly Al cladding, can vary. A case study of the engine
cowl of a Junkers 88 is presented below.
Correlation between the alloy manufacturing
process, the environment, artefact history and
corrosion forms
The Junkers 88, a bomber-fighter built in 1943, crashed
in 1944 in southern France after being shot down by a
British Mosquito. A fire was witnessed after the crash
(Collaveri 2016). In 2010, a few fragments were excavated,
including a fragment of an engine cowl. On the outside
plate (plate 1, AlCuMg2 alloy), large concretions are
present on the surface and only residues of paint remain.
The inside plate (plate 2, AlCuMg1 alloy) shows material
losses, especially on areas involved in the crash. Both
plates have undergone macroscopic pitting corrosion,
which can develop into exfoliation corrosion.
Figure 3 shows the SEM-BE images of the cladded
Junkers 88 plate 1 in cross-section (transverse plane)
and the corresponding EDS mapping. As shown by the
latter (Figure 3b), the concretions (exogenous elements)
include localised iron corrosion products. Under the
concretions, thick aluminium corrosion products are
83
present on the surface, while on the inner structure pits
with elements such as sulfur and phosphorus are seen.
Chlorine was also detected within the localised corrosion
products. All of these elements indicate interactions with
soil anions. Chlorides are the most aggressive species
as they can induce the breakdown of the passive layer,
leading to pit formation (localised corrosion).
An image of the pits within the Al cladding is provided
in Figure 4, including evidence of the evolution of the
corrosion attack inside the Al-cladded plate (Figure 4b).
Localised corrosion developed laterally along the surface,
within the cladding. The depth of the corrosion corre-
sponds to the end of copper diffusion – the result of the
hot rolling process – inside the aluminium cladding. The
resistance of Al cladding to corrosion was discussed in
detail by Walton et al. (1953). Pure Al cladding provides
good electrochemical protection, even in an aggressive
natural environment. It also confers cathodic protection
of the core alloy, such that corrosion will penetrate only
as far as the core alloy or diffusion zone. Exposure of the
Al cladding to the atmospheric environment (cycles of
humidity) results in the formation of corrosion products
such as aluminium hydroxides and/or sulfates. When
present in large amounts, they induce cracks in the Al
cladding layer, lifting it in some places and reaching the
bulk alloy in others.
Figure 3. SEM-BE image and
EDS maps of a cross-section
(transverse plane) of the
 Junkers 88 (plate 1)
Figure 4. SEM-BE images of a
cross-section (transverse plane)
of the Junkers 88 (plate 1):
(a) pitting corrosion starting
on the Al cladding layer and
(b) corrosion progressing
 within the Al-cladded plate
84  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
In Figure 5, the corrosion has reached the bulk alloy,
resulting in both intergranular and intragranular corro-
sion. The latter develops in the presence of humidity
and is triggered by the intermetallic precipitates located
mainly at the grain boundaries and by nano-size precip-
itates inside the grains (Figure 5b). These precipitates
suggest exposure to heat, either while the aircraft was
in use (proximity to the engine) or during the fire that
occurred after the crash.
The metallurgical observations demonstrate that an
aggressive environment, including the presence of chlo-
rine and sulfur, favours the degradation of the Al cladding
layer. Once the bulk alloy is reached, severe corrosion is
initiated due to the intrinsic corrosion susceptibility of
the alloy, accelerated by cycles of humidity.
The inside plate of the Junkers 88 (plate 2, AlCuMg1
alloy) also exhibits precipitation at the grain bounda-
ries and the same corrosion patterns as seen in plate 1.
Although it was expected that the alloy with the higher
Mg content (plate 1, AlCuMg2) would be less resistant
to corrosion, due to the increased formation of S-type
precipitates (DeRose et al. 2013), this was not the main
determinant of corrosion susceptibility in this case.
Rather, the heat-induced precipitation at grain bounda-
ries (present in both plates) played the larger role.
Complementary investigations are still needed, including
transmission electron microscopy imaging to identify the
nature of the nano-size precipitates and understand their
role in the intragranular corrosion attack.
Conclusion
During WWII, different types of aluminium alloys were
used by aircraft manufacturers. In most cases, Duralumin
or Super Duralumin (with a higher proportion of Mg)
was employed for both structural and non-structural
MODERN METALS
Figure 5. SEM-BE images of
the Junkers 88 (plate 1, rolling
plane): (a) general view,
(b) close-up showing nano-size
 precipitates within the grains
parts of the aircraft. However, corrosion of these Al-Cu
alloys was a well-known issue, which resulted in different
corrosion protection strategies, most commonly cladding
with pure Al for rolled products, anodisation or simply
an anti-corrosion primer for some extruded products.
As a result, more than 70 years later, depending on the
materials, in particular the original protective coating,
and on the environment at the aircraft crash site, the
alterations in the structural alloys are highly variable but
often include pitting and exfoliation corrosion. This study
focussed more specifically on the particular forms of
corrosion that affect Al-cladded alloys. Aluminium-based
alloys, even those that were protected, may further
degrade after their removal from aggressive environments
(marine or soil), as corrosion can continue due to expo-
sure to cycles of humidity, which can promote exfoliation
corrosion. Thus, future work in the PROCRAFT project
will focus on the cleaning and stabilisation of represent-
ative artefacts. The low amount of chlorine elements
detected within the corroded structure will allow for the
refinement of current research areas within the project.
In contrast to the dechlorination treatments used for iron
or copper-based metals, restoration and stabilisation will
require surface protection adapted to indoor or outdoor
environmental conditions. Innovative protective coatings
will be developed that take into account the surface condi-
tions, i.e. alloy with or without Al cladding, the corroded
metal and the painted surfaces. They will also be tailored
to the surface state while complying with cultural heritage
requirements regarding material compatibility and the
preservation of the original surface aspect.
Acknowledgements
This research was carried out as part of the PROCRAFT
project, within the JPICH Conservation and Protection
Call, supported by the following national funding organi-
FIRST STEP IN THE PROCRAFT PROJECT ON WWII AIRCRAFT HERITAGE: INVESTIGATION AND CONSERVATION OF THE ALUMINIUM ALLOYS
sations: Agence Nationale de la Recherche (ANR, France),
Ministry of Universities and Research (MUR, Italy) and
Ministry of Education, Youth and Sports (MEYS, Czech
Republic). The authors would like to warmly thank the
active participation of associations Aérocherche, ABSA-
3945, Ailes Anciennes Toulouse, Aérothèque, Aéroscope
in France and Air Club & Fun and Volandia in Italy as
well as museums Aeroscopia and Air and Space Museum
Le Bourget (France).
Notes
1
https://www.heritageresearch-hub.eu/project/procraft/
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Authors
Magali Brunet is a CNRS research scientist in mate-
rials science and since 2015 a member of the Cultural
and Industrial Heritage Materials team of the CEMES.
She studies the manufacturing processes and alterations
of historical aluminium alloys, using physicochemical
analysis techniques. She holds a PhD in microelectronics
engineering from University College Cork, Ireland
(2003), and a master’s degree in conservation and
restoration of cultural heritage from Paris 1 – Sorbonne
University, France (2015).
Luc Robbiola is a CNRS research engineer in cultural
materials science. He holds a PhD in metallurgy (1990)
and a master’s degree in conservation and restoration
86  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND MODERN METALS

of cultural heritage from Paris 1 – Sorbonne University protection in the field of cultural heritage, the corrosion
(1985). He is presently working at Toulouse University inhibition of metallic alloys in different environments,
in the TRACES laboratory. rebar corrosion behaviour in traditional and innovative
concretes and the corrosion behaviour of biomedical
Christophe Deshayes is a CNRS assistant engineer in
and industrial alloys produced by selective laser melting.
materials science. He has been working at the CEMES
since 1999. His expertise is on scanning electron micros- Jaromír Fišer has been an associate professor in machine
copy and mechanical testing. and process control in the Faculty of Mechanical Engi-
neering, Czech Technical University in Prague, since
Elena Bernardi has been an associate professor at the
2021. He received a PhD in technical cybernetics in 2004.
University of Bologna, Italy, since 2019. She received an
His main research interests are the analysis and synthesis
advanced degree in industrial chemistry in 2001 and a
of time-delay systems and industrial process control,
PhD in industrial chemistry in 2005. Her research and
including microclimate control in heritage buildings.
teaching activities are in the field of chemistry as applied
to the environment and for cultural heritage. The focus Tomáš Vyhlídal has been a professor in machine and
of her research is the effects of the environment and process control in the Faculty of Mechanical Engineering
pollutants on materials as well as on conservation of (FME), Czech Technical University in Prague, since 2012.
cultural heritage. He received a PhD in technical cybernetics in 2003. Since
2019 he has been the FME’s head of the Department of
Carla Martini has been an associate professor at the
Instrumentation and Control Engineering. His research
University of Bologna, Italy, since 2014. She received an
interests include mathematical modelling and the control
advanced degree in industrial chemistry in 1993 and a
of distributed parameter systems and processes, including
PhD in metallurgical engineering in 1996. Her research
the microclimate of heritage objects.
and teaching activities are in the field of metallurgy with
a focus on the surface engineering of metallic materials Jane Echinard is head of Arc’Antique, a conservation
and the conservation of cultural heritage metals. aboratory in Nantes, France, specialised in archaeological
artefacts from both marine and terrestrial environments.
Cristina Chiavari has been associate professor at the
She has graduate degrees from the Sorbonne University
University of Bologna, Italy, since 2021. She received an
in metal conservation (2005) and preventive conserva-
advanced degree in physics in 1997 and a PhD in electro-
tion (2012).
chemical engineering in 2003. Her research and teaching
activities are in the field of chemistry as applied to the Elodie Guilminot is a materials engineer (Polytech
environment and cultural heritage. Her research focuses Nantes, France, 1996) and in 2000 received a PhD in
on both the effects of the environment on materials and electrochemistry (Institut National Polytechnique de
the conservation of cultural heritage. Grenoble, France) for research on the conservation of
waterlogged wood/metal composites. She joined the
Andrea Balbo has been an associate professor at the
Arc’Antique laboratory (Nantes, France) as conservation
Engineering Department of the University of Ferrara,
scientist in 2006 to conduct and coordinate research
Italy, since 2020. He conducts research in the field of
projects. Her research interests include the corrosion of
materials science at the Corrosion and Metallurgy Study
metals and the development of restoration treatments.
Centre ‘Aldo Daccò’. His current research activity is
focussed on the corrosion phenomena of metal alloys and
its inhibition by means of different classes of substances
and coatings relevant to industrial applications and the
protection of cultural heritage.

Cecilia Monticelli is an associate professor in materials

science and technology in the Engineering Department of
the University of Ferrara, Italy, where she teaches mate-
rials science and technology and corrosion and protection
of metals. Her recent scientific interests include corrosion

DiscoveryMat: A Freeware Electrochemical Tool for the In
Situ Analysis of Aluminum Alloys in the Cooling Systems of
Historical Vehicles
Elodie Granget* Brice Chalançon
Haute École Arc Conservation- Musée National de l’Automobile de
restauration, HES-SO University of Mulhouse – Collection Schlumpf
Applied Sciences and Arts Western Mulhouse, France
Switzerland b.chalancon@museedelauto.org
Neuchâtel, Switzerland
elodie.granget@he-arc.ch
Abstract
Corrosion of aluminum alloys is frequently observed in the
cooling systems of functional vehicles dating from 1920 to 1940
in the Musée National de l’Automobile in Mulhouse, France.
This paper shows how DiscoveryMat, a freeware analytical
tool, has been successfully used for the in situ analysis of the
materials concerned. The tool is based on the monitoring of the
electrochemical behavior of metals in different test solutions
and relies on a database to propose possible alloy compositions.
The analysis of a corpus of detached parts representative of
this problem has made it possible to enrich the database, thus
Introduction
The Musée National de l’Automobile de Mulhouse’s
(MNAM) collection numbers over 600 vehicles, most
of which are technically functional cars. However, only
a few (80) can actually be driven. They benefit from an
annual maintenance service and at least one annual drive
around the museum’s circuit. A condition file attached
to each vehicle is updated with information about the
driving conditions and observations made during main-
tenance. This allows for a reassessment of the vehicle’s
functional status and, if deemed necessary, whether it
should be immobilized.
During these inspections, the conservation team noticed
a recurrent problem with the cooling system of some
early-20th-century cars. Aluminum alloy parts were
corroding rapidly, compromising the tightness of the
system. This problem was occurring on vehicles dating
from 1920 to 1940. The MNAM approached the Haute
École Arc Conservation-restauration (HE-Arc CR), in
Neuchâtel, Switzerland, and its research unit (UR-Arc
CR) to collaborate on understanding the problem.
Young Conservation Professional
Christian Degrigny
Haute École Arc Conservation-restauration,
HES-SO University of Applied Sciences and
Arts Western Switzerland
Neuchâtel, Switzerland
Christian.degrigny@he-arc.ch
*Author for correspondence
enabling the precise identification of the problematic aluminum
alloys in real conditions directly on the vehicles. The results of
these analyses showed that the corroded parts are all made of
Al-Cu(-Si) alloys, whereas the most recent and stable parts are
made of Al-Si alloys.
Keywords
DiscoveryMat, freeware analytical tool, alloy identification,
aluminum, car, cooling system
Condition report on the studied cars
The purpose of the cooling system is to remove excess
heat from the engine. A coolant flows around the heated
parts through the jacketed walls of the engine block (cast
steel) and the cylinder head (cast aluminum alloy). It
flows out of the engine through a system of pipes (cast
aluminum or copper alloy) and hoses (rubber) that
connect it to the radiator, where the liquid is cooled down
by ambient air and sometimes by a fan (Figure 1). Once
cooled, it returns back to the engine, where the cycle
starts again (Kennedy 1913). This coolant was originally
water but has since been replaced by commercial coolants
(Excell –35°C [Diframa] or MB 325.0 [Mercedes Benz]),
a mix of water, antifreeze, and other additives such as
corrosion inhibitors.
A condition report was carried out on a selection of
French manufactured cars that are currently or were
formerly functional, focusing on the aluminum parts of
their cooling systems (Table 1).
88  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND MODERN METALS

Figure 1. Simplified illustration of an engine, with the cooling system Figure 2. Corrosion issues on a water pump (Bugatti T30) and at the
in blue junction of a pipe and a hose (Bugatti T41)

Table 1. Different sets of French manufactured car parts dating from

1921 to 1939: (1) test set and (2) validation set for DiscoveryMat

BRAND MODEL YEAR CODE PARTS SET

pipe
water pump
Type 37 1926 B37 gasket
camshaft
Bugatti
Detached part

block
1. Test set

1928– pipes
Type 41 B41
1933 water pumps
Unknown ~1930 Bx pipe
Hispano-Suiza Type H6B 1938 H6B water pump
Panhard & Dynamic water pump
1936 PDJ
Levassor c. Junior piston
pipes
water pump
2. Validation set
Attached parts

Bugatti Type 30 1922 B30

camshaft
block
pipe
Simca Gordini Type 5 1937 S5 cylinder
head

Figure 3. Metal heavily corroded under the hose of a Bugatti T28

Corrosion was observed at the junction between
aluminum alloy pipes and rubber hoses on most of these
cars. As this assemblage is often imperfectly tight, it is
possible that it creates a confined zone of moisture at the
interface between the two materials. Local differences in
oxygen and ion(s) concentration are generated, inducing
an environment favorable to the start of corrosion. A
gelatinous and bulky product forms, probably composed
of aluminum hydroxide, and further compromises the
tightness of the system (Figure 2). In severe cases, the
rubber cracks and the hoses must be replaced if the
vehicle is to remain functional. When disassembled,
it can be seen that the same product has developed on
both the outer and inner surfaces of the pipe and has
sometimes consumed the metal significantly (Figure 3).
Aim of the project
The aim of this research project was to identify the
different aluminum alloys in the cooling systems of the
set of samples. This characterization could easily be done
in situ with a portable X-ray fluorescence (XRF) system.
However, this type of device is expensive and not easily
accessible for most museums. Within the scope of this
study, we wanted to test DiscoveryMat (Haute École Arc
2021), an analytical tool and free software developed by
UR-Arc CR that provides qualitative analyses of heritage
metals developing thin corrosion layers. The fact that
it is also portable, low-cost, and easy to use provides
DISCOVERYMAT: A FREEWARE ELECTROCHEMICAL TOOL FOR THE IN SITU ANALYSIS OF ALUMINUM ALLOYS IN THE COOLING SYSTEMS OF HISTORICAL VEHICLES
institutions that acquire it and are trained in its use with
new expertise (Degrigny et al. 2018).
Method
DiscoveryMat is designed to monitor the corrosion
potential (Ecorr) of a metal over time performed in three
different solutions (Evian mineral water, pH = 7.2;
potassium nitrate 1 wt%, pH = 5.9; sodium sesquicar-
bonate 1 wt%, pH = 9.5). It then compares the plots
obtained with those already entered into the database
of known composition determined by XRF. An algo-
rithm computes the distance of similarity (d) between
the plots of the material studied and those of all the
entries in the database. It takes into consideration the
difference in the slope and curvature of the plots for
the first 10 minutes (the initiation phase) and in the
values of the potential at the end of the measurement
(the development phase) (Degrigny et al. 2010). The
smaller the d, the more relevant the match. For this
study, a satisfactory match was established for d < 2000
(Granget 2020). The results are presented in the form
of a table of database entries classified in increasing
values of d, as well as superimpositions of the plots of
the material studied and those of each database entry.
This makes it possible to appreciate the greater or
lesser similarity of the shape of the plots and to discard
irrelevant proposals.
Previous work has refined the measurement protocol
(Degrigny et al. 2010) in order to obtain reproducible
and interpretable plots on heritage objects of various
copper (Degrigny et al. 2018), silver (Fontaine 2012), or
aluminum alloys (Despland 2018).
Table 2. Identification of detached parts of H6B, PDJ, B37, and Bx using DiscoveryMat and comparison with XRF analyses; d highlighted in gray
if > 2000
DiscoveryMat
Composition
H6B a Al, Si, Cu, Zn
H6B b Al, Si
PDJ a Ø 7178
PDJ b Ø 5579
PDJ c Ø 6851
B37 a Al, Si, Cu, Zn
B37 b Al, Si, Cu, Zn
B37 d Al, Si, Cu, Zn
B37 e Al, Si
Bx Al, Si, Cu, Zn
89
As the database of aluminum alloys is not very extensive
(only 42 entries, mostly wrought alloys), leading to prob-
ably poor results, it was essential to enrich it with alloys
from the automotive industry from between 1920 and
1940 in order to improve the relevance of the analysis.
This was carried out in two steps: first, electrochemical
measurements were performed on a first set of detached
car parts, which are easy to handle and enable the tool’s
applicability to be tested. They were completed with
quantitative XRF values (three-point measurement with
a Niton XL3t XRF handheld analyzer, 50 kV, Ag anode,
Thermo Fisher Scientific) to form new entries in the data-
base. Measurements were then carried out on a second
set of parts still attached to two cars, an approach more
in line with the in situ analyses envisaged by the MNAM,
to validate the relevance of the enriched database.
Results
The preliminary results on the detached parts show that,
even though d almost always exceeds the 2000 threshold,
it is often possible to identify the main elements in the
alloy. The parts seem to be made of either aluminum-sil-
icon alloys (Al-Si) or aluminum alloys containing silicon
(Si), copper (Cu), and sometimes zinc (Zn). According
to XRF analyses, most alloys are indeed from the Al-Si
or Al-Cu(-Si) alloy families (Table 2).
DiscoveryMat measurements were made in a second
phase on parts still attached to two vehicles: a Simca
Gordini 5 and a Bugatti Type 30. The plots were compared
to those of the database, completed or not by the new
entries from the detached parts. It is clear in Table 3 that
the updated database allowed better identification of the
XRF
d
1319 Al 90.6, Cu 6.5, Sn 1.7, Fe 0.7, Si 0.5
2008 Al 88.3, Si 10.1, Cu 0.8, Fe 0.6, Zn 0.1, Pb 0.1
Al 86.9, Cu 8.9, Ni 2, Fe 1.4, Si 0.5, Pb 0.3
Al 89.2, Cu 7.6, Ni 1.8, Si 0.7, Fe 0.7
Al 76.9, Si 12.6, Cu 10, Fe 0.5
4136 Al 85.3, Cu 11, Si 1.3, Zn 1.1, Fe 1.1, Pb 0.2
2085 Al 90, Cu 7.4, Fe 1, Zn 0.8, Si 0.7, Pb 0.1
3897 Al 89.6, Cu 6.7, Si 1.8, Fe 1, Zn 0.8, Pb 0.1
2504 Al 82.7, Si 13.4, Cu 2, Ni 0.8, Fe 0.8, Mn 0.2, Zn 0.1
1146 Al 83.2, Cu 9.9, Zn 3.2, Si 2.1, Fe 1.3, Pb 0.3
90  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND MODERN METALS

Table 3. Identification of attached parts of S5 and B30 using DiscoveryMat, with the database enriched, or not, with the entries from detached parts
and XRF analyses; d highlighted in gray if > 2000

Database without Database with

detached parts detached parts
Composition d Composition d XRF
S5 a Al, Zn, Cu, Si 2935 Al, Zn, Cu, Si 2935 Al 73.8, Si 21.3, Cu 2.8, Fe 1.3, Zn 0.3, Mn 0.3, Pb 0.2, Sn 0.1
S5 b Al, Si, Zn, Cu 4217 Al, Si, Cu, Zn 1390 Al 71.6, Si 12.9, Cu 9, Zn 4, Fe 1.3, Ni 0.5, Mn 0.3, Pb 0.2, Sn 0.2
B30 a Al, Cu, Si, (Zn or Mg) 4796 Al, Cu 8.4, Si 2.4, Fe 1.3, Zn 0.6, Pb 0.1, Ni 0.1 2651 Al 84, Cu 11.2, Si 2.3, Fe 1.2, Zn 1, Sn 0.2, Pb 0.1
B30 b Al, Zn, Cu, Si, Pb 4228 Al, Cu 10, Si 1–2, Fe 0.5, Zn 1187 Al 75.5, Cu 17.6, Zn 2.4,Si 2, Fe 1.5, Pb 0.4, Sn 0.6
B30 c Al, Si, Cu, Zn 6543 Al, Cu 11, Si 1.3, Zn 1.1, Fe 1.1, Pb 0.2 2436 Al 82.9, Cu 11.9, Si 2.3, Fe 1.4, Zn 1, Sn 0.3, Pb 0.2
B30 d Al, Cu 3284 Al, Cu 7–12, Si 1–2, Zn 0.5, Fe 1073 Al 77.5, Cu 16.5, Si 2.4, Zn 1.5, Fe 1.1, Sn 0.5, Pb 0.5
B30 e Al, Cu, Mg 2383 Al, Cu 7–12, Si 1–2, Zn 0.5, Fe 1438 Al 85.9, Cu 9.4, Si 1.7, Fe 1.8, Zn 0.9, Sn 0.2, Pb 0.1
B30 f Al, Si, Cu, Zn, Fe 6160 Al, Cu 11, Si 1.3, Zn 1.1, Fe 1.1, Pb 0.2 1870 Al 86.4, Cu10.2, Si1.5, Fe1, Zn0.7, Sn0.1, Pb0.1

alloys in most cases. Al-Cu(-Si) alloy families were accu-
rately found and a more relevant idea of the proportions
for the main elements was given. The better performance
of DiscoveryMat for these alloys is due to the 11 new
entries of similar composition added to the database
from the first set of detached parts. However, there was
no improvement for the part “S5a,” a hypereutectic Al-Si
alloy that is still not represented in the database.
Discussion
According to the XRF analyses, the parts are composed
of three main types of alloys from this period: hypereu-
tectic Al-Si alloys, eutectic Al-Si alloys with or without
Cu, and Al-Cu alloys ranging from 4 to 12% Cu and
containing Si, Zn, Ni, or Sn. Moreover, all corroded parts
are made of Al-Cu alloys or contain large proportions
of Cu (Figure 4).
These results are corroborated with what can be found in
historical and technical literature. Indeed, in the 1910s,
Al-Cu alloys such as Duralumin became widely used
(L’Aluminium français 1924) for the production of both
wrought and cast car parts, because they were lighter than
steel and also because the presence of copper improved
the mechanical strength of the metal. However, it quickly
became apparent that these alloys had poor corrosion
resistance. When used in casting, they produced porous
parts with a high chance of breaking when released from
the mold (Guillemot 1933). This may explain why, during
the 1910s and 1920s, in parallel with the search for a better
aluminum alloy composition for casting, efforts were made
to further lighten steel for engine castings (Bodet 1931).
Therefore, it is not surprising to find that the Al-Cu parts
from the cars were heavily corroded. These problematic
alloys can now correctly be identified by DiscoveryMat.

Figure 4. Proportions of Cu and

Si in the alloys of the studied
 parts
DISCOVERYMAT: A FREEWARE ELECTROCHEMICAL TOOL FOR THE IN SITU ANALYSIS OF ALUMINUM ALLOYS IN THE COOLING SYSTEMS OF HISTORICAL VEHICLES
In the 1920s, the family of Al-Si alloys, namely Alpax,
eutectic Si = 13 wt% (L’Aluminium français 1926), and
hypereutectic, Si > 13 wt% (L’Aluminium français 1924),
was created. Silicon conferred aluminum mechanical
properties similar to those provided by copper but
better corrosion resistance and casting properties. From
the second half of the 1920s, they slowly found their
place in the automotive industry, more specifically in
the casting of more complex engine parts subject to
friction or thermal stresses, such as pistons, cylinder
heads, and cooling systems’ parts (Guillemot 1933). This
information validates the results from the XRF analyses,
showing that all the latest and more stable parts from the
selected cars were made of eutectic and hypersilicated
Al-Si alloys. For example, the Hispano-Suiza water pump
had two parts (H6B a & b), one of which (HB6B b) was
surprisingly not corroded. The analyses showed that this
part was made of Al-Si alloy (Talbe 2); according to the
conservator, it was probably replaced a few years ago. A
precise identification of these two alloy families is not
yet possible with DiscoveryMat but could be achieved
by adding more entries to the database.
Conclusion
This study demonstrates the suitability of DiscoveryMat
as an in situ analytical tool for the qualitative identifi-
cation of aluminum alloys. With the new entries added
to DiscoveryMat’s database, it was possible to accurately
identify the Al-Cu alloy family as well as some secondary
elements of materials of similar composition.
The cars in the set of samples studied have aluminum
alloys in their cooling systems that are representative of
the transition period between 1920 and 1940: Al-Cu(-Si)
was used in older vehicles, whereas Al-Si was slowly
introduced during the 1930s. All the heavily altered
parts were made of Al-Cu(-Si) alloys, which have lower
corrosion resistance.
In addition to alloy identification, further study of the
corrosion process that occurs at the interface between
rubber and metal is necessary to better understand and
prevent this phenomenon.
Acknowledgments
The authors would like to thank the Musée National
de l’Automobile de Mulhouse for hosting the main
author during completion of her master’s thesis. This
91
internship was funded by the Swiss-European Mobility
Program grant. They would also like to thank HE-Arc
CR and Microcity in La Chaux-de-Fonds, Switzerland,
for providing access to facilities and equipment, as well
as the supervision required to conduct this study. Finally,
they would like to acknowledge Mr. Christian Vargel†,
an expert in aluminum corrosion, and Mr. Claude Riss,
from the Institute for the History of Aluminum, for their
expertise during the condition assessment.
References
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serie automobile. La revue de l’Aluminium 3: 47–50.
L’Aluminium français. 1924. L’Aluminium dans le châssis
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Degrigny, C., G. Guibert, S. Ramseyer, and G. Rapp,
and A. Tarchini. 2010. Use of Ecorr vs time plots for the
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and technical objects: The SPAMT Test Project. Journal
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low-cost electrochemical open-source hardware to
analyze heritage metals: Possibilities and limits. Current
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minium d’objets ethnographiques et caractérisation de
leurs produits de corrosion : analyse par voie électro-
chimique et par fluorescence X. Bachelor’s thesis, He-Arc
Conservation-restauration, Switzerland.
Fontaine, C. 2012. Analyse qualitative par voie élec-
trochimique des alliages à base d’argent : application
de l’outil CLAMTEC à ce type de matériau. Bachelor’s
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Granget, E. 2020. Corrosion des alliages d’aluminium des
circuits de refroidissement à eau de véhicules en contexte
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tauration, Switzerland.
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Haute École Arc. 2021. DiscoveryMat [online]. Available

at http://discoverymat.he-arc.ch:8080/ (accessed 28
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Authors
Elodie Granget graduated in 2020 from the master’s
program at HE-Arc CR in Neuchâtel, Switzerland, where
she specialized in metal conservation. Since 2021, she
has been working as a research assistant at HE-Arc CR.

Brice Chalançon graduated in mechanical engineering

from Polytech Orleans, France, in 2008, and completed
his master’s in conservation of technical, scientific, and
horology objects at HE-Arc CR in 2019. Since 2008, he
has been director of the workshop at the Musée National
de l’Automobile de Mulhouse, France.

Christian Degrigny received a PhD in analytical

chemistry from the University of Paris IV, France, in
1990. Since 2004, he has taught and conducted applied
research projects at HE-Arc CR and has specialized in
electrochemical diagnosis and treatment of historic and
archeological metals.
COATINGS, CONSOLIDANTS &
CORROSION INHIBITORS
A Comparison of the Long-Term Outdoor Performance
of Two Modern Paint Coating Systems and a Traditional
Lead-based Paint Applied to Historic Wrought Iron
Peter Meehan* Nicola Emmerson
School of History, Archaeology and School of History, Archaeology and
Religion, Cardiff University Religion, Cardiff University
Cardiff, UK Cardiff, UK
peter.meehan@hm-cc.uk EmmersonNJ@cardiff.ac.uk
Abstract
A real-time, five-year outdoor study compares the performance
of three paint systems (traditional oil-based, acrylic, epoxy
resin) applied to naturally corroded wrought iron, with their
surfaces prepared to Swedish Standard Sa 2.5 or Steel Surface
Preparation Standard St3. Interim data at two years reports
on gloss, colour change, pull-off testing and electrochemical
impedance spectroscopy measurements. Traditional oil-based
paint exhibited significant visual change, a modified alkyl paint
Introduction
Conservation of historic ironwork
Wrought iron corrodes readily in the atmosphere to
produce permeable, non-protective corrosion products
that laminate and spall, a process enhanced by regular
wet and dry climate events (Hoerlé et al. 2004). Coatings
are commonly used to control corrosion, but since their
limited lifespan makes this a costly process, research in
the field aims to identify the best-performing coatings
to support cost/benefit decisions. Decision-making in
the selection of coatings, surface preparation methods
and application protocols within heritage is mostly
based on best practice and well-established techniques
(Blackney and Martin 1998). Quantitative evidence of
coating performance is more often found in commercial
or industrial research. Unfortunately, rationales and
acceptable methods and outcomes in these sectors are
often governed by ethical and aesthetic decision-making
processes that differ from those used in historic contexts.
Conservation practices for coating historic iron may use
commercial standards alongside methodologies such
as flame cleaning, where variable control lies with the
individual (Emmerson et al. 2019). This does not align
with the needs of coating manufacturers. Many coatings
David Watkinson
School of History, Archaeology and
Religion, Cardiff University
Cardiff, UK
watkinson@cardiff.ac.uk
*Author for correspondence
underwent minor but visually undetectable changes and an
epoxy/acrylic coating remained unchanged. The oxide layer in
St3 controlled adherence of the coatings.
Keywords
protective coatings, wrought iron, electrochemical impedance
spectroscopy (EIS), colorimetry, pull-off testing, gloss
used commercially have performance characteristics that
require adherence to defined standards to guarantee
their service life. These normally involve specific surface
preparation and coating application methods, as well as
defining the necessary environmental parameters for a
successful coating application. Fulfilling much of this
guidance within historic contexts is difficult due to the
corroded nature of the material, limitations imposed by
differing ethical and aesthetic standards and the cash-
poor state of the sector.
Ethical constraints and numerous variables make
designing experimental research to replicate the reality
of conservation practice difficult to achieve, and compro-
mises may need to be sought. A major advance would
be to identify the ‘weak link(s)’ in the variable chain, i.e.
essentially identify which variable(s) dictate(s) coating
performance the most and, if possible, develop this
process to provide a rank order. This would facilitate
informed decisions when balancing factors like ethics
and aesthetics against longevity and cost/benefit.
While real-time testing and a representative sample
set are essential to underpin quantitative prediction of
coating lifespan, these factors can only offer an indication
A COMPARISON OF THE LONG-TERM OUTDOOR PERFORMANCE OF TWO MODERN PAINT COATING SYSTEMS AND A TRADITIONAL LEAD-BASED PAINT APPLIED TO HISTORIC WROUGHT IRON
of coating performance in the environment adopted for
the test procedure. Some quantitative methods such as
electrochemical impedance spectroscopy (EIS) (Cano
et al. 2010) can provide useful comparative data, but
this cannot be extrapolated to provide predictive insight
into service life performance due to the essential but
unrealistic test conditions and an absence of real-time
testing. Visual change, sometimes scaled according to
international standards, is useful, but the qualitative data
this produces may limit insight into the relative extent of
failure and the precise prediction of coating performance.
Following the concept of assigning value to both quan-
titative and qualitative indicators of performance, the
study reported here employs a mixture of quantitative and
qualitative assessment techniques to produce an integrated
insight into coating performance. Real-time testing of
historic wrought iron, with surfaces prepared according to
two commonly used techniques within historic wrought
iron preservation, is used to study the performance of three
coatings that represent traditional and modern approaches
within the sector. A single-pack, oil-based alkyd and a
two-pack epoxy resin/acrylic urethane are compared with
a lead-based linseed oil system traditionally used for the
long-term protection of iron. Their performance is assessed
using a range of criteria including their longevity, ease of
use, reversibility and health and safety issues. Hopefully,
the results will allow a reasoned assessment of their perfor-
mance, so that the conservator can make informed choices
about the materials and methods to use when painting
historic ironwork.
Aims and objectives
Aim:
• To determine the long-term, real-time performance
of two modern protective coating systems and one
traditional system for exterior ironwork.
Objectives:
• To coat samples of historic iron and control samples
of glass with one of three coating systems.
• To assess qualitatively the application of the coatings to
historic wrought iron relative to conservation practices.
• To expose the coated samples to outdoor conditions
for a period of five years.
• To assess the visual and protective properties of the
coating systems by colorimetry, gloss measurement,
pull-off testing, EIS and oxygen consumption at
12-month intervals throughout the study period.
95
This preliminary paper reports on the results of the first
24 months of outdoor exposure of the samples. Oxygen
consumption method (Matthiesen 2013) and results are
not reported as it is too early for meaningful data to be
presented.
Method
Sample material
Samples were produced from two rolled wrought iron
sheets from a 19th-century gasometer. Although wrought
iron is inhomogeneous by nature (Dillmann et al. 2004),
taking samples from just two rolled plates minimised the
risk of compositional differences. The sheets had thick-
nesses of 4 and 6 mm and were cut using a hydraulic guil-
lotine to avoid microstructural changes from heat-gen-
erating cutting processes. Corrosion during exterior
exposure has generated corrosion products including
magnetite, goethite and lepidocrocite on the surface as
identified by x-ray diffraction (Emmerson et al. 2019).
Surface preparation
The samples were prepared to two levels of cleanliness
prior to coating (Table 1). A total of 96 samples were
cleaned to Swedish Standard Sa 2.5 (ISO 8501-1:2007;
International Organization for Standardization 2007)
using abrasive blast cleaning to achieve a near-white
blast-cleaned surface (Joint Surface Preparation Standard
SSPC-SP 10; The Society for Protective Coatings 2007);
144 samples were cleaned to a Steel Surface Preparation
Standard St3 (ISO 8504-3:2018), achieved by thorough
hand and power tool cleaning to leave the metal surface
Figure 1. Sample surfaces uncleaned, cleaned to Sa 2.5 and St3 and
following application of the three coating systems
96  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND COATINGS, CONSOLIDANTS & CORROSION INHIBITORS

Table 1. Details of all samples as prepared for the range of analysis Characterisation of coatings as applied
techniques
Following application, the coating thickness, gloss and
Surface
No. of Dimensions Coating Analysis colorimetry measurements were recorded for each
preparation
samples (mm) system methods
standard coating. A control sample of the coating systems is
8 Sa 2.5 stored in the dark throughout the test period to allow
Oxygen
8 40 × 40 × 6 St3 for comparison with samples undergoing outdoor
consumption
8 Glass
exposure.
40 Sa 2.5
1
40 60 × 60 × 4 St3 EIS; gloss
Outdoor exposure
40 Glass
5 Sa 2.5 Colorimetry; Samples are mounted between strips of extruded ‘H’
150 × 150 × 4
5 St3 pull-off testing section PVC fixed to a stainless steel frame angled at
8 Sa 2.5 60° to the horizontal (Figure 2). Each sample frame
Oxygen
8 40 × 40 × 6 St3
consumption is fixed off the ground in a south-facing direction.
8 Glass The samples are exposed in a location whose condi-
40 Sa 2.5 tions are between a low (C2) and medium (C3) risk
2
40 60 × 60 × 4 St3 EIS; gloss environment category (BS EN ISO 12944-2:2017;
40 Glass International Organization for Standardization 2017)
5 Sa 2.5 Colorimetry; on the edge of a small inland town. Onset HOBO data
150 × 150 × 4
5 St3 pull-off testing
loggers record air temperature, relative humidity (RH),
8 St3 Oxygen
40 × 40 × 6 surface wetness and cumulative light exposure in real
8 Glass consumption
time throughout the outdoor sample exposure period.
8 St3
60 × 60 × 4 3 EIS; gloss This data will be collated to relate weather patterns to
8 Glass
coating performance.
5 Sa 2.5 Colorimetry;
150 × 150 × 4
pull-off testing

with a sheen appearance. Control samples of float glass

cut to the same dimensions, oil gilded and coated in
the same manner as the wrought iron samples allow for
examination of changes in the coatings over time inde-
pendent of the wrought iron substrate.

Coating
Sample coupons were brush painted with one of the three Figure 2. Samples mounted on their exposure frame with the
paint systems chosen (Table 2). environmental monitoring equipment fitted

Table 2. Details of the coating systems as applied to the samples

Coating No. Minimum dry film

Manufacturer Type Coating
system coats thickness (µm)
Kem-Kromik 489 zinc phosphate primer 2 75
Sherwin-Williams Protective
1 Alkyd Sherwin L654 micaceous iron oxide midcoat 1 75
and Marine Coatings
Kem-Kromik 530 gloss topcoat 2 30
Macropoxy L425 zinc phosphate primer 2 75
Epoxy Macropoxy 267 high-solid micaceous iron
2 Sherwin-Williams 1 125
oxide midcoat
Acrylic urethane Acrolon C237 sheen finish topcoat 2 50
Lead-based linseed oil Red lead primer 2
3 Traditional
(under licence) Lead carbonate finish coat 3
A COMPARISON OF THE LONG-TERM OUTDOOR PERFORMANCE OF TWO MODERN PAINT COATING SYSTEMS AND A TRADITIONAL LEAD-BASED PAINT APPLIED TO HISTORIC WROUGHT IRON 97

Assessment of coating performance reference electrode were inserted into the top. The circuit
was completed by connecting the sample terminal to form
Coating performance, both protective and aesthetic,
the working electrode. Synthetic rain was chosen as the
is assessed annually using oxygen consumption in a
electrolyte to match the real-time exposure environment
fixed RH, EIS, pull-off adhesion testing, colorimetry,
more closely. This was developed for the assessment of
gloss measurement and digital photography. As EIS and
copper alloys and steels in outdoor environments (Letardi
pull-off testing are destructive techniques, these samples
et al. 2016). It contains several soluble salts and is used at
(Table 1) are not returned to outdoor exposure. Oxygen
a 10× concentration. The analysis was carried out using
consumption samples are returned to outdoor exposure
an Ametek/Princeton Applied Research PARSTAT 3000A
after measurement, being remeasured each year.
potentiostat/galvanostat instrument, with the acquired
Electrical impedance spectroscopy data being processed using Rhd Instruments RelaxIS 3
impedance analysis software.
EIS can be used to characterise the behaviour of an
electrical system by applying a small electrical excitation Pull-off adhesion testing
signal (sinusoidal voltage) to the system and measuring
Adhesion of the coating systems was examined by pull-off
the response (current) created (Loveday et al. 2004,
testing according to BS EN ISO 4624:2016 (British Stand-
Orazem and Tribollet 2017). The frequency of the signal
ards Institution 2016). This measures the force required
is varied, and the resulting responses can be analysed
to pull-off a specified diameter of coating using hydraulic
using electrical methods (Cogger and Evans 1999). EIS
pressure. The technique records the highest pressure
has been used as a tool to test varying coating types since
required to detach all or part of the paint coating from
the mid-20th century and has recently been applied to
the substrate surface. Coatings might fail at the substrate
the field of heritage science (Amirudin and Thierry 1995,
surface or within/between coating layers.
Cano et al. 2010, Ramírez Barat et al. 2019). EIS spectra
are produced either showing the impedance Z (the ratio Each test area was lightly cleaned and abraded using a
of voltage over current) and phase angle F, known as a 3M Scotchbrite pad (7447) before degreasing with indus-
Bode plot, or in polar coordinates with real and imaginary trial methylated spirits. A 20 mm aluminium dolly was
elements (Nyquist plot). These plots provide information bonded to the paint surface at each test site using Araldite
on the performance of a coating, with impedance values 2021-1, a two-part methacrylate adhesive. Eight dollies
reducing as a coating begins to fail. were adhered to each sample and left for 24 hours for the
resin bond to form fully. The test area was separated from
One corner of each EIS sample was tapped with an M4
thread to fit an electrical connection post. The sample
was placed on a Gamry Instruments PTC1 paint test cell
(Figure 3). The cell was filled with 40 mL of electrolyte
before a graphite counter electrode and saturated calomel

Figure 4. A 150 × 150 mm sample coupon being prepared for pull-off

Figure 3. Painted coupon mounted in the test cell measurements
98  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
the surrounding adhesive using a cutting tool (Figure 4)
and adhesion tested using a DeFelsko PosiTest AT-A
pull-off adhesion tester.
Colorimetry
To assess colour change, 36 colorimeter measurements
were made on each large sample using a Konica Minolta
CM-700d portable sphere-type spectrophotometer every
12 months (Figure 5). Results are processed using Konica
Minolta SpectraMagic NX software. Colorimetry meas-
urements are compared with the previous measurement
12 months before and with the control samples stored in
the dark (Gilchrist and Nobbs 2017).
Figure 5. The Konica Minolta CM-700d colorimeter instrument and a
sample with overlaid template
Gloss
The gloss of a surface relates to its level of reflectivity and,
for paints, is defined under ISO 2813:2014/ASTM D532
(Chadwick and Kentridge 2015; International Organiza-
tion for Standardization 2014). The standard specifies a
method of using three geometries of 20°, 60° and 85° to
COATINGS, CONSOLIDANTS & CORROSION INHIBITORS
measure the gloss level of a coating by quantifying the
reflectance of the surface. A sample mount was used to
ensure the gloss measurement could be repeated in the
same position every 12 months; the gloss of each sample
was measured using a Rhopoint Novo-Gloss Trio 20/60/85
glossmeter and repeated after rotating the sample by 90°.
Results
Visible change
Neither the alkyd system nor the epoxy system samples
show any visible change after 24 months of outdoor
exposure. The lead/linseed oil system, however, exhibits
distinct change including chalking, shrinkage and
cracking of the finish coat (Figure 6).
Figure 6. Lead-painted sample before exposure (left) and after
24 months in outdoor exposure (right) showing chalking and cracking
of the finish coat
Electrochemical impedance spectroscopy
Representative EIS Nyquist plots are presented for all
coating systems and surface preparation methods at 12,
24 and 36 months (Figure 7).
Figure 7. Typical Nyquist
plots for the three different
coating types after 12-, 24- and
 36-month exposure
A COMPARISON OF THE LONG-TERM OUTDOOR PERFORMANCE OF TWO MODERN PAINT COATING SYSTEMS AND A TRADITIONAL LEAD-BASED PAINT APPLIED TO HISTORIC WROUGHT IRON 99

Pull-off adhesion testing
The results of pull-off testing at 12 and 24 months are
given in Figure 8 and Table 3. The average pull-off values,
their range and the mode of failure of the system are
provided. Pull-off testing was not carried out at 0 months
as the curing of the coating systems could not be guar-
anteed to be complete.
Colorimetry
The average colorimeter values as measured for samples
of each coating system at 0 and 24 months of outdoor
exposure are given in Table 4. The differences between the
values at 0 and 24 months are used to produce the dE*,
dL*, da* and db* values using CIE 2000, which express
the change in colour over the exposure time.

Gloss
The average gloss values for samples of each coating type
exposed for 0, 12 and 24 months are given in Table 5.

Figure 8. Boxplot of the pull-off values for samples coated with the three
coating systems prepared to Sa 2.5 and St3 showing the range of values
attained. The box represents the interquartile range, the horizontal line
within the box denotes the median, and the upper and lower whiskers
show the maximum and minimum values
Discussion
Visible change
After two years of outdoor exposure there have been some
measurable and observable changes to the paint coating
systems applied to the wrought iron samples. One of the
clearest signs that a coating may be beginning to lose its
protective properties is a change in its appearance. This

Table 3. Average pull-off values and modes of failure for samples coated with the three coating systems at 12 months

Surface Exposure Pull-off values (MPa)

System Mode of failure
preparation (months) Average Range
1 (Alkyd) Sa 2.5 12 5.9 4.2 Adhesion failure at primer/metal interface
Sa 2.5 24 5.9 3.1 Adhesion failure at primer/metal interface
St3 12 4.0 3.2 Cohesion failure within corrosion layer
St3 24 4.4 3.1 Cohesion failure within corrosion layer
2 (Epoxy) Sa 2.5 12 5.2 2.7 Adhesion failure at topcoat/midcoat interface
Sa 2.5 24 2.8 2.3 Adhesion failure at topcoat/midcoat interface
St3 12 5.5 1.4 Cohesion failure within corrosion layer
St3 24 3.9 2.8 Cohesion failure within corrosion layer
3 (Lead) St3 12 2.8 1.4 Adhesion failure at primer/topcoat interface
St3 24 2.0 0.9 Adhesion failure at primer/topcoat interface

Table 4. Colorimetry values expressed in the L*a*b* colour space with average values for samples at 24 months of exposure compared to values for
samples at 0 months of exposure to produce dE*, dL*, da* and db* values as a measure of change. The threshold for visible change is dE*ab ≥ 1.5

System (exposure
dE*ab(D65) L*(D65) a*(D65) b*(D65) dL*(D65) da*(D65) db*(D65)
months)
1 Alkyd (0) - 89.77 0.43 8.70 - - -
1 Alkyd (24) 1.91 (visible change) 89.57 0.81 6.93 −0.20 (darker) 0.39 (more red) −1.76 (less yellow)
2 Epoxy (0) - 90.62 1.78 7.29 - - -
2 Epoxy (24) 0.69 (no visible change) 90.00 1.74 7.47 −0.62 (darker) −0.04 (less red) 0.18 (more yellow)
3 Lead (0) - 65.14 −2.34 7.92 - - -
3 Lead (24) 10.96 (visible change) 70.48 0.78 −1.04 5.34 (lighter) 3.12 (more red) −8.96 (less yellow)
100  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND COATINGS, CONSOLIDANTS & CORROSION INHIBITORS

Table 5. Gloss values (GU) at 20°, 60° and 80° for samples of each coating system and the influence of surface preparation
coating type exposed outdoors for 0, 12 and 24 months
level. After 12 months the alkyd (System 1) and epoxy
Exposure Average gloss units (GU) resin (System 2) systems on surfaces blasted to Sa 2.5
System
(months) 20° 60° 85° exhibit the greatest bond strength, with overlapping value
0 35.41 75.10 83.32 ranges showing that there is no significant difference
1 (Alkyd) 12 20.21 62.18 74.62 between the two. Adhesive failure between the coatings
24 13.86 51.63 71.27 or between the topcoat and the dolly demonstrates that
0 4.04 9.98 19.63 the adhesive bond of the primer to the substrate metal
2 (Epoxy) 12 4.00 10.60 20.34
exceeds these values. For samples of alkyd and epoxy
24 3.89 10.39 19.96
systems prepared to St3, failure occurred within the
0 2.49 2.88 6.88
compact oxide layers remaining on the metal surface,
3 (Lead) 12 2.64 −1.13 1.47
showing that the weakest point in the protective system
24 2.97 1.45 0.08
is within the oxides themselves.

With lead-painted samples at 12 months, failure occurred

can serve as an early warning that the heritage metal-
work may be at risk. To date, this is only noticeable on
the lead-painted sample coupons (Figure 6). Observable
after 12 months, by 24 months the lead-based linseed oil
coating exhibits dramatic change in the appearance of
its finish coat. Not only has the surface lost much of its
colour, but it has also chalked, shrunk and cracked, likely
due to loss of binder. Despite the lack of visible change in
the alkyd and epoxy systems, the analytical techniques
applied here reveal that all of the coating types have begun
to show signs of deterioration.
Electrical impedance spectroscopy measurements
at the lowest forces. The failure at the interface between
the primer and the degraded finish coat layers is unsur-
prising given the extent of visible damage to the finish
coat, which includes shrinkage and cracking, demon-
strating poor adhesion to the undercoat.
Colour and gloss level changes
Both the colorimeter measurements and the gloss meter
results showed that the paint surfaces have become
altered. This is exhibited as subtle colour changes
(Table 4) and a gradual reduction in the gloss level of
the paint surface (Table 5).

EIS measurements taken after 12 months revealed that
for both sets of metal samples painted with the alkyd and
epoxy resin systems (Figure 7), the coatings were acting as
capacitors, essentially non-conducting, with an electrical
resistance of greater than 108 Ω cm2. This is confirmed by
creating an equivalent electrical circuit as a simulation.
For the lead-painted samples, the response was slightly
different (Figure 7). Electrical resistance was lower after
12 months (~106 Ω cm2) and had reduced to < 103 Ω cm2
after 24 months. The performance of the coating was
deteriorating, acting as both a resistor and capacitor. A
small amount of current (amps, W) is flowing through
the paint layers, but the coating provides increasing
resistance as the frequency (Hz) increases. For the alkyd
and epoxy coatings, the levels of electrical resistance had
reduced slightly after 24 months.
Pull-off tests
Examination of the pull-off test results (Figure 8;
Table 3) reveals differences in the strength of each
Colour change for the alkyd-coated samples (System 1)
falls just above the threshold for a visible change, although
this was not perceived by the observers. The colorimeter
values indicate that there has been a slight darkening of
the topcoat, which has become slightly more red and less
yellow. Changes in the epoxy-coated samples (System 2)
do not meet the threshold for visibility, but they exhibit
a slight darkening and have become less red and more
yellow. The biggest change is seen in the lead/linseed
oil-coated samples (System 3), whose change value
exceeds the visible threshold by 7 times and indicates
that the coating is lighter, more red and less yellow. This
corresponds well to the chalking of the finish coat and
the appearance of the red undercoat through the cracks
in the finish coat.
Gloss units (GU) are the measurement scale based
on a highly polished black glass standard that gives a
reflectance of 100 GU at a specified angle.1 The angle
of measurement is altered according to the level of
gloss. The measurements taken at 60° revealed that
A COMPARISON OF THE LONG-TERM OUTDOOR PERFORMANCE OF TWO MODERN PAINT COATING SYSTEMS AND A TRADITIONAL LEAD-BASED PAINT APPLIED TO HISTORIC WROUGHT IRON
the alkyd-coated (System 1) surfaces have reduced in
gloss level from a high (> 70 GU) to a medium gloss
(10–70 GU) level, even within the first 12 months.
For the epoxy (System 2), the gloss level has largely
remained unchanged after 24 months (Table 3). The
original acrylic urethane finish coats applied gave a
sheen rather than gloss finish. As the original level of
gloss was low (< 10 GU) the most appropriate measure-
ment values to use are at 85°. The lead-painted samples
showed significant changes to their gloss levels (Table 5).
The initial gloss level was very low (> 10 GU) at a meas-
ured angle of 85°, and this has reduced to almost zero
after 24 months of exposure.
Conclusion
This paper has reported on preliminary findings of a
five-year study examining the real-time performance
of three protective coating systems for historic wrought
iron exposed outdoors. Even in the limited exposure
period to date, it is possible to identify significant changes
in the traditional lead coating, which may continue to
perform a protective function for the iron substrate but
has completely failed in its aesthetic capacity. Aesthetic
changes in the alkyd and epoxy systems are minor, being
barely or not noticeable.
The findings reveal that preparing the surfaces to St3
means that with the alkyd and epoxy systems, the
corrosion product layers themselves are the primary
weakness in the protective system. This has implications
for heritage, where justifying the loss of original mate-
rial associated with blasting to near-white metal can be
challenging.
The initial results from the EIS measurements reveal
that the epoxy resin coatings are the best performing,
with the alkyd paints also maintaining a high level of
protection. The lead coatings show the greatest changes
in their performance.
The next three years will see coating performance chal-
lenged further by outdoor exposure, and the mode and
extent of any breakdown of the coatings will be reported
in future papers.
Notes
1
www.rhopointinstruments.com/faqs/how-is-gloss-
measured/
101
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 Young Conservation Professional

Keris Blade Protection – A Comparison of Traditional and

Contemporary Coatings

Janine Meier
Historisches Museum Basel
Basel, Switzerland
janine.r.meier@gmail.com

Abstract
Keris daggers are weapons and spiritual objects of unique cultural
significance from the Indonesian Archipelago. They challenge
conventional conservation efforts due to their composition,
fabrication techniques, and, in particular, the spiritual value
attributed to the traditional coating on the blade, which is
applied during ceremonial processes. This study presents a
comparison of contemporary and traditional coatings for keris
blades. Each coating was tested on multilayer steel coupons
reflecting keris blade properties (pamor) and standardized low-
alloy steel coupons. The coupons were then exposed to a stress
test to assess protective effectiveness. The results of this research
suggest that conservation strategies should include the use of
a traditional mixture of natural oils (coconut oil, sandalwood
oil, and ylang-ylang) to protect keris in museum environments.
Keywords
keris, kris, Indonesia, dagger, coating, traditional, etching,
corrosion

Introduction
The keris originates from the Indonesian Archipelago,
where it serves as a weapon, a holy object in ritual cere-
monies, and a personal symbol of protection, making it
crucial to cultural identity (it has been listed as UNESCO
intangible cultural heritage since 2005; UNESCO Office,
Jakarta 2005) (Figure 1). In Indonesia, spirituality is
present everywhere. In contrast to western culture,
spirituality is not seen as something that is directly
linked to religion. As religion changed over time, the
myths and traditions surrounding keris remained the
same.1 A keris is composed of a sheath, handle, and
blade fabricated of different alloys and various organic
materials. Keris blades are made from pamor, a tradi-
tional Indonesian multilayered steel, whose pattern
is emphasized by etching the surface with lime juice
and arsenic sulfide. The etching is renewed and a new
coating applied to the blade (Weihrauch 1996) during a
traditional annual ceremony. Most keris are not treated Figure 1. Four keris from the MKB. © JM, HE-Arc/MKB 2020

during their time in museum collections, leaving only

residues of coating material or coatings that are no longer
protective (Figure 2). In the traditional Indonesian
worldview, the coating not only serves as protection
for the blade material, but it is also believed to provide
spiritual nourishment. The loss of the nourishment
affects the intangible value, described in Indonesia as the
loss of contrast between the layers of the pamor, a matt
surface, and the absence of odor (Kerner 1995). In this
study, it is suggested that the protective coating layer of
the keris blade should be viewed as an integral part of the
104  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Figure 2. Keris (IIc 2118) from the MKB under visible light (VIS) and under
ultraviolet fluorescence (UVF) revealing the synthetic oil coating (FTIR
analyzed). © JM, HE-Arc/MKB 2020
object. Multiple studies have assessed protective coatings
(Dalewicz-Kitto 2016, Brüggerhoff 2001), but traditional
coating materials such as natural oils and multilayer steel
substrates have rarely been included. This study focuses
on the specific case of protecting keris blades in western
collections with the aim of guiding the development
of an integrated conservation strategy specific to their
cultural significance.
Methods
A collection of 144 keris at the Museum der Kulturen
Basel (MKB) was examined. Of these, 13 were analyzed
using X-ray fluorescence (XRF) and Fourier transform
infrared (FTIR) spectroscopy to determine the composi-
tion of the coating residues and blade materials. A stress
test was performed to compare the protective capability
of the coatings. Coatings and substrates were selected
based on the literature, analysis, and communication
COATINGS, CONSOLIDANTS & CORROSION INHIBITORS
with experts and collectors from various institutions. The
cyclical conditions during stress tests were selected based
on the literature and evaluation of the climatic conditions
in the museums and countries of origin.
Experimental setup
The following coupons were prepared: Six different coat-
ings (2. to 7.) were tested on coupons of three different
substrates (P, S, and K; see following section) as well as
on uncoated coupons as controls (1.). As a stress test,
all coupons were stored in varying climatic conditions,
whereas a reference group (X) was stored in stable condi-
tions with low relative humidity (RH). Furthermore, the
test included pamor coupons with residues from etching
(8.) and without etching (9.) (Figure 3).
Coupons
Three different substrates were selected: pamor multi-
layer steel coupons (P), produced and etched with
the traditional recipe of lime juice and arsenic sulfide
(Kerner 1995); low-alloy steel (S) (DC04 B (EN 10130));
and pre-corroded low-alloy steel (K) (corroded for two
weeks by daily cycles of room temperature, 50 °C and
100% RH).
Coatings
Three contemporary and three traditional coatings
were compared. The former, representing commonly
used museum coatings, consisted of a microcrystalline
Figure 3. Coupon groups
for stress test: uncoated (1),
contemporary coated (2–4),
traditionally coated (5–7) on
pamor (P), low-alloy steel (S),
and pre-corroded low-alloy
steel (K) substrate. Groups 8
and 9 comprise pamor coupons.
The X group represents the
reference coupons not included
 in the stress test
KERIS BLADE PROTECTION – A COMPARISON OF TRADITIONAL AND CONTEMPORARY COATINGS 105

wax (2., Cosmoloid H80, 20% in Shellsol T (w/w)), an Stress test

acrylic resin lacquer (3., Paraloid B-44, 20% in acetone
The coupons were exposed, at a slight angle, to a six-week
(w/w)), and paraffin oil (4.). The traditional coatings
stress test in a climatic chamber (Vötsch Typ VC 0020)
included coconut oil (5., 8.2, 9.2), a traditional mixture
with cycles of warm-humid (34 °C and 90% RH) and
(6.) of coconut oil, sandalwood oil, and ylang-ylang
cold-dry (18 °C and 40% RH) conditions with transition
(50%/25%/25% (w/w)), and a synthetic perfumed oil (7.,
phases of 30 minutes every 12 hours.
Kerisöl 2006). Currently, both blends of naturally odorous
oils (6.) and synthetic oils with added fragrances (7.)
Evaluation
are used during ceremonial processes. A single layer of
each coating was applied at room temperature on clean The coatings were evaluated according to four criteria:
(acetone-treated) coupons, using cotton cloths to apply ease of application, protective capacity, aesthetic prop-
the oil and brushes for the wax and acrylic resin, and erties, and maintenance. The coupons were evaluated
they were dried for three weeks. weekly during the stress test to document the develop-

Figure 4. Results after six weeks in

the climatic chamber with exemplary
coupons from each group and
corrosion evaluation by corrosion
degree according to the DIN norm EN
ISO 6270-2 and amount of corrosion
 spots

Figure 5. Results after six weeks in the

climatic chamber. Shows the corrosion
development and change of coating
 properties
106  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND COATINGS, CONSOLIDANTS & CORROSION INHIBITORS

ment of corrosion and visible changes in the coating with

a digital microscope. The corrosion protection was eval-
uated by determining the degree of corrosion according
to DIN EN ISO 6270-2 AHT (Deutsches Institut für
Normung e. V. 2017) and the number of corrosion spots.
Changes in the aesthetic properties were compared by
color-calibrated photographs.

Results
The traditional coconut oil-based coatings (5., 6.)
showed the best anti-corrosion properties across all
three substrates (Figure 4). Cosmoloid H80 (2.) prevented
Figure 6. Corrosion of uncoated coupons S, P, and K (200× magnification)
corrosion the least well across all tested coatings, with
light microscopic inspection revealing that corrosion
developed in small, uncoated areas due to cold applica-
tion. The two synthetic oils—paraffin oil (4.) and Kerisöl
2006 (7.)—achieved good corrosion protection but only
for a limited period of time. These coatings provided
protection for as long as they were visible as a glossy
surface film (Figure 5). The corrosion morphology varies
with different coatings and is highly dependent on the
substrate and degree of corrosion (Figures 6–8).

As expected, the degree of corrosion on the pre-corroded

coupons (K) was higher than on the non-corroded
substrates, and the uncoated coupons corroded more
than the coated coupons. On pamor coupons (P), the Figure 7. Corrosion of Cosmoloid H80-coated coupons S, P, and K (200×
corrosion developed across the two alloys of the multi- magnification)
layer steel. Additional tests indicated that residues of
the etching solution (8.) were not a source of corrosion
acceleration, and the lack of traditional etching (9.) did
not influence the corrosion process.

Most of the contemporary and traditional coatings

tested increased the contrast in the pamor pattern and
the gloss. However, the wax and coconut oil did not
have this effect on the pamor coupons. The spiritually
important odor requirement was only met by the tradi-
tional mixture (6.) and the Kerisöl 2006 (7.). None of the
coatings changed in color during the test. Dust particles
were observed on the sticky surface of the natural and
synthetic oils.
Figure 8. Corrosion of Paraloid B-44-coated coupons S, P, and K (200×
The oil coatings could be evenly applied to the coupons magnification)
except for the coconut oil, which produced nonuniform
Discussion
and thicker coating films. The Paraloid B-44 was chal-
lenging to apply evenly. The Cosmoloid H80 did not The mixtures of natural oil-based coatings provided
cover all of the coupon cavities when applied at room higher corrosion protection, better aesthetic charac-
temperature. teristics, and greater maintenance advantages than the
KERIS BLADE PROTECTION – A COMPARISON OF TRADITIONAL AND CONTEMPORARY COATINGS
synthetic oil, wax, or lacquer coatings. In addition,
natural oils are often less toxic and harmful to conser-
vators and the environment.
Due to the irregular surface on keris blades, coating
interventions are not entirely reversible, with residues
remaining on the surface. Consequently, the introduction
of a new material to the object, such as contemporary
coatings, must be carefully considered.
Coatings need to be renewed periodically. Therefore,
monitoring and renewal must be included in the conser-
vation strategy. Oil coatings can be renewed easily with
less time, which simplifies regular maintenance. Natural
oils (5., 6.) protect longer than synthetic oils (4., 7.)
and therefore lead to less frequent renewal cycles. The
stress test demonstrated the importance of scheduled
reapplication of synthetic and natural oils to prevent
accelerating corrosion due to dust particles adhering
to the oil coatings (Figure 9). For coconut oil-based
coatings, temperature fluctuations should be avoided
to prevent cyclical hardening and liquefying, which
results in an uneven coating film.
The corrosion morphology that arises when natural and
synthetic oil coatings lose their protective properties is
equivalent to corrosion observed on keris blades with
traditional coatings. However, the filiform corrosion
of acrylic coatings (Figure 10) is atypical and distracts
aesthetically from the highly valued pamor pattern.
Consequently, lacquer coatings are unsuitable for keris
blades.
It is important to recognize that cultural significance
and the goals of contemporary conservation are not
Figure 9. Dust particle on pamor coupon with paraffin oil coating (4) and
localized corrosion development (50× magnification)
107
Figure 10. Filiform corrosion under acrylic coating (FTIR analyzed) on
keris blade (IIc 22217) from the MKB (20× magnification).
© JM, HE-Arc/MKB 2020
intrinsically contradictory. According to the Burra
Charter of 2013, which defines ethics in conservation
and takes into account cultural significance, traditional
techniques should be favored if there are no conserva-
tional disadvantages (Australia ICOMOS 2013, Article
2.1/4.2). Since keris blades benefit from traditional
coatings, these techniques are recommended.
Conclusion
The results of this work suggest that traditional and
natural coating materials should be employed in
museum environments due to their superior protective
properties. The traditional approach used throughout
the Indonesian Archipelago for keris blade preserva-
tion adheres to ethical standards and historic aesthetic
qualities, while also providing an environmentally
conscious and user-friendly conservation approach.
Ideally, objects are protected from dust, monitored
regularly, and receive a periodic reapplication of the
coating. Additionally, preservation with a traditional
coating allows visitors to experience a nourished keris
in a traditional and spiritual sense as a blade with
enhanced contrast in the pamor layers and the intended
luster and odor. The fact that olfaction is an important
part of these objects offers a rather unexplored oppor-
tunity to use the sense of smell as a means to access
those objects. In conclusion, this study demonstrated
the necessity of studying traditional techniques and
the value natural products can add to contemporary
conservation methods.
108  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND COATINGS, CONSOLIDANTS & CORROSION INHIBITORS

Acknowledgments fellowship at The Metropolitan Museum of Arts, New

York, and is currently working in a permanent position
The author would like to thank the Haute École Arc
at the Historisches Museum Basel, Switzerland.
Conservation-restauration in Neuchâtel for providing
equipment and expertise, the Museum der Kulturen Basel
for the possibility to study its collection, and all experts
for generously sharing their experiences.

Notes
1
See article “Simpler keris cleansing ritual this year,” The
Straits Times, 21 May 1996, Singapore.

References
Australia ICOMOS. 2013. The Burra Charter 2013. The
Australia ICOMOS Charter for Places of Cultural Signif-
icance. Burwood: Australia ICOMOS Incorporated and
International Council on Monuments and Sites.
Brüggerhoff, S. 2001. Korrosionsschutz für umwelt-
geschädigte Industriedenkmäler aus Eisen und Stahl.
Bochum: Deutsches Bergbau-Museum.
Dalewicz-Kitto, S.J. 2016. Stopping corrosion around the
world: An investigation into protective surface coatings
on arms and armour. Journal of the Institute of Conser-
vation 39(1): 44–56.
Deutsches Institut für Normung e.V. (DIN). 2017. DIN
ISO 6270-2: Paints and varnishes – Determination of
resistance to humidity – Part 2: Condensation (in-cabinet
exposure with heated water reservoir), German version of
EN ISO 6270-2:2018. Berlin: Beuth Verlag.
Kerner, M. 1995. Der Keris im magischen Weltbild. Kirch-
dorf: M. Kerner.
UNESCO Office, Jakarta. 2005. Annual Report 2005.
Jakarta: UNESCO Office, Jakarta.
Weihrauch, A. 1996. Der Keris in Indonesien – Herkunft,
Bedeutung, Typenvielfalt und symbolischer Hintergrund
der Einzelelemente. Master’s thesis, Ethnology Seminar
of the University of Basel, Switzerland.

Author
Janine Meier’s professional education started with
an apprenticeship as a goldsmith. She completed her
master’s degree in conservation and restoration of
scientific and technical objects at the Haute École Arc
Conservation-restauration in Neuchâtel in 2020, after
which she worked at the Museum der Kulturen Basel and
the Bernisches Historisches Museum. She completed a
 Young Conservation Professional

Preliminary Investigation of the Use of Chitosan-based

Coatings for Outdoor Cultural Heritage Objects

Carlota Carvalho Nádia Silva Eduarda Vieira Patrícia R. Moreira*

Research Centre for Science and
Technology of the Arts (CITAR),
Universidade Católica Portuguesa
Porto, Portugal
camcarvalho@ucp.pt
Centre for Biotechnology and Fine
Chemistry - Associate Laboratory
(CBQF), Universidade Católica
Portuguesa
Porto, Portugal
ncsilva@ucp.pt
Research Centre for Science and
Technology of the Arts (CITAR),
Universidade Católica Portuguesa
Porto, Portugal
evieira@ucp.pt
Research Centre for Science and
Technology of the Arts (CITAR),
Universidade Católica Portuguesa
Porto, Portugal
prmoreira@ucp.pt
*Author for correspondence

Abstract
Outdoor art is continuously exposed to climatic factors and to
direct contact with the public, both of which pose challenges
for long-term conservation. This study examined the efficacy of
a chitosan-based coating and its applicability for metallic objects
such as outdoor sculptures. The chitosan film was applied on
stainless steel specimens using three different application
methods (paintbrush, spray, and syringe). Each specimen was
microscopically and colorimetrically examined before, during,
and after application of the coating and following aging tests.
Removal of the coating from the surface after 48 hours and after
aging was also tested, using cotton swabs soaked in acetone,
ethanol 96%, and water. The coating was not removable by
mechanical force alone, which instead was effective together
with water applied with a cotton swab, thus demonstrating
treatment reversibility. The coating’s wettability and stability
were determined by evaluating the changes in coated specimens
in contact with water (surface tension tests) and submerged
for 24 hours. Application of the coating using a paintbrush
resulted in the best adherence to the metal, considering the
structural characteristics of the test specimens. No dissolution
of the coating occurred from the immersed coated specimens.
These properties of the chitosan coating recommend its use for
outdoor applications.
Keywords
stainless steel, chitosan, coating, sustainability, public art

Introduction
For conservation and restoration professionals, effective
products that are sustainable, nontoxic, and have a low
impact on the user’s health and on the environment are
highly desired. Chitosan, a biopolymer obtained from
the shells of crustacean waste, is soluble in weak acids
but not in water and has the ability to form films that
are biodegradable and nontoxic (Giuliani et al. 2018).
Consequently, chitosan film has been proposed as a
sustainable alternative to coatings that are currently
commercially available (Moreira et al. 2018). Figure 1. Sculpture Eu Espero (1999), by Fernanda Fragateiro (MIECST –
Santo Tirso International Museum of Contemporary Sculpture)

In this study, the applicability and reversibility of a

chitosan coating on metallic stainless-steel specimens
were determined in order to evaluate the applicability of
this method to the sculpture Eu Espero (1999), a public
work of art by the artist Fernanda Fragateiro that consists
of a backless stainless-steel bench (Figure 1).
Materials and methods
Specimens and coating preparation and application
The chitosan film tested in this study consisted of a
low-molecular-weight chitosan solution prepared at a
concentration of 1% in 1% acetic acid and with a pH of 3.9
110  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
(Silva et al. 2018). The coating was applied to 27 stainless
steel specimens approximately 39 × 36 × 1 mm in size
using a paintbrush (PB) or syringe (SY) or as a spray (S).
Six replicates were established for the SY specimens and
12 each for the S and PB specimens. The coated S and PB
specimens were dried for 24 hours at room temperature,
and the SY specimens for 24 hours at 30°C.
Photography and optical microscopy
Each specimen was imaged before and after coating appli-
cation and the aging tests using a Canon EOS M50 camera
equipped with an EFM 28 mm, f/3.5 macro IS STM lens
together with a Dino-Lite Pro2 AM4000 microscope.
Image storage and processing were performed using
DinoCapture 2.0 software, version 1.5.39.C.
Colorimetric analysis
Color alterations were assessed by colorimetric meas-
urements, performed according to the CIELab method
using a Konica Minolta CM-700d spectrophotometer
with three sequential readings. The L*, a*, b* CIELab
parameters were recorded before and after application
of the chitosan film. The ∆E was calculated as:
∆E*=
The RGB color of the uncoated and coated specimens
and of the specimens after removal of the coating was
recorded. The same methodology was applied to evaluate
the color changes in the specimens in the aging tests.
Aging tests
Thermal aging was performed by placing the specimens
for 12 days in a 60°C incubator with a relative humidity
of 20%–25%. UV light aging consisted of 24-hour
exposures for 12 days using a UV black light source
(LAMP15TBL, 15 W, 365 nm), with the specimens placed
in a closed cabinet to create a darkroom. The aging tests
Figure 2. Application of the coating using a paintbrush (a), a syringe (b), and spray (c)
COATINGS, CONSOLIDANTS & CORROSION INHIBITORS
were conducted using chitosan-coated PB and S spec-
imens, with specimens PB1–PB3 and S1–S3 subjected
to thermal aging, and specimens PB4–PB6 and S4–S6
to UV light aging.
Reversibility tests
The reversibility of the chitosan film on the PB, SY, and S
specimens was tested by mechanical removal and through
solubility tests using swabs soaked in acetone, 96%
ethanol, and water, mimicking the method commonly
used to clean outdoor works of art. The reversibility of the
coating was also examined in specimens subjected to the
aging tests. Surface and color changes were characterized
and quantified using a Dino-Lite Pro2 AM4000 digital
optical microscope and a Konica Minolta CM-700d
spectrophotometer.
Wettability and surface tension tests
A representative specimen from each coating method
was submerged in 35 mL of water for 24 hours at room
temperature. Reversibility after water absorption was
tested by attempting to lift the film using tweezers and
to remove it with a dry cotton swab. Surface tension tests
were performed by placing a 0.2 mL drop of water using
) a pipette on the age-tested specimens (PB1, S1, PB4, S4).
Results and discussion
The metallic specimens had a smooth surface but an
irregular structure, with concave and convex areas. They
were thus representative of outdoor works of art and
appropriate for testing the applicability of the chitosan
coating (Figure 2).
Application using a paintbrush resulted in better adher-
ence of the coating to the metallic specimens. Spray
application also resulted in good adherence but in some
concave areas deposition was visibly excessive. Syringe
application of the chitosan film was deemed ineffective
PRELIMINARY INVESTIGATION OF THE USE OF CHITOSAN-BASED COATINGS FOR OUTDOOR CULTURAL HERITAGE OBJECTS 111

Method of ∆E standard RGB before RGB after Table 1. Difference in the CIELab
∆E parameter (∆E) before (PB, SY, S)
application deviation (SD) coating coating
PB / PB-CH 7.89 0.60 and after (PB-CH, SY-CH, S-CH)
coating, based on the average
SY / SY-CH 8.47 0.55
values of the parameters L*, a*,
S / S-CH 7.32 1.12
 and b*

due to excessive deposition of the film in concave areas

and thus large differences in the thickness of the coating
(Figure 3).

The ∆E of the CIELab values calculated before and after

application of the coating showed that the change in L*
(luminosity) accounted for the largest ∆E value. The
colorimetric analysis and conversion of the CIELab
parameters to RGB values showed that the coated metallic
specimens were opaquer than the uncoated specimens,
but the visual impact was minimal (Table 1).
The films could not be removed mechanically without
damaging the specimen (independent of the coating
Figure 4. Microscope observations of the metal specimens after
mechanical removal of the coating
method), thus demonstrating the good adherence of the
film to metallic surfaces under dry conditions (Figure 4).
Regardless of the application or aging method, the film
could only be removed using circular movements of a
cotton swab moistened in water. For the specimens aged
with UV light (PB4 and S4), the coating removed by this
method had yellowed. This observation was in line with
the CIELab data, in which the value of b* (an indicator
of yellowing) was twofold higher than that before UV
aging, indicative of yellower hues (Tables 2, 3).

Table 2. Difference in the CIELab parameter (∆E) for the uncoated

specimens and after removal of the coating using a cotton swab with
water and mechanical force

Uncoated specimens / Specimens after removal

∆E
of chitosan coating with water
Uncoated specimen / PB1 after removal 3.16
Uncoated specimen / PB4 after removal 2.53
Figure 3. Microscope observations of the metal specimens before (a, b,
c) and after application of the chitosan coating using a paintbrush (d, Uncoated specimen / S1 after removal 1.92
g) or syringe (e, h) or spray (f, i) Uncoated specimen / S4 after removal 1.36

Chitosan-coated specimens after 24h L* L* SD a* a* SD b* b* SD Table 3. Average CIELab values

of the specimens 24 hours after
PB 73.91 0.59 −0.04 0.02 −0.19 0.12
coating and the average CIELab
S 74.27 0.32 −0.08 0.1 0.35 0.25 values of the specimens after
Specimens after 12 days of aging L* L* SD a* a* SD b* b* SD 12 days of aging. Difference in
PB 60°C 69.30 0.56 0.13 0.10 1.21 0.13 the CIELab parameter (∆E) for
PB UV light 69.14 0.10 −0.17 0.13 2.50 0.24 the specimens 24 hours after
coating and for the specimens
S 60°C 69.93 0.33 0.27 0.15 1.18 0.20
subjected to 12 days of aging
S UV light 69.88 0.35 0.12 0.74 2.05 1.65
Chitosan-coated specimens after 24 hours / PB/PB S/S PB/PB S/S
Specimens after 12 days of aging 60°C 60°C UV light UV light
∆E 4.82 4.43 5.48 4.71 
112  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND COATINGS, CONSOLIDANTS & CORROSION INHIBITORS

Figure 5. Uncoated specimens PB4 (a) and S4 (b); coated specimens PB4 (c) and S (d) after UV aging; removal of the UV-aged coating from specimens PB4
(e) and S4 (f) using a swab soaked in water; specimens PB4 (g) and S4 (h) after removal of the coating using a swab soaked in water and mechanical force

After removal of the coating, the optical and mechanical
properties of the metal specimens were the same as before
the coating was applied (Figure 5).
After 24 hours of immersion of the coated specimen
in water, the coating applied by syringe could only be
removed without damaging the metal by using a dry
cotton swab and tweezers. The coatings applied by paint-
brush and by spray could not be removed mechanically.
The chitosan film applied was also resistant enough to
be submerged in or in contact with water for at least
24 hours without dissolving, but it could be removed
thereafter by wet swabbing (Figure 6).
Conclusion
The chitosan coating tested on the metal surfaces was
of low aesthetic impact in dry environments and thus
offers a promising approach to the conservation of metal
outdoor art works. While it was resistant to solubiliza-
tion in water for at least 24 hours, the coating could be
removed using wet swabs in water and the application

Figure 6. Surface tension tests and Dino Lite images of specimens PB1 (a, a.1), S1 (b, b.1), PB4 (c, c.1), and S4 (d, d.1). Wettability tests of specimens
S6, PB6, and SY6 (e). Detail of specimen SY6 during the wettability test (f)
PRELIMINARY INVESTIGATION OF THE USE OF CHITOSAN-BASED COATINGS FOR OUTDOOR CULTURAL HERITAGE OBJECTS 113

of mechanical force, thus demonstrating its reversibility.
Further investigation is needed to evaluate the impact of
UV aging on the coating.
Acknowledgments
(ESB–UCP). She is currently a PhD student at ESB–UCP
working on the development of new nanomaterials to
prevent biodeterioration of cultural heritage. Her main
areas of interest are microbiology, natural polymers, and
antimicrobial coatings and nanoparticles.

This work was supported by National Funds through Eduarda Vieira holds a PhD in conservation and
FCT – Fundação para a Ciência e a Tecnologia under the restoration of historical and artistic heritage. She is
projects BIONANOSCULP (PTDC/EPH-PAT/6281/201), currently an assistant professor at the School of Arts of
BIO4MURAL (PTDC/HAR-ARQ/29157/2017), and the Universidade Católica Portuguesa (Porto) and has
UID/Multi/50016/2019. been the director of CITAR since July 2019. Her main
interests are green conservation, conservation of decora-
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Abreu, F. Henriques, M.M.E. Pintado, and E. Vieira. 2018.
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Authors
Carlota Carvalho has a master’s degree in conservation
and restoration of cultural heritage, with a focus on
outdoor sculptures made of inorganic materials. She is
interested in research fields associated with sustainable,
preventive, and green conservation.

Patrícia R. Moreira holds a PhD in biotechnology, is an

assistant professor at Universidade Católica Portuguesa
(UCP), and coordinates the CITAR’s Focus Area of
Heritage, Conservation, and Restoration in UCP. She is
interested in innovations in the field of cultural heritage,
with an emphasis on biodeterioration, sustainability,
circular economy, citizen science, and green conservation.

Nádia Silva has a MSc in microbiology by the Faculty

of Biotechnology, Universidade Católica Portuguesa
Testing the Compressive Strength and Reversibility of
Consolidants Applied to Marine Archaeological Gray Cast
Iron
Erik Farrell* Molly K. McGath
The Mariners’ Museum and Park The Mariners’ Museum and Park
Newport News VA, USA Newport News VA, USA
efarrell@marinersmuseum.org mmcgath@marinersmuseum.org
www.marinersmuseum.org/ www.marinersmuseum.org/
Abstract
Excavations of the American Civil War ironclad USS Monitor
recovered significant quantities of graphitized cast iron, including
major engineering components, structural fittings, and two
7,200 kg XI-Inch Dahlgren shell guns. As is common in gray cast
iron objects from marine archaeological environments, these
artifacts have undergone graphitic corrosion, compromising
their structure. Over the last decade, a variety of consolidants
have been applied to these artifacts at The Mariners’ Museum
and Park, with varying degrees of success. Due to the high risk
of structural damage in graphitized material and the difficulty
in re-treating large, complex, mechanical objects, conservators
began investigating additional methods for the conservation of
cast iron. The end goal was to establish an overall preservation
system for large cast iron objects from Monitor, and specifically
to conserve the Dahlgren shell guns. The initial phase of research
into the efficacy of selected consolidants on graphitized
cast iron has been completed and is discussed in this paper.
Introduction
Upon launching in 1862, USS Monitor became the first
iron warship in the United States Navy, and the world’s
first commissioned warship with a rotating gun turret.
Although active less than a year before sinking, Monitor
revolutionized naval warship design. Archaeological
excavations occurred through 2004, and artifacts are
being conserved at The Mariners’ Museum and Park in
Virginia.
Large objects are inherently limiting; with the available
facilities, health and safety resources, and funding, some
treatments used on smaller objects are not possible. Cast
iron objects excavated from Monitor include numerous
large engineering components and two 7,200 kg Dahlgren
shell guns, all structurally compromised by graphitic
corrosion (Selwyn 2004, 110). Small objects from Monitor
can be graphitized through the full thickness, and larger
Jonathan Echerd
East Carolina University
Greenville NC, USA
echerdj18@students.ec.edu
www.ecu.edu/
*Author for correspondence
Different methods have been used historically to consolidate
graphitized cast iron (e.g., microcrystalline wax, various
Paraloid formulations). However, there has been comparatively
little research into the direct physical effects of consolidants
on the strength of the graphite layer. Additionally, many prior
methods have little consideration for the size of the object;
some treatments simply are not possible at the scale required
for Monitor. A study was undertaken to make quantitative
comparisons of consolidants for graphitized cast iron, using
compressive strength testing to directly measure their effects.
The reversibility of effective treatments was also investigated
and additional testing carried out on Owatrol oil to confirm its
suitability for large-scale use.
Keywords
Owatrol oil, consolidation, graphitized, cast iron, marine
archaeology
objects retaining core metal typically have a 10–20 mm
thick graphitized exterior. Cracking, spalling, and surface
losses are significant hazards, and similar difficulties have
been noted at multiple labs (e.g., McCarthy 2002, 213;
Mardikian et al. 2009, 85; Näsänen et al. 2013, 294–97).
Research into the efficacy and reversibility of consolidants
was carried out with these challenges in mind.
Consolidation
Three test materials were used. Archaeological mate-
rial from SS Columbus (1850) was obtained from the
Maryland Archaeological Conservation Laboratory at
Jefferson Patterson Park and Museum (A-series samples).
Additional samples (S-series) were synthesized by elec-
trolytically de-alloying ASTM A48 Class 40 gray cast iron
(Figure 1). Vine charcoal (C-series) was used as a third
TESTING THE COMPRESSIVE STRENGTH AND REVERSIBILITY OF CONSOLIDANTS APPLIED TO MARINE ARCHAEOLOGICAL GRAY CAST IRON
material. Although less directly analogous to cast iron
due to the lack of iron degradation products, charcoal
is more physically homogeneous and was included to
better facilitate direct comparisons between consolidants.
Figure 1. Cross-section of a synthetic sample showing graphitized outer
layer and iron core. Image courtesy of The Mariners’ Museum and Park
Consolidants were identified based on desired properties
for large cast iron objects from Monitor. The goals were to
increase the compressive strength of graphitized cast iron
after desalination and drying were complete and to test
feasible application/reversal methods. The size of some
artifacts from Monitor is restrictive; direct immersion
of the largest objects requires approximately 15,000 L of
solution, making solvents untenably hazardous for direct
application. Several potential aqueous and non-aqueous
consolidants were identified based on a literature review:
microcrystalline wax (North 1987, Hamilton 1999),
Acrysol WS-24, Paraloid/Acryloid formulations, Poligen
ES 91009 (Degrigny 2008, Wolfram et al. 2010), and
Owatrol oil (Mardikian 2020).
Microcrystalline wax was not included in the testing
panel. Facilities are not available to heat enough wax
to immerse objects the size of Monitor’s Dahlgrens
and cannot be realistically obtained. Its reversibility is
also limited; although nominally reversible in boiling
water, studies show this is not the case (Johnson 1984,
72). Epoxies and (poly)urethanes likewise were not
tested despite historical use (e.g., North 1987, 230–31;
Hamilton 1999, 71–72) due to their limited reversibility
115
and the high probability of runaway reactions in epoxies
at large scales.
Acrysol WS-24 is an aqueous emulsion of an acrylic
copolymer. It has a near-neutral pH of 7.2, a Tg of 40 °C,
and is nominally reversible in strong alkali. Although
a higher Tg was desirable in case of an environmental
failure, WS-24 otherwise met the requirements for a
consolidant and was tested at 5%, 10%, and 25% v/v. A
single sample was also tested in a 1:7:2 ratio by weight
of WS-24 solids:isopropanol:water as a check against
problems in pure aqueous application methods (Phillips
1987, 146).
Various Paraloid acrylics exist; for efficiency, only one
was tested. Based on Tg, B-44 and B-48N were preferred
candidates, and ultimately B-44 was tested due to local
availability. Despite the inherent limitations of solvent-
born applications, 5% w/v B-44 in acetone was tested.
Poligen ES 91009 is an aqueous emulsion of ethylene wax,
identified in the PROMET project as a potential barrier
coating (Argyropoulos et al. 2013, 508). Unfortunately,
Poligen could not be obtained; multiple attempts to
contact US and European distributors went unanswered.
Aquacer 8527, an aqueous emulsion of a modified
polyethylene wax with nominally similar properties
to Poligen, was tested in its place. No previous testing
had been carried out, and additional testing would be
required to determine aging characteristics if the treated
strength was suitable. Aquacer was tested at a 75% v/v
concentration in deionized (DI) water.
Owatrol oil is a proprietary alkyd oil that acts as a
consolidant, corrosion inhibitor, and vapor barrier. This
material has been successfully used on graphitized marine
archaeological cast iron, including a large gun from CSS
Alabama (Mardikian 2020, 20). Owatrol is theoretically
soluble in strong alkali, but prior testing on cuttlefish
bone samples indicated some damage may occur during
removal (Ternisien 2011).
Density changes
Consolidants were applied by immersion for two weeks,
followed by desiccation until sample weights stabilized.
In total, 42 samples of each material were used, with each
consolidant applied to 6 of each sample material and
6 held as controls. Density was used to track changes,
derived from direct measurements of mass and dimen-
sions (Tables 1, 2).
116  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND COATINGS, CONSOLIDANTS & CORROSION INHIBITORS

Table 1. Average density before consolidation Testing

Material* Mean ± SD (g/mL)
Samples were allowed to dry in constant < 10% RH for
A 2.3753 ± 0.2283
approximately 30 days before testing. Compressive force
S 1.8397 ± 0.3603
tests used an Instron 5900R universal testing machine
C 0.2149 ± 0.0146
(Figure 2), with maximum strength determined by the
* Key: A = archaeological material from SS Columbus (1850);
S = synthetic graphitized cast iron; C = carbon (charcoal)
failure load of the sample.

Table 2. Average change in density

Mean ± SD
Material Consolidant
(percent increase)
Control 0
Owatrol 8.62 ± 1.47
5% B-44 0.92 ± 0.13
A 5% WS-24 2.08 ± 0.32
10% WS-24 2.10 ± 0.37
25% WS-24 2.49 ± 0.37
75% Aquacer 2.78 ± 0.33
Control 0
Owatrol 23.49 ± 5.34
Figure 2. Instron
5% B-44 2.59 ± 0.42
5900R universal
S 5% WS-24 4.88 ± 0.74
testing machine.
10% WS-24 5.80 ± 0.65 Image by
25% WS-24 8.44 ± 1.96 Jonathan Echerd,
75% Aquacer 9.33 ± 2.89 East Carolina
 University
Control 0
Owatrol 307.09 ± 18.82
Samples were first loaded into the Instron compres-
5% B-44 38.36 ± 4.15
sion testing plates set with a preload of 5 N to create a
C 5% WS-24 4.74 ± 0.82
common starting point for all samples. C- and A-series
10% WS-24 6.49 ± 0.99
25% WS-24 13.71 ± 2.18
were tested directly on the instrument plates, and an
75% Aquacer 39.88 ± 4.59 aluminum fixture plate was used to maintain the same
orientation for S-series samples and prevent slip under
Owatrol consistently provided the greatest increase in load (Figure 3). Load was increased gradually until
density across all sample materials, and Aquacer the failure, recording load, time, and displacement for each
second greatest. case (Figure 4).
In S- and A-series, WS-24 increased density by the third-
largest amount, with greater increases correlating to
greater concentrations of WS-24 in the immersion bath,
followed by Paraloid B-44 with the least increase. In iron
samples, WS-24 solutions de-emulsified; this behavior
is known, and one additional sample was consolidated
in 1:7:2 WS-24 solids:isopropanol:water (Phillips 1987,
146). This composition prevented de-emulsification
but removed the material’s primary benefit (aqueous
application).

In C-series, B-44 had markedly greater uptake into the

sample than any WS-24 application, with low-concentra- Figure 3. Sample in testing setup using fixture plate to maintain
tion WS-24 causing the least increase in density. orientation. Image by Ed Howard, East Carolina University
TESTING THE COMPRESSIVE STRENGTH AND REVERSIBILITY OF CONSOLIDANTS APPLIED TO MARINE ARCHAEOLOGICAL GRAY CAST IRON 117

High variability was experienced, and failure was often

hard to define. Some samples crumbled while load
continued to increase, not meeting the numerical defi-
nition of failure. Failure modes differed; some samples
completely collapsed, while others only cracked along
the leading edge. The degree of variability can be attrib-
uted to multiple factors, including sample geometry and
differences in material degradation.

Five control samples were tested for A- and S-series, and

six for C. Three samples were tested for each consolidant/
material pairing. Consolidant tests were compared to
control groups in a series of independent, two-tailed
t-tests, with results shown in Table 3.

None of the S-series tests show significance; the small

sample size and large standard deviation mask any effects.
Owatrol, B-44, and 10 and 25% WS-24 intuitively appear
effective, but this cannot be stated with confidence.
However, these samples may still be used to support and
reinforce results achieved in other sample materials, and
S-series samples were extremely useful for use in later
reversibility testing due to their easy availability.

Figure 4. Load-deflection curve showing failure, and visual failure of The A-series is more directly useful. Although still
sample. Image by Ed Howard, East Carolina University irregular, these samples are small pieces cut from a single

Table 3. Results

Mean ± standard deviation Significant Effect size

Material Consolidant
(Newtons) p < .05 (Hedge’s g)
Control/none 1190.60 ± 181.50 N/A N/A
Owatrol 2316.67 ± 495.75 Yes 3.49
5% B-44 2248.67 ± 144.14 Yes 6.23
A 5% WS-24 1864.33 ± 541.09 No 1.95
10% WS-24 1356.00 ± 305.32 No 0.72
25% WS-24 1627.50 ± 570.50 No 1.44
75% Aquacer 1574.67 ± 135.34 Yes 1.06
Control/none 818.40 ± 470.30 N/A N/A
Owatrol 1025.67 ± 453.93 No 0.46
5% B-44 1821.67 ± 761.77 No 1.74
S 5% WS-24 960.33 ± 83.81 No 0.38
10% WS-24 1522.00 ± 519.86 No 1.48
25% WS-24 1250.67 ± 893.97 No 0.68
75% Aquacer 441.00 ± 108.81 No 1.00
Control/none 42.00 ± 3.79 N/A N/A
Owatrol 86.00 ± 6.38 Yes 9.40
5% B-44 59.67 ± 6.55 Yes 3.72
C 5% WS-24 52.67 ± 7.36 Yes 2.10
10% WS-24 60.33 ± 4.99 Yes 4.40
25% WS-24 56.33 ± 13.89 No 1.77
75% Aquacer 65.67 ± 4.50 Yes 5.91
118  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
large fragment of cast iron spall and are somewhat more
homogeneous as a result. The A-series still has a high
standard deviation, but significant increases in compres-
sive strength can be seen in Owatrol, B-44, and Aquacer.
The C-series is more regular in density than either of the
iron samples, but, lacking iron corrosion products, is less
directly analogous to graphitized marine archaeological
cast iron. However, the lower standard deviation means
these tests may be a better measurement of consolidant
strength.
Bearing these factors in mind, several materials show
acceptable results. Paraloid B-44 shows significant effect
in both A-series cast iron and C-series carbon, with the
greatest effect size of any tested material in the A-series
samples. Although not significant in and of themselves,
the S-series results support this. However, B-44 is a
solvent-borne treatment; large objects could be treated
using a vacuum bag (limiting the volume of solvent
required), but the treatment would be irreversible in
practice because solvent volume in reversal cannot be
easily limited in a similar manner. On smaller objects,
this treatment is feasible.
Owatrol likewise shows significant effect in both A- and
C-series tests, with supporting evidence from S-series.
It has the greatest effect size of any consolidant in the
C-series and the largest mean breaking load in the
A-series, although the high standard of deviation results
in a lower effect size than B-44. Unlike B-44, Owatrol
hydrolyzes in strong alkali, making it theoretically revers-
ible in aqueous media.
Aquacer’s effectiveness is ambiguous. In charcoal samples,
Aquacer outperforms B-44, and the material is second
only to Owatrol in increasing density. In the A-series
there is a significant increase in resistance to compressive
force, but the effect size is relatively small in comparison
to Owatrol and B-44, indicating a lower magnitude of
effect by the consolidant on the samples’ strength. In
the S-series, strength is less than the control group,
although not to a statistically significant degree. Given
the observed decrease in the S-series and the compara-
tively minor increase in the A-series, Aquacer could not
be recommended without additional testing, although it
does show some promise.
WS-24 is unsuitable. All three concentrations failed to
show significant improvements in any cast iron samples,
and the effect in the charcoal samples was minimal.
COATINGS, CONSOLIDANTS & CORROSION INHIBITORS
Based on these results, Owatrol and B-44 were identified
as the best candidates for consolidation of graphitized cast
iron. Of these two, only Owatrol was considered feasible
both to apply and remove from large objects.
Reversibility
The reversibility of Paraloid formulations, including
B-44, is sufficiently known that additional testing was
not considered necessary (e.g., Horie 1987, 106–108;
Down et al. 1996). At the scale of Monitor’s largest objects,
acrylics are irreversible in practice due to the quantity
of solvent required. The reversibility of Owatrol oil has
had limited study; work by Ternisien (2011, 56–60) on
consolidated cuttlebone indicated this process was likely
damaging, but additional data was required.
Testing
Graphitized cast iron samples for the reversibility study
were numbered R1–R15:
• Samples R1–R7 were impregnated with Owatrol and
aged at ambient temperature (22 °C) and 10% RH
for 43 days.
• Samples R8 and R9 were control samples with no
Owatrol present, which were taken through the
same reversibility testing to differentiate damage
from handling versus damage specifically caused by
Owatrol.
• Samples R10–R15 were impregnated with Owatrol
and aged 377 days prior to testing.
Initial testing of Owatrol’s solubility in aqueous NaOH
between 1% and 10% (w/v) showed all concentrations
were effective. The 10% concentration was fastest and was
chosen going forward. The same effect was achieved in
approximately twice the time using 1% (w/v) NaOH and,
at scales where cost or safety concerns make a 10% solu-
tion prohibitive, a lower concentration may be preferable.
Samples were immersed in NaOH until the solution
turned dark brown, then changed into successive
NaOH baths until clear. During this process the solu-
tion remained the consistency of water; a clear, viscous
gel collected on the object surfaces and in the container;
and, in some instances, a white, hard, waxy substance
formed on the object surface. When placed into DI water
to remove NaOH, the solution began discoloring again,
and it was found that alternating NaOH and DI water
baths was more effective. Reversal behavior differed
TESTING THE COMPRESSIVE STRENGTH AND REVERSIBILITY OF CONSOLIDANTS APPLIED TO MARINE ARCHAEOLOGICAL GRAY CAST IRON
between samples aged 43 and 377 days; younger samples
required 42 days in alternating NaOH and DI water baths,
whereas older samples required 73 days. This increase in
reversal time likely reflects more complete crosslinking of
the material; although still fully reversible after one year,
this behavior represents a potential long-term concern
on the scale of years to decades.
All samples lost mass greater than the amount of Owatrol
present, except R13, which retained mass equivalent
to 3.7% of the Owatrol. Assuming 100% efficiency
in Owatrol removal (Figure 5), the other samples
lost between 0.5% and 2.7% of their starting mass of
graphitized iron, with an average of 1.2%. The uncon-
solidated control samples lost 1.2% and 1.1%, indicating
that damage from Owatrol removal does not significantly
differ from damage as a result of equivalent handling.
Losses presented as slight rounding of the sharp edges
of the samples. Structural damage was only noted in R1
(crushed during FTIR analysis) and R11 (slightly chipped
while handling during a solution change).
Figure 5. FTIR spectra of iron sample with Owatrol (red) and after reversal
(black). FTIR has limited ability to detect Owatrol below the surface
layer, and although FTIR and weight loss indicate complete removal of
Owatrol, in practice some residue likely remains. Image courtesy of The
Mariners’ Museum and Park
Chemical characterizations
Owatrol oil is an alkyd-based polymer, chemically a
polyester mixed with glycerol (or other polyols) and
organic acids through ester bonds. Alkyds can be broken
down via saponification of these ester bonds at high pH,
producing alcohol and carboxylate functional groups.
Fatty acid carboxylates bond to iron, particularly at grain
boundaries; their removal is facilitated through neutral-
water rinsing, which interrupts the bond (Kanicky and
Shah 2002, Lundgren et al. 2007, Lobzenko et al. 2021).
The aqueous solubility of fatty acids decreases with
119
decreasing pH, requiring balance between neutralization
to dissociate them from iron and neutralization to the
point of insolubility. While active rinsing with DI water
after the NaOH bath was rapidly effective on test tokens
of uncorroded metal reported by Ternisien (2011), the
method of alternating DI water and NaOH baths used
here was equally effective and requires less infrastructure
at a large scale. Using static baths is likely slower, although
differences in the test materials make it impossible to
directly compare these times.
Preliminary characterization of Owatrol was carried out
using a Bruker Alpha attenuated total reflectance-Fou-
rier transform infrared (ATR-FTIR) spectrophotometer
to collect spectra from 4000–400 cm−1, with 64 scans
collected at a resolution of 4 cm−1. A background spec-
trum was collected prior to measurement under the same
conditions. The spectra were interpreted using Bruker’s
OPUS software version 7.8 Build: 7,8,44.
Results
Figure 6. Owatrol (red) matched with a 65% soybean oil alkyd (blue).
Image courtesy of The Mariners’ Museum and Park
Owatrol aged naturally for 50 days at ambient conditions
(approx. 21 °C and 50% RH) matched with Nicodom
library entry 01628 for an alkyd oil made with 65%
soybean oil (Figure 6). Some peaks do not match the
soybean oil alkyd, indicating other materials in the
Owatrol alkyd. Mass spectroscopy analysis would be
useful to identify the components more clearly (and to
monitor potential formula changes by the manufacturer).
Detection of Owatrol in iron samples is complicated
by changes to the carbonyl peak in the presence of Fe2+
ions. This is indicative of an interaction between the
carbonyl group and iron cations; the exact nature of
this interaction has not been characterized but is likely
indicative of bonding behavior. As a result of this, FTIR
120  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
of an iron-Owatrol mixture shows the carbonyl peak
decreases and shifts from a single peak at ~1740 cm−1 to
two peaks: one still at ~1740 cm−1 and another closer to
1630 cm−1 (Figure 7). This was first seen when looking
for Owatrol in the consolidated samples, and when
the strong carbonyl peak at 1740 cm−1 was not visible,
additional testing was performed to evaluate the effect
of cation coordination with the carboxylates (Otero et al.
2014). Other than potentially indicating some bonding
behavior with iron (which would likely contribute to
Owatrol’s strength as a consolidant), this peak shift
has no direct effect on the treatment. However, the
peak shift must be accounted for when using FTIR to
detect residual Owatrol in samples before and after
reversibility testing.
Figure 7. Owatrol mixed with neutralized 1000 ppm Fe2+ Ricca standard
(blue), and Owatrol control (red). Image courtesy of The Mariners’
Museum and Park
Conclusion
Although FTIR and changes in sample mass serve to
partially characterize the reversal behavior of Owatrol,
additional testing is required. Several samples have
been retained from each treatment phase, which will be
sectioned and analyzed with SEM-EDS in a follow-up
study to help characterize penetration of the consolidant
and reversibility beyond the surface layer.
Paraloid B-44 demonstrated a broadly equivalent consoli-
dative function, and its aging properties are better known.
Unfortunately, the technical and regulatory challenges of
large-scale solvent baths to reverse the treatment limit
Paraloid’s applicability on Monitor.
Based on experimental results and pending future work,
Owatrol oil is recommended for treatment of large,
heavily graphitized cast iron from Monitor. Although
the application is non-aqueous, it is less hazardous than
COATINGS, CONSOLIDANTS & CORROSION INHIBITORS
solvent-born applications at large scale and is readily
applied in a fitted vacuum bag as demonstrated by
Mardikian (pers. comm. 2020). Crucially, the material
seems highly reversible in aqueous alkali with minimal
damage, an essential criterion at the scale necessitated
by Monitor’s objects. This combination of properties—
application in a fitted bag to reduce solution volume,
good consolidation and strengthening, and aqueous
reversibility—is utterly invaluable for the treatment
of large, graphitized marine archaeological cast iron
artifacts.
Acknowledgments
Many thanks to Nichole Doub and the Maryland Archae-
ological Conservation Laboratory at Jefferson Patterson
Park and Museum, Dr. William Howard and the Depart-
ment of Engineering at East Carolina University, and
the entire staff at The Mariners’ Museum and Park for
material support and assistance with this research.
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Authors
Erik Farrell is an objects conservator at The Mari-
ners’ Museum and Park (TMMP). He worked previ-
ously as an archaeological conservator at TMMP for
USS Monitor (1862) and at North Carolina Department
of Natural and Cultural Resources for Queen Anne’s
Revenge  (1718). He received his master’s degree in
conservation from Durham University.
Molly K. McGath, PhD, is a research scientist at The
Mariners’ Museum and Park. She received her doctorate
in materials science and engineering with a focus on
conservation science and her master’s degree in organic
chemistry from the University of Arizona. McGath
previously conducted research at the Arizona State
Museum, The Library of Congress, the United States
National Park Service’s National Center for Preservation
Technology and Training, the Smithsonian Institution’s
Asian Art museums and Museum Conservation Institute,
the United States National Gallery of Art, and Johns
Hopkins University.
Jonathan Echerd is a mechanical engineering student at
East Carolina University, focusing on engineering design.
He works as a project engineer and draftsman in Wash-
ington, North Carolina, and has previous experience
in engine and machine shops specializing in NASCAR
crate engines.
Materials list
Acrysol™ WS-24 (acrylic colloidal dispersion)
Talas: www.talasonline.com/Acrysol-WS-24
122  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND COATINGS, CONSOLIDANTS & CORROSION INHIBITORS

Aquacer® 8527 (aqueous emulsion of a modified poly-

ethylene wax)
BYK: www.byk.com/en/products/additives-by-name/
aquacer-8527

ASTM A48 C40 Cast Iron (91.9%–94.2% Fe, 3.25%–3.5% C)

SpeedyMetals: www.speedymetals.com/pc-4273-8388-
58-rd-gray-cast-iron-class-40.aspx

Charcoal (willow charcoal, 7–9 mm diameter)

Amazon: www.amazon.com/MyArTool-Char-
coal-Sketching-Drawing-Approx/dp/B07XRSXBCG

Owatrol® oil (alkyd drying oil)

Owatrol: www.owatrolusa.com/product/owatrol-oil/

Paraloid™ B-44 (methyl methacrylate/ethyl acrylate

copolymer)
Talas: www.talasonline.com/Paraloid-B-44
Calcium Sulfonate: Adsorptive Inhibitors for Metal
Conservation?
Eva Wentland
Independent conservator
Co-founder of InduKon – Network for the Conservation of Industrial Heritage
Berlin, Germany
e.wentland@indukon.eu
Abstract
Dewatering fluids are used prior to and during the application
of a corrosion protection system to dry surfaces through water
displacement and to form water-repellent films. Dewatering
fluids originated in the 1930s and their development was
boosted during World War II, as a means to protect equipment
recovered from sunken supply ships. The technology was
subsequently adopted by the electroplating, aircraft and
pipeline industries as well as by other commercial sectors.
In Germany, dewatering fluids such as RC T4/20 are used by
conservators, mainly craftsmen, for the conservation of metal
objects. RC T4/20 contains calcium sulfonate as an adsorptive
inhibitor but its efficiency, and that of other dewatering fluids,
has not been scientifically investigated for industrial heritage
applications or metal conservation in general. We conducted
Introduction
Industrial heritage structures of iron and steel are often
subjected to atmospheric corrosion, due to wet-dry
cycles that result in the formation of corrosion stratig-
raphies, mainly consisting of magnetite (Fe3O4), goethite
(α-FeOOH) and lepidocrocite (γ-FeOOH) (Dillmann
et al. 2003). Wet-dry cycles comprise three stages. In
phase 1 (wetting), a 60% relative humidity (RH) suffices
to produce electrolytes, which then catalyse the reac-
tion of lepidocrocite crystals on an existing corrosion
layer with the underlying iron. Lepidocrocite acts as
an oxidation reservoir and its reduction balances the
anodic dissolution of iron cations. Phase 2 (wetness)
begins when the reducible lepidocrocite is depleted
and the cathodic reaction shifts towards oxygen reduc-
tion. During phase 3 (drying), lepidocrocite and other
compounds formed during phase 1 are re-oxidised
to iron(III) compounds. Every wet-dry cycle causes
further corrosion and modifies the composition of the
corrosion stratigraphy. Every drying phase includes the
potential formation of the α-structure of inert goethite,
a literature review of the functional principles of dewatering
fluids as well as an experimental study of the efficiency of a
range of dewatering fluids and coating systems in preventing
atmospheric corrosion processes in pre-corroded steel samples.
The latter tests demonstrated that RC T4/20 and Conrasin
dewatering formulations are able to wick deeply into joints
and crevices while hydrophobising the wetted surfaces, thus
conferring good protection of lap joints. In combination with
an oil-based binder and coating, dewatering fluids can offer
effective corrosion protection.
Keywords
metal conservation, industrial heritage, calcium sulfonate,
adsorptive inhibitors, dewatering fluids
the most stable modification of iron oxyhydroxides. As
an inactive, non-conductive component, inert goethite
is unaffected by wet-dry cycles and its stable crystalline
structure does not dissolve in water (Dillmann et al.
2003, Morcillo et al. 2011).
In industrial heritage structures, uniform and crevice
corrosion occur during wet-dry cycles. Uniform corro-
sion results from the production of differential aeration
cells on metal surfaces under the same atmospheric
conditions, leading to a uniform attack of the surface.
Crevice corrosion is localised and develops in the crevice
geometries formed by a metal surface and any other
metal or nonmetal surface. Examples are joint interfaces
of structure connections, the debris resulting from dirt
or corrosion products and failed coatings (Figure 1).
The anodic dissolution reaction within the crevice takes
place within an acidic microenvironment, which strongly
catalyses the formation of corrosion products (Patel and
Bowman 2018).
124  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Figure 1. Crevice corrosion (Patel and Bowman 2018)
The determining factor for the overall rate and severity
of atmospheric corrosion processes is the length of time
an electrolyte is present on the surface (Hœrlé et al.
2004). Permanently wet regions corrode faster and more
severely than regions that are exposed to the atmosphere
and therefore dry quickly after wetting. Cooper et al.
(2004) demonstrated a high degree of water retention
in overlapping regions of pristine steel sheet samples
and even higher water retention within corroded spec-
imens. The same study showed that short periods of
wetting can saturate corroded crevices; however, as the
drying phase (phase 3) is very long, corrosion processes
inside the crevice can actively continue even under
dry ambient conditions due to electrolyte retention. A
comparison of the severity of atmospheric corrosion
processes clearly showed that the most severe damage to
iron and steel structures is caused by crevice corrosion,
whereas uniform corrosion may promote the formation
of goethite crystals, thus producing corrosion layers that
over long periods of time may confer a protective effect
(Dillmann et al. 2003).
Corrosion prevention strategies
Coatings
The most common method of corrosion prevention for
industrial heritage structures is the application of polymer
coatings to produce a layer on the metal surface that
acts as a barrier to the external atmosphere. Key aspects
considered to be critical for the success of coatings are
their longevity and/or their thickness (Brüggerhoff
2007, CONSIST 2008, Considine et al. 2010). However,
wet-dry cycles can proceed beneath the coatings because
polymeric materials are permeable to moisture and
oxygen. When moisture diffuses through a coating, the
underlying corroded surfaces containing lepidocrocite
crystals can continue to corrode, since they are not
dependent on oxygen access, as explained above. The
process worsens as soon as the coating becomes damaged.
COATINGS, CONSOLIDANTS & CORROSION INHIBITORS
Moreover, moisture can readily penetrate the corroded
layer, which is unlikely to dry beneath the coating, and
in the case of corroded crevices can remain entrapped
beneath the coating layer. As crevices seldomly reach the
drying phase (phase 3) of the wet-dry cycle, the formation
of inert goethite is unlikely, and crevices serve as large
oxidation reservoirs.
Stratmann (1994) suggested that corroded surfaces can
be protected by lessening the reactivity of lepidocrocite
crystals. In laboratory environments, the direct conver-
sion of lepidocrocite to goethite may be possible. For
practical applications, however, Stratmann proposed
the covalent bonding of suitable organic monomers to
inhibit the interaction of moisture with the atmospheric
pollutants that diffuse through the coating material.
Dewatering fluids
In Germany, dewatering fluids have been used in industry
and by conservation craftsmen for several decades. In the
following, we present a brief literature review, performed
to gain insights into the composition of the different
dewatering fluids and their working principles.
One of the first mentions of dewatering fluids can be
found in the proceedings of a symposium, held in London
in 1950, on temporary corrosion protection. Several
of the articles dealt with or mentioned amphipathic
substances that strongly increase corrosion protection
when added to coating compositions (Sell 1950). Formu-
lations containing these surfactants were referred to as
dewatering fluids and were alleged to remove moisture
from metal surfaces by ‘preferential wetting’ (Hollis
1950). In this process, amphipathic molecules interrupt
the bonding of water molecules to the metal surface,
allowing those molecules to evaporate and the persisting
amphipathic molecules to form strong covalent bonds
with the metal surface in their place. The mechanism is
based on the strong electronegativity of the amphipathic
molecule’s polar head group, which exceeds that of water,
thus favouring water displacement.
A comprehensive article dealing with the history of
dewatering fluids appeared in Galvanotechnik, an elec-
troplating journal, in 1962. According to that article,
dewatering formulations were in use before World War II,
but their development was accelerated by the increasing
need of allied troops for corrosion protection of valuable
material salvaged from their sunken cargo ships. In the
CALCIUM SULFONATE: ADSORPTIVE INHIBITORS FOR METAL CONSERVATION?
recovery of the material, dewatering fluids offered a more
efficient process than flushing the salvaged structures
with fresh water, hot air drying and coating. The same
author compared dewatering fluids to solutions of lanolin
in mineral turpentine with an additive of a water-dis-
placing compound, thus combining drying and coating.
The use of dewatering fluids subsequently entered the
private sector, namely in machine workshops, electro-
plating and other undertakings that require the removal
of water from metal surfaces after certain production
stages (Steet 1962).
A lecture series from 1963 presented the concept of ‘ener-
gy-less’ drying with dewatering fluids, as an alternative
to the high energy consumption of drying plants. Rather
than the adsorption or evaporation of water, it would
involve the replacement of liquid films (Energielose
1963). Table 1 lists possible compositions of dewatering
fluids as proposed by Zoltowski (1973). Anionic addi-
tives such as sulfonates were shown to have the highest
efficiency in displacing water (Zoltowski 1973).
Table 1. Composition of dewatering fluids (from Zoltowski 1973)
Function Type
Solvent Primarily white spirit
Surface-active Amphipathic molecules with a hydrophilic head
additive and hydrophobic tail; those additives with polar
groups containing sulfur or nitrogen (fatty amines
or sulfonic acid derivatives) were usually most
effective
Film former Mineral oils, lanolin or other with eligible dry film
characteristics
Cooper et al. (2005) examined the penetration behav-
iour and water displacement of corrosion prevention
compounds (CPCs) that contained water-displacing
agents, and particularly those with wide application in
the aircraft industry. In aluminium aircraft construction,
lap joints require corrosion protection as they are prone
to crevice corrosion. In this setting, a CPC must be able
to penetrate vulnerable areas and displace any moisture.
The authors of that study developed a successful proce-
dure to assess penetration depth and water displacement.
In 2009, O’Donoghue et al. proposed the use of high-
ratio calcium sulfonate alkyds (HRCSA), an engineered
coating material based on calcium sulfonate, as the
monomeric raw material. HRCSA consist of copoly-
merised calcium sulfonate complexed with calcium
carbonate. The former has an inhibitory function while
the latter neutralises the acidic microenvironment inside
125
crevices. HRCSA contain calcite platelets. On the one
hand, the platelets prolong the moisture diffusion path
and increase film stability. On the other hand, perme-
ating moisture is actively buffered towards alkalinity,
thus helping to mitigate acidic microenvironments
beneath the coating. ‘High ratio’ describes the ratio of
active calcium sulfonate that successively adsorbs on
the metal surface (O’Donoghue et al. 2009). HRCSA
coatings have been recommended by Departments of
Transportation in some states in the USA for the refur-
bishment of historic bridges (Patel and Bowman 2018).
The effectiveness of dewatering fluids comes from their
ability to wet surfaces entirely while deeply penetrating
crevices and cracks, where they displace water and
leave a protective layer (Figure 2). Their total efficiency
depends on the molecular structure of the adsorptive
inhibitor, the surface charge of the metal and the type of
electrolyte. They are effective when the protective layers
are adherent, insoluble and prevent electrolyte access
to the metal surface. The adsorption strength depends
upon the electronegativity of the metal or oxide surface
and the inhibitor molecule. Water molecules on surfaces
can be displaced only if the reciprocal forces between the
inhibitor and the surface are greater than those between
water and the surface (Revie 2011).
Figure 2. Adsorptive inhibitors (Sastri 2011)
A recent article by Sharma et al. (2019) examined the
molecular dynamics of the adsorption of surfactant-type
inhibitors on metal surfaces. According to the authors,
the hydrocarbon tail of the inhibitor molecule is typically
12 to 18 carbon atoms long. While the polar head group
establishes the link between inhibitor molecule and
metal surface, the hydrophobic tails, pointing towards
the solution, influence the formation of a self-assembled
monolayer (SAM), which is the key step resulting in a
protective function.
Dewatering fluids in conservation
In the 1970s, Stefan Lasch-Abendroth, a craftsman and
conservator, employed methods used for drying processes
in electroplating to the conservation of steel objects. In
126  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
collaboration with Kurt Kalle, a self-employed chemist,
they developed the product Kadosin T4/20, which is still
being sold under the designation RC T4/20 by the family
business (RC Kalle). RC T4/20 is a water-displacing
agent for the ‘thermal-energy-less’ drying of metal
surfaces (Lasch-Abendroth, personal communication,
15 May 2019). Its precise components are unknown,
but it is assumed to be a blend of aliphatic and aromatic
hydrocarbons, with small amounts of lanolin, microcrys-
talline wax and, most importantly, calcium sulfonate.
Calcium sulfonate is an amphipathic compound that is
often included as the adsorptive inhibitor in dewatering
fluids. The resultant forces between metal and calcium
sulfonate are stronger than those between metal and
water, resulting in preferential wetting and the forma-
tion of a monomolecular layer of calcium sulfonate on
the metal surface. The polar heads of calcium sulfonate
molecules face the metal surface while the nonpolar tails
point towards the atmosphere, yielding a water-repellent
surface. With its strong wicking power, calcium sulfonate
can penetrate deeply into crevices, such as those that
form between gusset plates, and into material capillaries.
The resulting surfaces have a very high water repellence
that hinders electrolyte adsorption, thus preventing
atmospheric corrosion. Although RC T4/20 is scarcely
mentioned in the conservation literature, interviews by
the author revealed that craftsmen use it to facilitate rust
removal and to dry surfaces and crevices. After surface
cleaning, practitioners apply several layers of RC T4/20,
pure at first and then as an additive to Owatrol oil, a blend
of natural resinifying oils and alkyds.
In conservation practices, there has been very little
research into the functional principles and general
performance of dewatering fluids. The above literature
review and the following experimental study, examining
the efficiency of a range of dewatering fluids, mostly
containing calcium sulfonate, were performed as part
of the author’s master’s thesis, under the auspices of the
University of Applied Sciences Berlin. The aim was to
create a base of knowledge for further discussion and
research, with a particular focus on the use of dewa-
tering fluids in the preservation of industrial heritage
structures exposed to the outdoor environment.
Experimental
Several experiments were carried out to assess the
performance of dewatering formulations. Two of these
COATINGS, CONSOLIDANTS & CORROSION INHIBITORS
are discussed. Experiment 1 assessed the longevity of
the corrosion protection effect within lap joints, and
experiment 2 the kinetic behaviour of dewatering fluids,
by examining their penetration depth and velocity.
Method
Eight commercially available products were chosen as
test fluids (fluids 1–8, Table 2). Since dewatering fluids
are mostly designed for short-term protection, they
usually contain only small amounts of binding agent,
making additional protective layers necessary (Bena-
vides 2009). Owatrol oil (fluid 9, Table 2) was chosen as
the additional coating material, in accordance with the
conservation practice determined from interviews. Two
clear conservation coatings commonly recommended
for outdoor exposure (CONSIST 2008) were tested as
well: OKS 2100, a corrosion-prevention wax, and a
water-curing one-component polyurethane (fluids 10
and 11, Table 2).
Experiment 1
Fluids 1–9 (Table 2) were tested by applying them onto
samples in incremental layers: (1) two layers of dewa-
tering fluid; (2) two layers of dewatering fluid with a
topcoat of a 50:50 blend with Owatrol oil; (3) two layers
of dewatering fluid, an intermediate layer of a 50:50
blend with Owatrol oil and a topcoat of pure Owatrol
oil. The samples consisted of pre-corroded Q-Panel
standard steel sheet substrates (76 × 127 × 0.81 mm).
Each set-up contained three samples (9 samples per
fluid, 78 in total). A lap joint was created by bolting
together two pre-corroded steel sheets using two
M8 screws and a torque of 12 Nm. The samples were
spray-coated in three groups and assembled as shown
in Figure 3. After drying, the coated samples were
weighed to three decimal places and then transported
to the Hamburg Port Museum in desiccated packaging,
where they were mounted onto a rack in compliance
with ISO 8565:2011 (International Organization for
Standardization 2011) (Figure 3). The set-up was placed
on a harbour crane, where it remained for 12 months.
At the end of the outdoor exposure cycle the samples
were dismantled. The inner surfaces of the lap joints
were examined for the extent of active corrosion and
the size of the effectively hydrophobised surface area
was established by visual assessment. After thorough
drying and removal of any loose particles, the samples
CALCIUM SULFONATE: ADSORPTIVE INHIBITORS FOR METAL CONSERVATION? 127

Table 2. Test fluids

Name Substances Company Selection criteria

1 RC T4/20 Hydrocarbons, wax, presumably RC Kalle In use by conservation craftsmen in Germany since the 1990s
calcium sulfonate
2 Anticorit® DF 6000 Hydrocarbons, inhibitor unknown Fuchs Fluid 3 without binding agent
3 Anticorit® DFW 6301 Hydrocarbons, wax, calcium sulfonate Fuchs Considered by the DBU-project for transparent corrosion
(1<5%) protection in the 1990s (Brüggerhoff 1999)
4 Anticorit® DFO 6301 Hydrocarbons, oil, calcium sulfonate Fuchs Fluid 4 with oil as binding agent
(1<5%)
5 Brunox® Turbo Spray Hydrocarbons, oil, sulfonic acids, Brunox® Representative of common penetrating oils
sodium salts
6 Teroson® VR 610 Hydrocarbons, oil, nonylphenol, Henkel Has been in use in combination with Owatrol oil at the
1,2,4-trimethylbenzol, MoS2 Adhesives Hamburg Port Museum for the maintenance of outdoor
objects
7 Conrasin Hydrocarbons, wax, calcium sulfonate Conrads® Lacke Developed on the basis of RC T4/20
(1<3%)
8 White Spirit Hydrocarbons - Chosen as reference medium without inhibitor compound,
used by Jaßmann to increase penetration depth of Owatrol
oil (Boellinghaus 2021)
9 Owatrol® Oil Hydrocarbons, resinifying natural oils, OWATROL® – Binding agent with considerable penetration strength
alkyds Groupe DURIEU
10 EK-PUR Transparent, water curing one Conrads®-Lacke State of the art transparent conservation medium following
component polyurethane Brüggerhoff 1999 and CONSIST 2008
11 OKS® 2100 Corrosion protection wax containing OKS® State of the art transparent conservation medium following
calcium sulfonate Brüggerhoff 1999 and CONSIST 2008

were weighed again to record the change in mass due

to material loss. The results are presented as the average
value from the three samples in a sample set.

Experiment 2
For manageability, only fluids 1, 2, 6, 7 and 8 (Table 2)
were tested pure and in a 50:50 blend with Owatrol oil.
Fluids 10 and 11 were chosen to enable a direct compar-
ison with established coating materials. Two sets of
samples (A and B) were made from pre-corroded Q-Panel
standard steel sheet substrates (76 × 127 × 0.81 mm)
and acrylic glass (76 × 100 × 5 mm). Each set contained
three samples (6 samples per test fluid, 78 in total) and
the average value was determined. For set A, a lap joint
was created by bolting an acrylic and a pre-corroded
steel sheet together using four M8 screws and a torque
of 16 Nm. The lap joint interface had a crevice depth of
100 mm, a crevice width of 76 mm and a crevice height
ranging from < 50 μm around the bolts to > 300 μm in
border areas with less surface pressure. Set B comprised
two pre-corroded steel sheets with joints prepared as in
set A (Figure 4).

A precision dropper was used to apply 100 μL of test

Figure 3. Set-up for experiment 1: rack on a harbour crane at the fluid at the centre of the crevice mouth of the levelled
Hamburg Port Museum with indicated sample numbering sample. Another 100 μL of test fluid was added after 60
128  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND COATINGS, CONSOLIDANTS & CORROSION INHIBITORS

and 120 s. The flow front in set A was traced after 30,
90, 150 and 210 s and after 48 h. Set B was disassembled
after 48 h. The lower steel sheet was then dipped into
demineralised water. The hydrophobised, water-repel-
lent areas were traced and their surface areas recorded.
Set A samples were evaluated by comparing the pene-
tration velocity to the size of the wetted area, and set B
samples by determining the size of the hydrophobised
surface area.

Figure 5. Results of experiment 1: gravimetric sample analyses

Figure 6. Detail
of experiment
1. Lap joint
surfaces of sample
112, RC T4/20 as
dewatering fluid
only: considerable
active corrosion, no
Figure 4. Set-up for experiment 2   hydrophobisation

Figure 7. Detail of
Results and discussion experiment 1. Lap
joint surfaces of
Experiment 1 sample 333, DFW
6301 as dewatering
The main findings were:
fluid with Owatrol
• A free exposure of 12 months was too short a time- oil topcoat: no
frame to allow distinct gravimetric analyses; the values active corrosion,
of all samples varied between +1.84 g and −2.98 g. hydrophobisation of
  the entire interface
However, because the standard deviation was surpris-
ingly low, the derived tendencies were still informative
(Figure 5). Figure 8. Detail
of experiment
• Uncoated samples scored worst and had the greatest
1. Lap joint surfaces
material loss, as there was no hydrophobisation and of sample 932,
substantial active corrosion occurred within the lap Owatrol oil with
joint. no dewatering
fluid: some
• There was no noteworthy corrosion protection of active corrosion,
samples treated with dewatering fluid only (Figure 6). hydrophobisation
• Samples coated with fluids 1, 3, 4 and 7, applied using of three quarters of
a 50:50 topcoat, showed partial hydrophobisation   the interface

inside the lap joint.

• Products 1, 3 and 7 showed very promising results
when applied according to layer system (3): as total
hydrophobisation of the lap joints, no active corro-
sion and only a slight mass increase were observed
(Figure 7). Pure Owatrol oil was not able to protect
the entire joint interface (Figure 8).
Experiment 2
The results of set A and set B differed, perhaps because
the smooth surface of the acrylic glass posed less resist-
ance to wetting than did those samples with corrosion
products on both sides of the crevice.
CALCIUM SULFONATE: ADSORPTIVE INHIBITORS FOR METAL CONSERVATION?
The main findings were:
• For set A, the best results were obtained with fluids 1
and 7, as they penetrated quickly and deeply into lap
joints, creating a hydrophobising effect on the inner
joint surface (Figure 9).
• Similar to water only, RC T4/20 was able to wick into
crevice heights of < 0.05 mm, hydrophobising the
entire inner surface, including the screw connections.
As reported by Müller and Tostmann (2017), critical
crevice heights that strongly induced crevice corrosion
ranged from 0.01 to 0.5 mm.
• For set B, the hydrophobised surface areas achieved
with the pure dewatering fluids, namely RC T4/20
(100%) and Conrasin (75%), were considerably larger
than those obtained with pure Owatrol oil (70%),
wax (13%) or single-component polyurethane (0%).
The results of the 50:50 blends of dewatering fluid
and Owatrol oil were between those of RC T4/20 and
Owatrol oil (96%) (Figure 10).
Figure 9. Results of experiment 2: penetration rate of test fluids, time
vs surface area
Figure 10. Results of experiment 2: effective hydrophobisation of lap
joint interfaces, size of the surface area
129
Conclusion
Among the tested fluids, the characteristics of RC T4/20
and Conrasin were consistent with those of dewatering
formulations identified in a literature review. This study
showed that an effective dewatering formulation based
on the adsorptive inhibitor calcium sulfonate will:
• readily wet surfaces and penetrate deeply into occluded
regions, reaching critical crevice geometries not
covered by conventional corrosion protection systems
• displace water and dry the metal
• form a hydrophobic film that tightly adheres to the
surface on a molecular level, effectively lowering the
reactivity of metal surfaces such that water will not be
able to wet the surface.
By protecting not only the surfaces but also the critical
interfaces of connecting parts, these formulations will
allow significant corrosion protection of inevitably
corroded historic steel structures. Indeed, dewatering
formulations containing calcium sulfonate can reduce
the reactivity of corroded surfaces containing lepi-
docrocite crystals, as proposed by Stratmann already
in 1994.
To provide long-term corrosion protection, dewatering
fluids must be integrated into a system containing
a coating material. When used in combination with
Owatrol oil, the performance of dewatering fluids is
improved, especially at incremental concentration ratios
that successfully fill up capillaries and crevices. Other
strategies should also be explored.
The application of formulations such as RC T4/20 or
Conrasin on corroded metal surfaces did not result in a
notable visual difference. For indoor exposure, however,
with fluctuating relative humidity and the danger of
condensation, the long-term effectiveness of these
barrier layers remains to be assessed. Finally, calcium
sulfonate-based formulations might also provide unob-
trusive but effective corrosion protection also for more
delicate metal objects.
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Author
Eva Wentland is a freelance conservator specialised
in metals and modern materials. She is member and
co-founder of InduKon, Network for the Conservation
of Industrial Heritage. Recent projects were the conser-
vation of two harbour cranes in the city of Hamburg, as
well as the completion of her master thesis with the title:
“Transparent conservation of large heritage objects in
outdoor exposure – Dewatering fluids, an investigation
CALCIUM SULFONATE: ADSORPTIVE INHIBITORS FOR METAL CONSERVATION? 131

for use in conservation”. In 2017 she received a bache-

lor’s degree in conservation and restoration of modern
materials and technical heritage from the University for
Applied Sciences in Berlin. She has been employed as a
conservator in the Germany Mining Museum and has
worked and completed internships in several museums
and freelance conservation studios, where she has
focussed on composite objects from everyday life or with
an industrial context.
 Young Conservation Professional
Investigating a Sustainable Alternative: L-Cysteine
as a Non-Toxic Corrosion Inhibitor for Copper Alloy
Conservation
Emilie Tréhu* Dean Sully
Museum of Fine Arts Boston UCL Institute of Archaeology
Boston MA, USA London, UK
etrehu@mfa.org d.sully@ucl.ac.uk
*Author for correspondence
Abstract
Treatments consisting of 1-, 6- or 24-hour immersion in 1, 3
or 5% (w/v) solutions of L-cysteine in deionised water were
compared to a standard benzotriazole (BTA) treatment using
artificially corroded copper alloy (brass) coupons. The results
were assessed by visual observations, gravimetric measurements
and microscopy/spectroscopy and suggested that L-cysteine
treatments consisting of a higher concentration and longer
immersion time were more effective than the standard
Introduction
The presence of nantokite (copper(I) chloride) beneath
more stable layers of oxide and carbonate corrosion
poses a well-known threat to archaeological copper
alloy objects. With moisture, nantokite oxidises to form
powdery green copper(II) chloride hydroxides, such as
paratacamite, in a catalytic reaction, eventually causing
the corrosion of any remaining metal in a process known
as bronze disease (Grayburn et al. 2015, 222; Selwyn
2004, 67).
Conservation approaches, such as chloride removal and
environmental control, are often supplemented by the
use of corrosion inhibitors. Since 1967, benzotriazole
(BTA, C6H5N3) has been the primary corrosion inhibitor
for copper alloy conservation (Sease 1978, 81–82). BTA
is popular in conservation due to its established use
and simple application that does not require removing
pre-existing corrosion products or interfere with objects’
metallic composition. The resulting dark-green appear-
ance is generally deemed an acceptable conservation
surface (Golfomitsou and Merkel 2004, 346, table 1).
However, BTA loses efficacy within five years, is an
environmental and health hazard, is more effective on
copper than on its alloys and exhibits reduced efficacy in
low-pH environments (i.e. chloride ion-rich pits caused
BTA treatment. Immersion time had a greater effect than
concentration, although surface changes increased with both.
Limitations in the experiment offer insights into further research
that could determine L-cysteine’s suitability for conservation.
Keywords
L-cysteine, benzotriazole (BTA), copper alloys, corrosion
inhibitors, bronze disease
by bronze disease) (Abu-Baker et al. 2013, 29; Gravgaard
and van Lanschot 2012, 14, 23).
Conservation corrosion inhibitors must exhibit high
inhibition efficiency, long-term stability, safety for
handling and reversibility, while being readily avail-
able, easy to maintain in storage and relatively low cost
(Abu-Baker et al. 2013, 230). The amino acid L-cysteine
(HO2CCH(NH2)CH2SH) is non-toxic, biodegradable,
relatively inexpensive and easily produced at high purity
(El Ibrahimi et al. 2020, 743). Its sulfur atom is a strong
electron donor, resulting in the enhanced adsorption
of L-cysteine to copper and its alloys and thus in the
formation of a stable copper–cysteine complex on the
object’s surface (Abu-Baker et al. 2013, 230). Additionally,
L-cysteine can act as a zwitterion, allowing a positive
charge under acidic conditions, such as those in chloride
corrosion pits, in turn increasing chemisorption with the
copper (Gravgaard and van Lanschot 2012, 15).
Three previous studies examined L-cysteine as a corro-
sion inhibitor for archaeological copper alloys (Gravgaard
and van Lanschot 2012, Abu-Baker et al. 2013, Argy-
ropoulos et al. 2017), but systematic comparisons with
BTA are lacking. In this study a standard BTA treatment
was compared with selected variations in L-cysteine
INVESTIGATING A SUSTAINABLE ALTERNATIVE: L-CYSTEINE AS A NON-TOXIC CORROSION INHIBITOR FOR COPPER ALLOY CONSERVATION 133

treatment to assess the effects of the treatments. The 2006, 392). Following treatment, the coupons were aged
mechanism of inhibition was not investigated. simultaneously in a Memmert ICH260L climate chamber
at 80% RH and 25°C for 42 days (Leygraf and Graedel
Experimental design 2000, 17, as cited in Golfomitsou 2006, 114).

Factors for testing

Due to time and resource limitations, a single BTA treat-
ment was employed based on Golfomitsou (2006) and the
standard traditionally used at the Museum of London: a
1-hour immersion in 3% w/v (0.26 M) BTA in industrial
methylated spirit (IMS). Without a current standard for
L-cysteine use in conservation, three concentrations and
immersion times were assessed (Table 1). Deionised water
was identified in previous studies as the most efficient
solvent for L-cysteine (Gravgaard and van Lanschot
2012, Abu-Baker et al. 2013, Argyropoulos et al. 2017).
Low (1% w/v, 0.08 M), intermediate (3% w/v, 0.25 M)
and high (5% w/v, 0.4 M) concentrations were chosen to
compare the range of previously tested L-cysteine concen-
trations to the standard BTA treatment. As Gravgaard
and van Lanschot found no difference in efficacy between
24-hour and 7-day L-cysteine immersions of bronze
samples (2012, 15–16), 1-, 6-, and 24-hour immersions
were selected in this study for comparison with the
standard BTA treatment.
Data analysis
In consultation with Stavroula Golfomitsou (personal
communication, 25 June 2019), due to time and resource
limitations it was determined that the most appropriate
techniques for evaluating the experimental results for this
short-term study were visual observations, gravimetric
measurements and scanning-electron microscopy with
energy-dispersive X-ray spectroscopy (SEM-EDS). All
coupons were documented after pre-corrosion, treatment
and accelerated ageing with photography and observa-
tion at 52.5× magnification using a Dino-Lite Pro HR
AM7000/AD7000 5-megapixel digital microscope. The
visual observations evaluated the aesthetic effects of
the inhibitors for conservation use. The coupons were
weighed after pre-corrosion, after treatment and during/
after accelerated ageing. An equation of mass change
over time was used to calculate the percent inhibition
(%I) (Faltermeier 1999, 125), with the standard BTA
treatment representing the control group:

%I
= (control weight change − test weight change) × 100
Table 1. Test parameters
| control weight change |
Test Inhibitor Immersion
Inhibitor Solvent
name concentration time
After accelerated ageing, a representative coupon from
BTA BTA 3% (0.26 M) IMS 1h
A L-cysteine 1% (0.08 M) Deionised water 1h
each test group was chosen based on the Dino-Lite
B L-cysteine 1% (0.08 M) Deionised water 6h
documentation for SEM-EDS analysis, performed
C L-cysteine 1% (0.08 M) Deionised water 24 h using the parameters listed in Table 2. EDS line-scans
D L-cysteine 3% (0.25 M) Deionised water 1h allowed estimation of the distribution of Cu, Zn, Cl, O,
E L-cysteine 3% (0.25 M) Deionised water 6h C, N and S on the coupons’ surfaces, and SEM analysis
F L-cysteine 3% (0.25 M) Deionised water 24 h allowed comparison of the surface morphological features
G L-cysteine 5% (0.4 M) Deionised water 1h (Abu-Baker et al. 2013, 23; Golfomitsou 2006, 128–29).
H L-cysteine 5% (0.4 M) Deionised water 6h
Table 2. SEM-EDS analytical parameters
I L-cysteine 5% (0.4 M) Deionised water 24 h
Carl Zeiss EVO 25 variable pressure SEM with
Instrument electron microprobe and Oxford Instruments
Coupon preparation Aztec X-ray spectrometer

As brass alloys were underrepresented in previous Accelerating voltage 20.00 kV

Data collection time/
studies, in this study 20 × 50 × 1 mm brass coupons Dead time
100 s/35%–40%
(37% Zn/63% Cu) were selected for testing. The coupons Working distance 8–10 mm
were pre-corroded following the Faltermeier procedure Magnification 90–330×
(Faltermeier 1995, 124). Five coupons for each test group Image type Secondary electron (SE)
were immersed in each inhibitor for the selected time, Method used for EDS
Point and ID
then oven-dried for 30 minutes at 50°C (Golfomitsou collection
134  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND COATINGS, CONSOLIDANTS & CORROSION INHIBITORS

Results

Visual observation
Figure 1 shows a representative coupon from each test
after pre-corrosion (before treatment). Figure 2 shows
those coupons’ immediate colour change after inhib-
itor treatment (before accelerated ageing) and Figure 3
shows those coupons after 42 days of accelerated ageing.
The change between Figures 1 and 2 is consistent with
a general trend in L-cysteine immersion time across

Figure 3.
Representative
coupons after
accelerated
 ageing

all concentrations: a green colour change after 1 hour,

purple areas after 6 hours, and grey/white surfaces after
24 hours. Higher concentrations caused the darkening
of green and purple areas and increased the surface area
and thickness of the purple and white layers. The change
Figure 1. between Figures 2 and 3 shows that 1-hour treatments
Representative produced dark-green and purple mottled surfaces, and
coupons after coupons in the 6-hour treatments were covered in soft
 pre-corrosion
bright-green, white and light-blue corrosion products,
whereas the 24-hour treatments retained areas of pink
metal, ringed by light-blue and purple corrosion prod-
ucts. The grey appearance of L-cysteine on bronze
coupons was noted by Abu-Baker et al. (2013, 236) and
Gravgaard and van Lanschot (2012, 19), but the colour
changes in our samples were more purple than grey,
perhaps due to the coupons’ brass composition.

Gravimetric
Table 3 shows the average %I for each L-cysteine group,
calculated against the average change for the BTA group as
the control. The higher the %I recorded for the L-cysteine
test groups, the more effective the treatment compared to
the BTA treatment. Figure 4 depicts the trends in the %I
values shown in Table 3. The %I of the 1-hour immer-
Figure 2.
sions followed a negative trend over time, whereas the
Representative
coupons after 24-hour immersions followed positive trends from day 7
inhibitor post-treatment onwards. A longer-term assessment would
 application reveal whether this positive trend is maintained.
INVESTIGATING A SUSTAINABLE ALTERNATIVE: L-CYSTEINE AS A NON-TOXIC CORROSION INHIBITOR FOR COPPER ALLOY CONSERVATION 135

Table 3. Average %I of tests A–I compared to BTA

Test name Percent inhibition after treatment (AT) and at each weigh-in day (D)
AT 1D 2D 7D 14D 18D 35D 42D
A −14.29 100.00 66.67 75.00 57.14 53.85 0.00 −9.10
B −171.43 216.66 166.67 125.00 135.71 146.15 166.67 172.73
C −328.57 266.66 222.22 162.50 178.57 184.62 191.67 209.10
D 0.00 116.66 77.78 68.75 14.29 15.38 25.00 18.18
E −57.14 183.33 133.33 106.25 107.14 107.69 91.67 90.91
F −200.00 250.00 200.00 156.25 164.29 169.23 175.00 172.73
G 14.29 133.33 66.67 68.75 28.57 23.08 0.00 9.10
H −57.14 216.66 144.44 100.00 100.00 107.69 100.00 90.91
I −242.86 350.00 288.89 200.00 214.29 223.08 233.33 254.55

SEM-EDS tities of Cu, Cl and O (Figure 6), corresponding to

copper(II) chloride hydroxides such as paratacamite.
Figure 5 shows a representative SEM image from each Extensive EDS scans across the surfaces of the L-cysteine-
coupon’s surface. The EDS analysis of the voluminous treated coupons indicated that the elements similarly
mounds seen on the BTA coupon identified large quan- associated with the copper(II) chloride hydroxides were

Figure 4. Trends in tests A–I’s %I compared to BTA

Figure 6. SEM-SE images and spectrum 10 from BTA coupon as an

example of the voluminous mounds also seen on A, B, D, E and G

Figure 7. SEM-SE images and spectrum 102 from coupon C as example

Figure 5. SEM image from each test’s representative coupon of the small bunches also seen on H, F and I
136  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Figure 8. SEM-SE images and spectrum 37 from coupon I as an example
of the flat expanses above small bunches also seen on F
only similarly visible on tests A, B, D, E and G, corre-
sponding to the voluminous mounds seen in the SEM
images (cf. Figure 5). By contrast, EDS scans of the small
bunches seen in the SEM images of C, F, H and I showed
a much lower Cl content and a much higher S content,
suggesting the presence of copper–cysteine complexes
and the reduced presence of possible copper(II) chloride
hydroxides, evidenced by the absence of the voluminous
mounds (Figure 7). The flat expanses above the small
bunches on tests F and I corresponded to the grey crusts
seen on those coupons. The corresponding EDS scans
showed an even higher S content (Figure 8).
Conclusion
After treatment and before ageing, the lower concentra-
tions and immersion times of L-cysteine caused a colour
change that included a dark-green surface very similar
to that resulting from BTA treatment. The other treat-
ments created uneven purple, grey and white surfaces.
The 24-hour treatments, however, retained more of the
coupons’ pre-ageing pink-brass colour. BTA treatments
are normally followed by a protective coating, such as a
Paraloid acrylic lacquer, which could reduce L-cysteine’s
greying effect to an acceptable dark-brown/grey, thus
mimicking the stable patinas expected as a visual standard
for copper alloys (Gravgaard and van Lanschot 2012,
17–20, figs. 4, 5). The gravimetric results suggested that
L-cysteine’s inhibitive efficacy increases with concentra-
tion and immersion time, but that the immersion time
has the greatest effect. The trends in %I over 42 days of
accelerated ageing suggest that a 24-hour immersion of
L-cysteine is more effective than BTA treatment as an
inhibitor for brass coupons. According to the SEM-EDS
COATINGS, CONSOLIDANTS & CORROSION INHIBITORS
results, higher concentrations and immersion times may
create a stronger inhibitive film due to the sulfur atom of
L-cysteine complexing with the copper alloy substrate,
with a 24-hour immersion as the most effective. Together,
our findings suggest the efficacy of 24-hour immersion
in L-cysteine in deionised water as a corrosion inhibitor
treatment for copper alloys. While the treatment time is
longer than the standard BTA treatment, L-cysteine offers
the advantage that it is more environmentally sustainable.
In order to assess L-cysteine’s suitability as a routine
conservation treatment, further tests should include a
narrower range of concentrations as well as other alloys
that allow testing for possible dezincification in brass and
the influence of the mobility of other elements. Studies
of L-cysteine’s long-term efficacy under ambient ageing
conditions and analyses using a broader range of analyt-
ical techniques (XRD, FTIR, XPS, Raman spectroscopy)
should also be pursued prior to experimenting with
corrosion surfaces on heritage objects (Golfomitsou
2006, 137).
Acknowledgements
This research was undertaken as part of the lead author’s
dissertation for the MSc in Conservation for Archae-
ology and Museums at the Institute of Archaeology
(IoA), University College London (UCL), under the
supervision of Dr Dean Sully. Thank you to Dr James
Hales and Dr Agnese Benzonelli for facilitating access
to the climate chamber at the IoA and Dr Tom Gregory
for facilitating and assisting with SEM-EDS analysis at
the IoA’s Wolfson Archaeological Science Laboratories.
Thank you to Helen Ganiaris, Rebecca Lang and Luisa
Duarte for their feedback during development of the
experiment and facilitating access to the resources of the
Archaeological Conservation Laboratory at the Museum
of London. Thank you to Dr Stavroula Golfomitsou, Mari
Gravgaard and Susi Pancaldo for sharing their own expe-
riences and research with copper alloys and L-cysteine,
which inspired and shaped this project.
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TECHNICAL STUDIES
Sustainable Growth of Mewari Mail Makers: Traditional to
Contemporary Practices
Vandana Singh
The City Palace Museum
Udaipur, Rajasthan, India
singhvandanavs@yahoo.in
Abstract
In the age of cutting-edge technologies, artisanal methods are
gaining increasing appreciation. In India, the community of
karigars (craftsmen and -women) consists mostly of daily-wage
earners. This research examines one such group, traditional
Mewari chain-mail makers. There are no written sources
describing the material culture of this community, although
chain mail was in high demand in the past. Over the years, as
chain mail has become almost exclusively of historical interest,
chain-mail making is being abandoned, as artisans use their
skills to make objects of contemporary interest. This research
explored how chain-mail-making skills are being sustained but
Introduction
The City Palace Museum, Udaipur, India, houses an arms
and armour collection from the late 15th to the 18th
century that consists of complete sets of body armour,
trousers, helmets and armguards of soldiers and cavalry
as well as armour for women and children. As part of a
conservation project, the armour was examined scientifi-
cally. However, despite the large-scale production of mail
in the past, its provenance is largely unknown and there
are no written sources or other information identifying
the craftsmen who made the armour or the workshop
where they worked. Thus, in this study a survey was
conducted in Mewar, Rajasthan, India, where chain mail
is still produced by a few craftsmen, mostly from a single
family. Craftsmen who had switched to contemporary
practices were also interviewed. The survey showed that
the mail produced today is very similar in appearance
to medieval riveted mail and that its makers continue to
take pride in their work.
Tracing the development of body armour in India
Weapons and armour have been prized in India since very
early times. Defensive armour was introduced into India
also adapted as well as issues related to the participation of
craftswomen. The collective knowledge gained from the Mewari
mail makers was put into practice as part of an ongoing Arms
and Armours Conservation project at the City Palace Museum,
Udaipur, where it will contribute to a better understanding of the
armour collections housed in this and other museums.
Keywords
Mewar, mail makers, karigars, baghtar, armour, riveted rings,
traditional craftsmen, craftswomen
by Indo-Aryan peoples after 2000 BC (Bryant 2001).
Armour was prominently mentioned in the Rigveda,
the oldest known Indian Vedic Sanskrit text (between
1500 and 1000 BC) (Jamison and Brereton 2014). Vedic
warriors wore armour made of rhinoceros and deer skins
but some wore metal armour called varman, which is
described in the Rigveda as sewn armour or a coat of mail
that covers the whole body. Armour is also mentioned
in the Arthashastra, an ancient Indian Sanskrit treatise
on military strategy from 321–296 BC.
Medieval chain mail armour was light and flexible,
balancing the defensive capabilities of the armour with
the offensive capabilities of the wearer. By the late 14th
century, this flexible defence was reinforced with rigid
plates to cover vital areas of the torso. Later on, to cope
with the intense heat, soldiers decreased the weight
of their armour. Eventually, however, due to technical
advancements and the increased reliance on archery, most
soldiers, except those in the cavalry, did not wear heavy
metallic body protection. This development accompanied
a transition from mail and plate armour to a new type
of armour strongly influenced by contemporary Persian
SUSTAINABLE GROWTH OF MEWARI MAIL MAKERS: TRADITIONAL TO CONTEMPORARY PRACTICES 141

designs, in which a ‘four mirrors’ (chahar a’ineh) type of small and specialised workshops in the princely states of
armour, composed of four plates secured by straps, was India, including those where mail-making was performed
worn over a mail shirt (zerah baghtar) (Bottomley and by karigars (craftsmen). In addition to Mewar, many
Bowstead Stallybrass 2000). As muskets became widely mail-making workshops were located in Hyderabad.
used, in the 16th century, soldiers sought protection Sophisticated tools and expertise were not available at
against projectiles, thus favouring closely modelled the local level but were probably concentrated within
plate cuirass over mail armour. Musket-proof cuirasses a more extensive arms-manufacturing workshop. Skill
consisted of two layers of metal plate, one softer than the was acquired in a very structured manner, with strict
other. The outer layer was designed to absorb a bullet’s rules and methods. Mohammad Baig further added
energy, and the thicker, softer inner layer to slow the that, traditionally, wire was drawn manually, a highly
bullet and thus limit its penetration. strenuous task. Challa is a local term for iron rings. Each
challa was annealed many times during the mail-making
According to its construction technique, mail armour
process. The earlier challa had round holes for riveting,
can be divided into three main categories: armour made
whereas later forms had wedge-shaped holes. The ends
of riveted rings, armour made of alternate rows of riveted
of the challa were pierced together or sometimes welded
and solid rings, and armour made of butted rings (Sharma
with heat. This was a slow process requiring precision and
1986). In rivetted iron rings, wire at the end ring is flattened
dedication. At this stage, the challa were joined together
and punched to receive a rivet. Until the 18th century, the
to shape the baghtar (mail shirt). In traditional construc-
majority of Indian mail was characterised by alternate rows
tion, according to Mohammad Baig, the production of
of riveted and solid rings (welded) made with a 4-in-1
a full baghtar from start to finish might take a year. The
pattern (Metcalf 2001). However, by the end of the 18th
initial, laborious production tasks were left to apprentices
century, this stronger mail was increasingly replaced by
and assistants. Then, the most skilled task was done by
more decorative butted mail (Richardson and Bennett
the master craftsman, who would have been supplied
2015), in which the ends of the ring were simply butted
with the necessary rings and rivets.
together, not joined. Butted iron, copper and brass rings
can be arranged in a horizontal chevron or zig-zag pattern.
The addition of brass and copper rings to the traditional
iron structure enabled craftsmen to produce fine mail with
a range of geometrical designs. However, as the insecure
method of fixation was useless in battle, this armour was
mostly made for ceremonial purposes.

The art of armour making

The most important source of information for this
research was the Mirza’s family, a family of traditional mail
makers from Mewar. The title Mirza was conferred upon
the family, who continued to use it when they migrated
to Udaipur 60 years ago from Karauli, Sawai Madhopur,
in Rajasthan. Mirza Ishtakar is the only member of the
family who continues to dedicate himself to assuring Figure 1. Two generations of Mirza’s family: 99-year-old Mirza Mohammad
Baig (right) with his older son (middle) and his younger son Ishtakar (left)
that the tradition in which he was trained grows and
flourishes. All other family members have entered other However, for the last 40 years karigars have used a tool/
professions. The Mirza’s family has been engaged in machine for ring-making and riveting (Figure 2) that also
mail-making for at least 150 years. Ishtakar’s training flattens the ring and punches a hole into it. According
and knowledge came from his father, Mirza Mohammad to the size of the ring, the flattening frame is adjusted.
Baig, who learned it from his father (Figure 1). In talking As demonstrated by Ishtakar, the riveted rings are made
about the history of armour-making in India, 99-year-old by winding a wire on a rod so as to resemble a spring
Mirza Mohammad Baig said that there had been many (Figure 3). After the ring has been made, the link that
142  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
goes through the hole is severed and the ring is slid off
the rod. Next, the burma – an upper attachment of the
hole-punching machine – is removed to complete the
rivet (Figure 4b).
Figure 2. Ring-making tool/machine
Figure 3. Wire winding on the rod to form a spring
Women at work
Mirza Ishtakar’s wife Shahnaaz Beg also makes riveted
rings and assists him in other tasks in the workshop
(Figure 4). Normal body armour usually weighs 12–15 kg,
depending on the design or construction. For the 4-in-1
pattern, in which each ring passes through four others,
tens of thousands of repetitions and therefore extraordi-
nary patience are required. Shahnaaz, who learned from
her husband, is highly skilled and has been helping in the
workshop for 14 years while continuing to maintain the
family’s household. Unfortunately, her work in armour-
making receives little social recognition, to the point that
when asked what she does she replied: ‘Nothing much.
We become soldiers in an invisible army and acquire
skills to survive’.
TECHNICAL STUDIES
A prerequisite for broader social recognition of both
craftsmen and craftswomen is that they value their own
work. Therefore, the couple was invited to demonstrate
their skills in the conservation laboratory at the City Palace
Museum, Udaipur (Singh and Seth 2021). In this more
appreciative environment, they worked alongside conser-
vators in restructuring and repairing damaged mail armour
(Figure 5). For Shahnaaz Beg, in addition to taking pride in
her work, this opportunity gave her a sense of progress in
gaining social acceptance as a skilled craftswoman.
Figure 4. Shahnaaz Beg demonstrating the process of making rived
rings using a machine
Figure 5. Shahnaaz Beg and Ishtakar repairing lost areas of mail and
plate armour at the arms and armour conservation laboratory, The City
Palace Museum, Udaipur
Reproduction of armour by contemporary
chain-mail makers
Mirza Mohammad Saeed Ahmad is a close relative of
Mirza Ishtakar who moved to the city of Meerut, Uttar
Pradesh (Figure 6). He is no longer involved in traditional
mail-making but instead makes weapons and armour
for use by the Historical Medieval Battle Association
SUSTAINABLE GROWTH OF MEWARI MAIL MAKERS: TRADITIONAL TO CONTEMPORARY PRACTICES
(HMBIA), an international sports organisation created
to develop, support and promote HMB, which combines
a true sport with the preservation of historical cultural
heritage.1 Among historical re-enactment groups, espe-
cially those whose focus is on antiquity or the Middle
Ages, mail is commonly used both as practical armour
and as a costume. Reproductions are much less expensive
to procure and to maintain than historical ones and allow
craftsmen such as Mirza Mohammad Saeed Ahmad to
earn more money in less time.
Figure 6. Mirza Mohammad Saeed Ahmad at his workshop. He is a maker
of contemporary armour for the Historical Medieval Battle Association
(HMBIA) for participants in HMB, an international sport
Shri Gopilal Lohar is 75 years old (Figure 7) and a
third-generation craftsman in a family of traditional inlay
blacksmiths well-known particularly for their produc-
tion of ornamental weaponry in Udaipur, Rajasthan.
Previously, Shri Gopilal was a traditional weapons
manufacturer but he now contributes to innovation in
traditional craftsmanship, with a wide-ranging business
that includes customers in Europe and the US. In the early
19th century, the Maharana of Udaipur was so impressed
with the craftsmanship of Gopilal ancestors that he
granted them royal patronage and gifted them lands in
perpetuity. Initiated into the craft by his grandfather and
constantly encouraged by his father, Shri Gopilal none-
theless distanced himself from the traditional Mewari
form of blacksmithing to become famous for his exclu-
sive blade-making skills. Today, with his son, he runs a
workshop equipped with traditional as well as advanced
machinery (Figure 8). His use of technology has allowed
him to provide customisation on a large scale. He was
143
Figure 7. Shri Gopilal Lohar at his workshop
also honoured by the Government of India with its ‘Shilp
Guru’ award, for excellence in traditional craftsmanship.
In a discussion of the evolution of chain mail armour
in India, Gopilal cited Bundi, Alwar, Rampur, Bhinder
and Sirohi as arms manufacturing centres in Medieval
India. Those in Bundi and Alwar included numerous mail
makers. At that time, armour production was expensive,
due to the amount of time and material required to make
a mail shirt. In addition to production by local small
workshops, armour was exported from northwest India
through horse trading with Iran and Afghanistan.
Abbas Ali Sagar, a 79-year-old master tailor by profes-
sion, used to visit the conservation laboratory at the City
Palace Museum to translate the Arabic inscriptions on
the weapons. He provided several important observations
about the different mail items. For example, chain mail
is not uniform across the object, as the mail is thick and
chunky at the upper chest, finer towards the shoulder,
and even finer towards the wrist. Cavalry armour is knee
length and spilt up the front and up the back, allowing
the wearer to sit astride a horse. The armour at the
knee is very fine. A true karigar would create mail with
varying size rings to allow for flexibility and a precise fit.
A properly fitted mail that does not restrict movement
requires a considerable investment of work.
Conclusion: A treasure of talent at risk
Mewari karigars continue to pass along their knowledge
and traditions. Most of these craftsmen come from the
same background or even family. Today, they still take
pride in their identity as artisans and in being Mewar
karigars, despite having switched to the production
144  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Figure 8. Use of traditional smelting and forging methods in the
manufacture of weapons and armour at the workshop of Shri Gopilal
Lohar
of contemporary items using modern practices. Their
knowledge allows them to adapt inherited traditions to
the contemporary context without compromising their
pride as karigars. However, as materials and techniques
evolve, a body of meta knowledge has developed that
enables this community to quickly adjust their practices
to modern times.
In India, there are thousands of karigars earning a living
using traditional techniques that have been passed down
TECHNICAL STUDIES
through generations and which make up the cultural
and artistic fabric of India. However, the economic and
human costs of the 2020–2021 pandemic caused many of
these craftsmen to lose their livelihoods, if not their lives.
It is thus all the more important to recognise, protect and
value their skills, which are irreplaceable. An important
lesson of the pandemic is the need for an ecosystem that
can protect and expand this community, as their skills
will contribute to India’s prosperity. Furthermore, the
skills of craftswomen remain invisible, as women are
often considered unskilled and unproductive. Efforts to
ensure the public acknowledgement of women workers
as a skilled society are urgently needed.
Acknowledgements
Incorporation of traditional practices into contempo-
rary practices would not have been possible without
the interest and support of Shriji Arvind Singh Mewar
of Udaipur, Chairman and Managing Trustee of the
Maharana Mewar Charitable Foundation. The author
thanks all karigars of Mewar, Rajasthan, who shared
knowledge about their material culture, and the technical
staff Dhwani Meghani and Srabani Gayen who partici-
pated in the project.
Notes
1
See https://hmbia.info/ (accessed 14 March 2020).
References
Bottomley, A. and H. Bowstead Stallybrass. 2000. Galva-
nised Indian mail. In Royal armouries yearbook 5, 133–38.
Leeds: Royal Armouries Museum.
Bryant, E. 2001. The quest for the origins of Vedic culture:
The Indo-Aryan migration debate. Oxford: Oxford
University Press.
Jamison, S.W. and J.P. Brereton, transl. 2014. The Rigveda:
The earliest religious poetry of India, 3 vols. Oxford:
Oxford University Press.
Metcalf, S. 2001. The treatment of mail on an arm guard
from the armoury of Shah Shuja: Ethical repair and in
situ documentation in miniature. V&A Conservation
Journal 37: 4–6.
Richardson, T. and N. Bennett. 2015. Indian arms and
armour, 2nd ed. Leeds: Royal Armouries.
SUSTAINABLE GROWTH OF MEWARI MAIL MAKERS: TRADITIONAL TO CONTEMPORARY PRACTICES 145

Sharma, R.K. 1986. The military system of the Mewar

(Udaipur) State (ca. 800 to 1947 A. D.). Central Asiatic
Journal 30(1/2): 116–40.
Singh, V. and H. Seth. 2021. The synergy of craft, conser-
vation, and cutting-edge technology: Conservation of
arms and armour at the City Palace Museum, Udaipur,
India. In Transcending Boundaries: Integrated Approaches
to Conservation: ICOM-CC 19th Triennial Conference
Preprints, Beijing, 17–21 May 2021, ed. J. Bridgland. Paris:
International Council of Museums.

Author
Vandana Singh is head of the Metal Conservation Labo-
ratory at the City Palace Museum, Udaipur. She is the
owner of the Heritage Preservation Centre Kalasampadaa
and co-founder of the Centre for Art Conservation and
Research Experts, LLP in New Delhi. Her interdiscipli-
nary research focuses on uniting traditional knowledge,
conservation and science, and exploring the material
culture of a traditional metal craftsmen community of
South Asia.
Development of Mexican Bell Documentation Tools and
Methodologies
Jannen Contreras Vargas*
National School of Conservation, Restoration and Museography (ENCRyM),
National Institute of Anthropology and History (INAH)
Mexico City, Mexico
jannen_contreras_v@encrym.edu.mx
Daniela Lira Pacheco
National School of Conservation, Restoration and Museography (ENCRyM),
National Institute of Anthropology and History (INAH)
Mexico City, Mexico
daniela_lira_p@encrym.edu.mx
Ángel E. García Abajo
National Coordination of Conservation of Cultural Heritage (CNCPC), National
Institute of Anthropology and History (INAH)
Mexico City, Mexico
angel_garciaabajo@inah.gob.mx
Abstract
Mexican bells suffer from theft, melting, recasting, and other
forms of destruction, along with a lack of documentation that
can be used to support prosecution. This paper describes the
process begun in 2015 to develop specific documenting tools
and methodologies to help preserve Mexican bells, and the first
complete documenting exercise performed on 98 bells at the
Historic Center of Oaxaca, Mexico, in 2019. The first step was
to fill a form with information about each bell’s characteristics
and location, sound and use, state of conservation, fastening
Introduction
Smashing historic bells by throwing them from their
towers prior to melting and recasting is a common
but shocking practice in Mexico. Often, broken bells
are simply left lying on the ground outside buildings.
Bells fulfil a variety of relevant social functions and
document metallurgical techniques and history, but
the absence of appropriate records makes it easy for
bells to end up stolen, melted, and recast, or otherwise
lost without trace.
In this context, the development of a complete docu-
mentation methodology was inspired by the theft of two
18th-century bells for scrap from Escobedo, Montemo-
relos, a small town in northern Mexico. The Metallic
Heritage Conservation Laboratory at the National
School of Conservation, Restoration, and Museog-
raphy (ENCRyM) began a rearguard action in 2015
Francesc Llop Álvaro
Conservatory of Music “Joaquín Rodrigo”
Valencia, Spain
frllop@gmail.com
Francesc Llop I Bayo
Retired anthropologist
Valencia, Spain
083038@gmail.com
Fanny Magaña Nieto
Oaxaca INAH Center, National Institute of Anthropology and History (INAH)
Oaxaca, Mexico
fanny_magana@inah.gob.mx
*Author for correspondence
system, and, where possible, architectural context. The
inventory included a photographic record, sound recording,
metallographic sampling, and chemical analyses. The selection
criteria were based on accessibility, date of manufacture, and
functionality as ringing instruments.
Keywords
bells, bell frames, documentation, information gathering,
inventory
with the organization of the Seminario Permanente de
Conservación de Campanas [Permanent Bell Conser-
vation Seminar].
The current structure of the methodology was strongly
influenced by specialists such as Francesc Llop I Bayo,
an anthropologist and bell ringer at the Cathedral of
Valencia, Spain, who pioneered bell documentation that
resulted in the database <campaners.com>. In addition,
the assistance from Soledad Díaz Martínez of the Cultural
Heritage Institute of Spain (IPCE) was instrumental in
the development of conservation data forms and method-
ologies (Contreras Vargas et al 2015). The first complete
documentation using these tools was performed on the
bells from the Historic Center of Oaxaca, Mexico, in
2019. This work describes the tools developed to provide
a proper response to this problem.
DEVELOPMENT OF MEXICAN BELL DOCUMENTATION TOOLS AND METHODOLOGIES
Mexican bells
Compared to European countries where bells can be
found dating from the 11th century, such as in San
Lorenzo or Laurentina, the oldest in Spain, bells and
the bell-making tradition are relatively new in Mexico.
Christian traditions reached Mexico in the 16th century.
Metallographic studies on Mexican bells carried out by
our team have demonstrated that the casting quality was
quite different from that in Europe. One of the main
reasons for this was the constant scarcity and high price
of materials such as tin. Another was the increasing need
for bells by the new Catholic churches, compounded by
the absence of a structured body of artisans, such as a
guild of bellfounders, that could provide training, rules,
and impose standards. These factors and the use of inap-
propriate clappers resulted in bells suffering from early
deterioration, including deformations, fractures, and
detachment of elements, along with a lack of recognition
of these elements as part of Mexican cultural heritage.
The net result was that bells ended up being neglected
and discarded.
The destruction of bells has also been the result of various
social conflicts, such as wars, during which their metal
would be melted down to make cannons. Today, the
destruction of bells by recasting is conducted by artisan
bellfounders under the approval of civil and religious
authorities, who are unaware of the law and wrongly
believe these actions to be right and even needed.
It must be said that recasting is a destructive procedure.
The crystalline structure and composition of the alloy is
lost, as is the surface layer, decorations, and inscriptions,
even the profile and exact size, as often these features are
not analyzed, documented, or accurately reproduced.
The lack of records on historic bells, such as their char-
acteristics and date of manufacture, etc., has inhibited
prosecution of those who have destroyed these unique
pieces of our material cultural heritage. The lack of
records also means that it is impossible to even measure
how much has been lost. However, under the legal frame-
work supporting the National Institute of Anthropology
and History (INAH), which protects Mexican cultural
heritage, all of the movable cultural property in religious
buildings from prior to the 20th century constitutes part
of the country’s heritage, including bells.
147
Documentation
Documentation is a key part of research and conser-
vation. Documenting and recording are often wrongly
confused and assumed to be synonymous, at least in the
Spanish-speaking world. For this project, documenting
the information was seen as a complex and constant
task requiring processes for recording, searching, and
compiling, followed by revising and expanding what
already existed (Nagel 2009, 8). Letellier and Eppich
(2011, 119) have defined this process as “the systematic
collection of information and archiving of records in
order to preserve them for future reference.” The action
of documenting must take into consideration the level
of detail, scope, and methods applicable, and the forms
in which records should be kept and made available.
For bells, this data includes observations about their
properties, chemical and physical alterations, the various
analytical techniques and their results, and even the
decision-making process in the event that a conservation
intervention is required (Appelbaum 2007, 394).
What and how much to document?
The documenting tools developed required an under-
standing that bell conservation involves the study of
material elements, sound, the meaning and function of
sound, the meaning and social function of the bell, and
the specific language of this kind of cultural heritage,
with all its elements, problems, and the way they interact.
The experiences of Dr. Francesc Llop I Bayo and his
inventory of Spanish bells were combined with the
Conservation and Repair of Bells and Bellframes: Code
of Practice issued by the UK’s Council for the Care of
Churches (2011), whose documenting and conserva-
tion criteria refer to the age and uniqueness of bells and
their sound. However, since the bell-making tradition in
both Spain and the UK differs significantly from that in
Mexico, which has a far shorter history, the documenta-
tion must also include bells made during the 20th century.
The initial scope was to prepare a documenting tool that
would be accessible to bell ringers, sacristans, and bell
enthusiasts, so that they could complete a database of bells
that needed to be protected. However, it soon became
clear that only conservators could readily document, fill,
and use the tool, as it included concepts on preventive
conservation, deterioration dynamics, and tangible and
intangible characteristics.
148  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND TECHNICAL STUDIES

carillon. It also records the type of architectural element

to which it is attached (belfry, campanile, bell tower), the
fastening system—since it is possible for swinging bells
to lose their wooden counterweight (headstock) and
stop working—, and the characteristics of the fastening
system.

Interaction with bell specialists and enthusiasts at confer-

ences during the conservation process allowed the tool to
be expanded with the different names used in the country
for the parts of bells, supports, and architectural features.

Figure 1. Part of the team seen while recording data on the size of the bells

The conservation data forms

The conservation data forms developed since 2015 were
tested in the field and then corrected and improved. After
the 2017 earthquakes in Mexico, it was evident that it was
necessary to record the yokes, headstocks, wheels (even
though Mexican bells usually have no wheels), etc., and
all kind of supports, as well as important information
on the architectural features of bell towers, bell gables,
etc. This was in order to understand how they interacted Figure 3. Two views of the damage seen on bells after the 2017
and to record relevant data to analyze why these architec- earthquake: on the left, a collapsed bell in a bell tower; on the right, the
result of a weakened wooden counterweight
tural elements were damaged and had even failed, thus
helping to prevent recurrence of the same problems as In the absence of chemical analysis in the field, composi-
far as possible. tion is inferred through visual inspection of the metal and
The current form documents the location of the building, corrosion products. Data on the state of conservation of
the location of the bell within the building, and the name the striker/clapper and its fastening system, as well as the
of the person in charge of filling out the form. It includes bell’s fixing, are also recorded, along with the decorations
general measurements and notes on whether the bell is and any engraving on the surface, since this information
swinging or fixed, and whether it is part of a clock or is very important to place it in its historical context.

Figure 2. The conservation data form developed by our team

DEVELOPMENT OF MEXICAN BELL DOCUMENTATION TOOLS AND METHODOLOGIES
The second, and last, page is dedicated to recording all
visible damage, such as corrosion, dirt, deformation,
cracks, fractures, and signs of vandalism. Thus, the data
as a whole creates a picture of the bell both as a utilitarian
object and a historical document of the building and the
community to which it belongs.
First inventory
The most complete result was the inventory of the bells
at the Historic Center of Oaxaca. This was carried out
with guidance from the staff and students from ENCRyM,
Dr. Francesc Llop I Bayo, musician and bell specialist
Dr. Francesc Llop Álvaro, lecturers and students from
the School of Conservation and Restoration of the West
(ECRO) in Mexico, and different INAH work centers.
The inventory covers 98 bells in 31 buildings, most of
which are Catholic churches. The inventory includes
photographic records, sound recordings for 61 bells,
and metallographic sampling and analysis of 47 bells.
Its publication is intended to encourage other groups to
undertake similar documentation in order to create a
national inventory.
Basic features
Primary characterization information was obtained via
direct observation and by using measuring tapes and
laser measurement devices.
The team was aware that visual assessment is limited
by subjectivity, knowledge, skill, and access to the bells.
However, getting access to churches and bell chambers is
not easy. Obtaining permission can take a considerable
amount of time, also travelling to the location, so conser-
vators may not have much time to devote to each bell.
This is a critical point, as Mexico has a massive number of
bells. Visual identification of materials and a conservation
assessment are useful guides, but, whenever possible,
data from chemical analysis, metallography, or X-ray
fluorescence (XRF) spectroscopy should be included.
Photographic record
The original plan to take a photographic record involved
inspection teams using portable ladders, cameras, tripods,
and even cycloramas in the narrow and high stairwells
of the bell towers. However, the access, security, and
safety limitations, and significant quantities of bird and
bat guano, quickly reduced the arsenal of photographic
149
tools to selfie sticks and cell phones with acceptable photo
quality—as suggested by Dr. Llop I Bayo from the begin-
ning—and the photos to whatever could be collected by
two people under regular outdoor lighting conditions.
Using these devices, the team recorded different views of
the bells, including from the exterior, from a safe place
inside the belfry.
Figure 4. Photographic records of bell exteriors taken with a selfie stick
A total of 98 bells were documented in this fashion
with good quality photographs that can be used as
legal evidence in the event of any wrongdoing. The
team is aware that using a drone would also permit safe
and secure digital video and still recording, but that is
currently not a possibility.
Sound characterization
One of the most important and irrecoverable losses that
occurs when bells are recast or removed is their sound—
which is part of the day-to-day life of a population. The
sound of 61 of the 98 bells was recorded. These recordings
were carried out under the guidance of Dr. Francesc Llop
I Bayo using a Tascam DR-44WL recorder and processed
and analyzed using the methodology developed by Dr.
Francesc Llop Álvaro to document the sound of Spanish
cathedral bells (Llop Álvaro 2017).
Analysis of the sound begins by studying the different
frequencies that make the complex sound produced by
the bells. The bell profile controls the sound to a great
extent. Its distinctive partials––which are audio charac-
teristics, since the basic striking note is just one of the
sounds a bell makes when struck––are identified. The
most important partials are the harmonics. Inharmonic
partials follow a different rule (Rossing 1984, 440–47).
For the analysis of the recordings, Wavanal software,
created by William A. Hibbert, was used. Hibbert (2008)
developed this software for his doctoral thesis, but it is
important to note that it was designed to analyze tuned
150  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
bells, such as those used in carillons or clock bells. Subse-
quent analysis and elaboration of the results was therefore
essential. By collecting the results of the different partials,
an image of the bell’s acoustic behavior could be created.
Figure 5. Sound record taken at a bell tower with the help of the church’s
bell ringer
The importance of this data lies in the fact that it allows
researchers to determine the predominant audio struc-
tures of Mexican bells––if that can be said to exist––and,
where possible, help to re-create it in the case of a cracked
or lost bell.
Metallographic characterization
During the initial study in 2015, nine of the bells from
the Cathedral of Oaxaca were analyzed using noninva-
sive analysis techniques, specifically XRF spectroscopy.
However, this method only characterizes surface concen-
trations of elements. The bulk composition can differ
significantly from the surface, especially in objects that
have undergone heat treatment, as was seen in several
of the bells analyzed.
Furthermore, XRF equipment has important restrictions
in terms of air transport and is awkward to work with in
the tight and frequently unsafe spaces inside bell towers.
These management and occupational safety and health
TECHNICAL STUDIES
issues were resolved in 2019 by taking metallographic
samples for laboratory analysis. The samples provide
stratigraphic evidence of coatings and their thickness
over the original cast alloys. All of the sectioned samples
were catalogued for future reference and may be useful
in the event of a bell being destroyed, allowing those
responsible to be prosecuted.
During the 2019 program, a total of 47 samples were taken
from the most accessible bells. Sampling was conducted
in the least damaging way possible by making tangential
cuts in inconspicuous areas that had no structural effect
on the bell at the loops (cannons) or at the outer edge of
the lip. For broken bells, the sample was taken from the
fracture area, since this provides the maximum amount
of metallurgical data. Sample sizes were typically 3 or
4 mm long by 1–2 mm wide for bells in good condition
and slightly larger on fractured bells. The samples were
prepared for metallographic analysis and surveyed with
optical and scanning electron microscopy (SEM), while
the chemical analysis was performed by energy-dispersive
X-ray spectroscopy (EDS).
Figure 6. Sampling and analysis process: (1) on-site sampling, (2) sample
preparation, (3) ready sample, (4) SEM-EDS analysis, (5) metallographic
study under optical microscopy
Due to the composition and metallographic studies
carried out on the bells since 2015 (García et al. 2015),
it is clear that the casting quality of most Mexican bells
is quite different from that in Europe. This finding was
confirmed by the bells in Oaxaca, which differ signifi-
cantly in composition from the normal European “bell
bronze” standard (78% Cu-22% Sn). Of the 56 bells
analyzed, only one had a content of 22% Sn, with the
average being only 5.5%. One of the alloys, from a bell
made in 1870, was closer to brass than bronze because
of its zinc content.
DEVELOPMENT OF MEXICAN BELL DOCUMENTATION TOOLS AND METHODOLOGIES
Analysis also determined the presence of different surface
materials, such as patinas, coatings––such as paintings––,
and gilding, on 12% of these bells. This is very impor-
tant, since these materials are usually removed during
“conservation” processes, such as abrasive cleaning, as
it is commonly, and mistakenly, believed that bells have
no relevant surface materials.
Figure 7. Ternary diagram of the Sn-Zn-Pb composition of the bells at
the Historic Center of Oaxaca. Copper is the main constituent
Ongoing work
The records were compiled during 2019, but the pandemic
stopped much of the project from being completed.
Currently the data is being uploaded onto a single data
system (SUR) at the INAH. However, unfortunately,
according to Mexican law, only cultural objects prior to
the 20th century can be added. Since 20th-century bells
need protection as well, a parallel database has been
created. Meanwhile, Dr. Llop I Bayo is adding data on
the bells to the General Inventory of Oaxaca Bells on the
well-known platform www.campaners.com.1
The team is also constructing a conservation-focused
catalog with information and relevant conservation
conclusions for the 23 bells in the main temples of the
Historical Center of Oaxaca: Santo Domingo, Basilica
of la Soledad, and the Cathedral. This catalog includes
all the collected data, including metallographic analysis
and the sounds recorded.
Future developments in sound recordings will include a
more in-depth examination of the complex strike note to
determine what defines the profiles (shapes) of Mexican
bells in relation to this factor. This can only take place
once there are enough recorded sounds of Mexican bells
to have a broad and statistically representative sample.
151
Conclusion
The documenting tools and methodologies developed
and described in this paper were intended to be a
means of protecting bells and their sounds. While they
demonstrated their usefulness, it is necessary to develop
other, simpler processes to facilitate the recording and
protection of as many bells as possible. Carrying out
documentation in places such as belfries involves diffi-
culties and safety hazards due to the dimensions and
obstructions inherent to these spaces, and bird and bat
guano, so simpler strategies––such as the use of cell
phones and selfie sticks over ladders and professional
cameras, sampling instead of using XRF, and taking
simple sound recordings in the bell chamber, leaving
more complex tasks for the laboratory––proved to be
the most useful.
Acknowledgments
We would like to thank María Álvaro, the conservators
Soledad Díaz, Marcela López, Salem Ojeda, Gabriela
Peñuelas, David Vega, Inés Mejía, and Urani Correa, our
fellow teachers and students at ECRO, the Alfredo Harp
Helú Oaxaca Foundation (FAHHO), and Ryszard Rodys
for their kind support.
Notes
1
 àgina oficial dels Campaners de la Catedral de València
P
[Official page of the Bell Towers of the Cathedral
of Valencia (in Catalan)] (accessed 18 April 2022).
http://campaners.com/
References
Appelbaum, B. 2007. Conservation treatment method-
ology. Burlington: Butterworth- Heinemann.
Contreras Vargas, J., G. Peñuelas Guerrero, I.M. López,
and D. Pascual Cáceres. 2015. Tañendo problemas: La
conservación de campanas sonoras en México. Un semi-
nario permanente. CR. Conservación y Restauración 7:
55–61. https://revistas.inah.gob.mx/index.php/cr/article/
view/12029
Council for the Care of Churches. 2011. The conservation
and repair of bells and bellframes. Code of practice, 2nd
rev. ed. London: Church House Publishing.
García, A., J. Contreras, G. Peñuelas, and M. López.
2015. Caracterización de dos campanas de composición
y fracturas atípicas. In MetalEspaña 2015. Actas del II
152  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Congreso de Conservación y Restauración del Patrimonio
Metálico, Segovia, Real Casa de Moneda, 1–3 October
2015, eds. E. Cano and J. Barrio. Madrid: Universidad
Autónoma de Madrid.
Hibbert, W.A. 2008. The quantification of strike pitch
and pitch shifts in church bells. PhD thesis, Department
of Design, Development, Environment and Materials,
Faculty of Mathematics, Computing and Technology,
The Open University, UK. https://doi.org/10.21954/
ou.ro.0000add2
Letellier, R. and R. Eppich, eds. 2011. Recording, documen-
tation and information management for the conservation
of heritage places, 1st ed. London: Routledge.
Llop Álvaro, F. 2017. Las campanas en las catedrales
hispanas. Análisis, significado cultural, conservación y
rehabilitación. Doctoral thesis, University of Valencia,
Spain. https://roderic.uv.es/handle/10550/59835
Nagel, L. 2009. Manual de registro y documentación de
bienes culturales. Santiago: Centro de Documentación
de Bienes Patrimoniales.
Rossing, T.D. 1984. The acoustics of bells: Studying the
vibrations of large and small bells helps us understand the
sounds of one of the world’s oldest musical instruments.
American Scientist 72(5): 440–47.
Authors
Jannen Contreras Vargas is a conservator with
a degree from the National School of Conservation
(ENCRyM) in Mexico, an MSc in forensic conservation
(University of Lincoln, UK), and a PhD in ancient world
studies (Universidad Autónoma de Madrid, Spain). She
has been a lecturer of conservation methodology and
applied chemistry at ENCRyM since 2001. Since 2015
she has organized seminars and conferences on bell
conservation in Mexico.
Daniela Lira Pacheco is a conservator with a degree
from the National School of Conservation (ENCRyM) in
Mexico, which she completed with a dissertation entitled
“Analysis of intervention possibilities in fractured sounding
bells.” She is a member and organizer of the seminar on bell
conservation, part of the Metallic Heritage Conservation
Laboratory (LCPM), and co-supervisor of ENCRyM’s
Metals Conservation Workshop Seminar.
Ángel E. García Abajo is an associate researcher at
Mexico’s National Cultural Heritage Conservation Coor-
TECHNICAL STUDIES
dination Body (CNCPC-INAH) and a lecturer at the
National School of Conservation (ENCRyM) in Mexico.
He has a degree in chemical sciences, with a specialization
in metallurgy, from Complutense University of Madrid
(UCM) in Spain. He has studied historical metallurgy
since 1996 and is a PhD candidate in ancient world
studies (Universidad Autónoma de Madrid, Spain).
Francesc Llop Álvaro trained as a pianist at the
Conservatori Professional de Música de València (CSM)
in Spain and the École Normale de Musique de Paris
Alfred Cortot in France. He has a PhD in art history
from the Universitat de València (UV) in Spain, for
which he wrote a thesis entitled “Bells in the Hispanic
cathedrals. Analysis, cultural significance, conservation,
and rehabilitation.” Currently, he is a lecturer at the
Conservatori Superior de Música “Joaquín Rodrigo” de
València in Spain.
Francesc Llop I Bayo has a PhD in social anthropology
from Complutense University of Madrid (UCM) in Spain.
He joined the Dirección General de Patrimonio de la
Generalitat Valenciana in 1988, where he was head of
the archaeology and ethnology department from 1991
to 2001 and head of the museum department from 2002
until his retirement in 2014. He has been involved in the
conservation of about a hundred bells and bell towers,
including roughly twelve cathedrals. Along with Mari
Carmen Álvaro Muñoz, he has documented thousands
of bell ringers. He manages the website http://campaners.
com with information about bells, bell ringers, and bell
ringing.
Fanny Magaña Nieto is a conservator specializing in
the conservation of musical instruments. She trained
at the National School of Conservation (ENCRyM) in
Mexico and is coordinator of the conservation depart-
ment at the INAH Oaxaca Center (CINAHO). She is a
member of the Mexican Organ Studies Seminar and the
Mexican Bell Conservation Seminar and has overseen
the management of conservation projects for cultural
heritage affected by the 2017 and 2018 earthquakes
and the project to catalog bells in the Historic Center
of Oaxaca.
Corrosion Detection by Color Change Using Crowdsourced
Photographs. Preliminary Results of the MIPAC Project

Blanca Ramírez Barat* María Teresa Molina Emilio Cano

National Centre for Metallurgical
Research, Spanish National
Research Council (CENIM-CSIC)
Madrid, Spain
blanca.ramirez@csic.es
National Centre for Metallurgical
Research, Spanish National
Research Council (CENIM-CSIC)
Madrid, Spain
mt.molina@cenim.csic.es
National Centre for Metallurgical
Research, Spanish National
Research Council (CENIM-CSIC)
Madrid, Spain
ecano@cenim.csic.es
*Author for correspondence

Abstract
One of the most obvious signs of metal corrosion is color change.
This phenomenon could be used to assess the corrosivity of
the indoor environment in museums and collections in other
institutions. The MIPAC project is therefore developing a
preventive conservation tool for monitoring the impact of the
indoor environment on cultural heritage materials, based on the
color changes associated with deterioration. The changes are
assessed by analyzing photographs taken with cell phones and
provided by museum visitors and staff through an app. A color
reference chart was designed, in which metal coupons are used
as dosimeters. CIELAB color coordinates are extracted from the
images and adjusted using the color references with a calibration
algorithm. This approach allows the preventive conservation
of cultural heritage from both a scientific-technological and
a social perspective, since it involves public participation in
the conservation of museum collections. However, for this
monitoring approach to be valid, the correlations between
color change and corrosion extent need to be determined in
order to explore the possibilities of quantifying the extent of
corrosion from the calibrated photographs. This paper presents
the preliminary results of a validation study, based on tests
of a series of copper and silver coupons exposed in museum
showcases for 6, 12, and 18 months. Color and corrosion
extent measured by gravimetry and galvanostatic reduction
showed the good correlation between some of the colorimetric
information and the corrosion thickness. Although the uneven
distribution of surface corrosion complicates the establishment
of a correlation between corrosion and color change, this issue
can be tackled by a localized evaluation of the corrosion obtained
by electrochemical reduction.
Keywords
preventive conservation, color, monitoring, image analysis,
corrosion

Introduction
The degradation of metals and other cultural heritage
materials is commonly associated with changes in their
visual appearance, especially their color: silver objects
darken and tend to blacken upon exposure to sulfur
gases; copper turns reddish during the first stages of
oxidation and then darkens or assumes a greenish
color as corrosion proceeds; iron changes from silvery
to reddish with the formation of rust layers; and lead
darkens due to the formation of thin lead oxide layers,
shifting to whitish as thicker carbonate layers are formed.
As corrosion processes are the result of ambient condi-
tions, the color changes of metal references can serve
as an indicator of corrosive environments. Thus, the
aim of the MIPAC project1 is to develop a tool that can
be used to monitor the impact of the environment on
cultural heritage materials, based on the color changes
associated with metal corrosion. The basis of this tool is
the relationship between color and corrosion, the ability
to monitor color changes through image analysis, and
the use of citizen science.
The use of metals and the changes in their appearance as
dosimeters to detect aggressive environmental conditions
is well established and is the basis of the well-known Oddy
test. Colorimetric and spectrophotometric methods have
been used elsewhere to determine the color changes in
metals as indicators of corrosion (Tétreault et al. 2003,
Lafuente et al. 2013), but a quantitative correlation
between color change and corrosion extent (quantified
as loss of mass or thickness of the base metal, or as the
thickness of corrosion layers) has not been established
154  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
due to several difficulties (Lafuente 2017). For instance,
Ankersmit (2001) reported uneven tarnishing on flat
silver samples and an unreliable correlation with the
percent color change.
In the MIPAC project, crowdsourced photographs rather
than spectrophotometers are used in color evaluation,
with the aim of establishing a quantitative correlation
between color change and corrosion extent. The feasi-
bility of using cell phone photographs to monitor color
changes was demonstrated by Brigham et al. (2018). The
use of citizen science as a data collection method has two
major advantages: first, it does not require investments
of additional resources by the museum, and second, it
actively involves the public in museum practices and the
conservation of museum objects.
In the MIPAC’s approach, copper and silver strips acting
as dosimeters are mounted as a color reference chart for
use in image calibration, as shown in Figure 1 (Ramírez
Barat et al. 2021). The “MIPAC panels” are displayed in
the locations to be monitored.
Figure 1. MIPAC panel for the monitoring of color changes of metal
coupons. The color chart was printed using UV resistant inks on acid-free
paper covered with propylene
For image collection, a dedicated app2 was created that
allows for better control of the cell phone camera and the
automatic uploading of photographs to the image-pro-
cessing servers. The integration of a gamification scheme
in the app promotes user engagement.
To extract the color information from the photographs, an
image calibration system was designed and subsequently
validated in collaboration with the Visual Telecommuni-
cations Applications Research Group (GATV) from the
Technical University of Madrid (UPM) (Barbero-Álvarez
et al. 2020, Barbero-Álvarez et al. 2021a). MIPAC panels
are photographed by visitors and the images are then
processed and calibrated by applying linear and spatial
calibration algorithms to obtain corrected L*a*b* coor-
TECHNICAL STUDIES
dinates of the metal dosimeters, which are then related to
the extent of corrosion. The robustness of the calibration
method and its ability to adjust for the color differences
in cell phone images from different cell phones have
been demonstrated (Barbero-Álvarez et al. 2021b), and
tests with real metal samples conducted. The results
have thus far shown that color changes are detected with
a high degree of confidence, as shown by comparisons
with direct colorimetric measurements made using a
spectrophotometer (Table 1) (Ramírez Barat et al. 2021).
This allows at least to detect significant changes in the
metal dosimeters that act as indicators of the presence
of harmful emissions in a museum showcase or location.
Table 1. Measured and calculated L*a*b* coordinates for a silver
coupon (from Ramírez Barat et al. 2021)
12A_Ag Measured Calculated
L* (10°/D65) 72.44 68.45
a* (10°/D65) 5.00 4.64
b* (10°/D65) 26.82 26.55
An important step to improve the precision and reliability
of the method is to establish a quantitative relationship
between color changes and corrosion extent. Ideally, a
calibration curve between color coordinates and corro-
sion thickness would allow to measure the corrosion
of metals and classify the corrosivity of a museum
environment, using the MIPAC panels as dosimeters.
Accordingly, we examined the correlation between
corrosion extent and color change in copper and silver
coupons exposed to real museum environments for up
to 18 months at the National Museum of Science and
Technology (MUNCYT) and at the museum of the
Chemistry Faculty of the Complutense University, both
located in Madrid.
Experimental
To analyze the relationship between color and corro-
sion extent, 1 × 5 cm copper and silver coupons were
cut, drilled, sanded with P1200 grit, and mounted on
a MIPAC color reference panel (Figure 1). The panels
were placed inside four different museum showcases
(labeled S1 to S4), two in each of the two aforementioned
museums (Figure 2).
Additional sets consisting of 12 coupons of each metal
were hung on plastic racks, according to ISO 11844-2
standard (International Organization for Standardization
2020), and exposed in the same locations. From this racks,
CORROSION DETECTION BY COLOR CHANGE USING CROWDSOURCED PHOTOGRAPHS. PRELIMINARY RESULTS OF THE MIPAC PROJECT 155

Corrosion was measured by gravimetry as mass gain,

with the values then transformed to the thickness of the
corrosion layer by assuming that the composition of the
corrosion layer was silver sulfide (Ag2S) for the silver
coupons and cuprite (Cu2O) for the copper coupons.
The plot of the corrosion layer thickness versus the
colorimetric coordinates L*a*b* is shown in Figure 3.
The most evident feature of both metals is a reduction
in lightness as the thickness of the corrosion layer
increases. For the silver coupons, changes in the a*
axis are minimum, but a tendency toward yellowing is
evident by the increase in b*. The chromaticity changes
Figure 2. The MIPAC panel monitoring inside a showcase at the Faculty in the copper coupons are smaller, as the hues are
of Chemistry of Complutense University, together with a set of copper
and silver coupons on plastic racks (left side) slightly warmer, with a minimum increase of a* and a
moderate increase of b*.
four coupons of each metal were extracted after 6, 12,
and 18 months to measure the color change and quantify
the corrosion extent by gravimetry and galvanostatic
reduction, following the procedures established in ISO
11844-2 standard. For the electrochemical measurements,
a GAMRY Interface 1000 potentiostat was used, together
with a three-electrode cell with a Ag/AgCl reference
electrode, a graphite counter electrode, and deaerated
KCl 0.1 M as the electrolyte, with constant N2 bubbling.
Reduction was done in delimited areas of the coupons
using a vinyl tape mask. The four coupons at each time
point were subjected to gravimetric evaluation, while
reduction was performed on six areas of one coupon for
each showcase and exposure time.

Color was measured in the L*a*b* color space using a

Konica Minolta CM-700d spectrophotometer with an
∅ 6 mm mask, D65 as the illuminant, and an observer
angle of 10°. Six color measurements were performed,
in the lower, central, and upper parts of each side of
the coupon, to obtain an average value per coupon. Six
measurements were also made in each reduced area.

Results and discussion
The metal coupons showed mild corrosion after expo-
sure in the museum cases, with differences observed
depending on the location. Visually, the silver coupons
had a yellowish hue that was clearly darker at the edges
and in the lower area of the coupon. By contrast, the
copper coupons underwent only slight changes, not
perceivable at first sight, as they remain within their
natural reddish color range.
Figure 3. Correlation between corrosion thickness (measured using the
gravimetric method) and the L*a*b* coordinates for silver and copper
As previously indicated, the distribution of corrosion
is visibly irregular, particularly for silver. In addition to
the concentration of the corrosion at the borders of the
coupons, a comparison of the average values of L*a*b*
for the lower, center, and upper areas of different sets of
coupons (Table 2) showed that the lower areas are gener-
ally darker and yellower (lower L*, higher b*).
156  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND TECHNICAL STUDIES

The fact that the gravimetric determination of the mass or Table 2. L*a*b* coordinates in the lower, central, and upper areas of
thickness of the corrosion products provides an average exposed silver coupons. The average values for each set of samples at
four different locations (S1–S4) after 6, 12, and 18 months of exposure
value for the whole surface detracts from the accuracy of are shown
the correlation between the color and concentration of the
L* (10°/D65)
corrosion products. Therefore, the extent of corrosion was
sample/
also assessed by galvanostatic reduction, using localized exposure time
bottom σ center σ up σ
areas of the silver coupons. Up to six circular areas of S1 / 6 m 87.01 1.27 87.08 1.17 87.48 1.22
several silver coupons were isolated with tape and galva- S2 / 6 m 91.01 0.88 91.21 0.86 91.26 0.91
nostatically reduced. The corrosion layer thickness was S3 / 6 m 91.37 0.87 92.04 0.53 91.81 0.54
calculated using Faraday’s law, following the ISO 11844-2 S4 / 6 m 88.31 2.46 88.47 2.65 86.25 3.53
standard (ISO 2020). Color was also measured in those S1 / 12 m 84.44 2.44 85.45 2.85 85.48 2.34
areas. The results and a comparison with the gravimetric S2 / 12 m 88.99 1.39 89.85 1.38 89.57 1.59
data are presented in Figure 4. The most evident difference S3 / 12 m 91.49 0.54 90.91 0.50 91.77 0.14
is that the electrochemical techniques indicate a more S4 / 12 m 92.58 1.18 92.71 1.07 92.42 1.74
pronounced color variation with the increasing thickness S1 / 18 m 76.19 5.20 78.81 4.08 78.07 4.33
of the corrosion layer. The reduction of a defined area,
S2 / 18 m 82.38 2.59 85.94 1.56 86.91 1.12
coincident with the area of measured color, increases the
S3 / 18 m 91.21 0.67 91.27 0.46 92.39 0.48
sensitivity of the method. In the gravimetric method,
S4 / 18 m 84.74 1.28 86.93 2.26 86.30 1.44
which provides average values for the whole coupon, the
a* (10°/D65)
higher concentration of corrosion products at the edges
sample/
is reflected in the weight gain but not in the color varia- bottom σ center σ up σ
exposure time
tion. These results show that a localized measurement of S1 / 6 m 0.31 0.37 0.25 0.32 0.14 0.32
color together with electrochemical reduction solves the S2 / 6 m −0.47 0.14 −0.41 0.15 −0.35 0.12
unreliability of color measurements in flat silver samples S3 / 6 m −1.38 0.29 −1.19 0.27 −1.23 0.16
reported by Ankersmit (2001). S4 / 6 m 0.53 1.19 1.09 0.98 2.11 2.09
S1 / 12 m 0.57 0.55 0.41 0.74 0.20 0.62
While the data thus far suggested that the variation of
S2 / 12 m −0.25 0.16 −0.20 0.15 −0.18 0.21
L*a*b* coordinates is more or less linear, the number
S3 / 12 m 0.57 0.11 0.41 0.07 0.20 0.13
of items in the data set at this stage of the project is too
S4 / 12 m −0.25 0.33 −0.20 0.07 −0.18 0.51
small to draw final conclusions.
S1 / 18 m 4.08 3.07 2.50 1.78 2.80 2.25
To test the applicability of the MIPAC system, the color S2 / 18 m 1.19 1.07 0.36 0.58 0.10 0.54
coordinates extracted from a photograph of a real metal S3 / 18 m 0.04 0.12 −0.10 0.04 0.22 0.52
coupon from the MIPAC panel (Table 1) obtained in a S4 / 18 m −0.48 0.43 −0.52 0.68 −0.66 0.31
previous work (Ramírez Barat et al. 2021) are included b* (10°/D65)
in Figure 4, labeled as 12A_Ag. The corrosion layer sample/
bottom σ center σ up σ
thickness of this coupon (part of another project) was exposure time
also calculated by gravimetry and galvanostatic reduction S1 / 6 m 14.41 2.86 14.28 2.56 14.38 2.28
of the whole surface. S2 / 6 m 9.47 1.22 8.94 1.02 8.41 0.61
S3 / 6 m 17.90 3.10 16.37 2.50 17.90 2.57
Although this is only one data point, and its value fell
S4 / 6 m 18.29 5.21 18.50 5.24 22.47 7.69
at the extreme of the calibration range for corrosion
S1 / 12 m 22.09 3.54 21.16 5.25 22.68 4.72
layer thickness, for which only a small number of data
S2 / 12 m 14.96 4.17 12.46 2.56 12.79 1.90
are available, it can be considered a reasonable result.
S3 / 12 m 10.89 0.48 10.69 0.42 11.76 1.21
With the use of gravimetric values, the lightness value
S4 / 12 m 15.06 3.37 13.13 3.26 14.38 4.99
of 12A_Ag was much lower than the general trend (even
S1 / 18 m 39.60 10.84 36.12 7.86 36.43 9.02
compared to the spectrophotometric value of 72.44): a*
S2 / 18 m 30.47 5.06 21.86 1.87 20.31 1.41
was slightly higher while b* fit well. With the galvanos-
S3 / 18 m 11.23 1.89 10.52 2.19 8.81 1.10
tatic results, fitting was satisfactory for the L* and a*
S4 / 18 m 27.66 4.25 23.97 5.91 22.68 3.76
coordinates. For the b* coordinate, however, the value
CORROSION DETECTION BY COLOR CHANGE USING CROWDSOURCED PHOTOGRAPHS. PRELIMINARY RESULTS OF THE MIPAC PROJECT
was expected to be yellower. As the calculated coordi-
nate was close to the true measured one, the apparent
mismatch cannot be attributed to the calibration method.
A possible explanation is the evolution of colors in
silver tarnishing, particularly along the yellow-blue axis.
Tarnish layers initially have a yellowish color, but they
can later acquire bluish tones and thick layers become
black. Consequently, the trend in the evolution of the b*
coordinate may differ depending on the thickness inter-
vals. This behavior was suggested in previous works in
which colorimetric measurements were used to quantify
silver tarnishing, based on comparisons of reflectance
(in %) with an ideal reflecting diffuser (Ankersmit 2001,
Ankersmit et al. 2013).
Figure 4. Correlation between corrosion thickness and the L*a*b*
coordinates for silver. Comparison of gravimetric and galvanostatic
reduction results. The L*a*b* coordinates of sample 12A_Ag extracted
from an image of a MIPAC panel and then calibrated are also plotted vs.
corrosion thickness, calculated by gravimetry (12A_Ag G) and following
galvanostatic reduction (12A_Ag R)
Conclusion
The results presented in this work, on the tarnishing
of silver and copper coupons exposed to real museum
157
environments for up to 18 months, showed that for both
metals the amount of corrosion correlated well with the
color changes. While the main change was in lightness,
a good correlation with the chromaticity changes was
also observed.
The problem of the dispersion of the data due to uneven
tarnishing can be largely solved by using localized
reductions and color measurements in small areas of
the coupons.
Further studies, at longer exposure times and in different
museum environments, are necessary to understand
the correlations for thicker corrosion layers. This work
is currently in progress, with more complete results
expected in the coming months.
The good correlation between corrosion and color change
as well as the good results obtained in the calibration of
photographs, as reported in previous work by the authors,
are very promising for the proposed MIPAC system.
Its full implementation will provide a flexible, scalable,
and low-cost solution to the collection of conservation
data in addition to encouraging society’s commitment
to its heritage.
Acknowledgments
This work was funded by the Comunidad de Madrid,
European Regional Development Fund and European
Social Fund, projects MIPAC-CM (Y2018/NMT-4913)
and TOP-HERITAGE (S2018/NMT4372), and Ministerio
de Ciencia, Innovación y Universidades, grant PRE2018-
086667. Development of the methodology was made
possible in part by a collaboration between the National
Museum of Science and Technology (MUNCYT), the
Faculty of Chemistry of the Complutense University of
Madrid, and the Museum of Science and Technology
of Catalonia (MNACTEC), which provided space for
the panels in their scientific-technical collections. The
authors also acknowledge the support of the CSIC
Interdisciplinary Thematic Platform “Open Heritage:
Research & Society (PTI-PAIS)”, Drs. Iván Díaz and
Santiago Fajardo, for their suggestions and support in
carrying out the galvanostatic reductions, and Once34
Ltd. for printing the color charts.
Notes
1
 onitorización por procesado de imagen y ciencia
M
ciudadana para la conservación de materiales del patri-
158  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
monio cultural (MIPAC-CM) (Monitoring by image
processing and citizen science for the conservation of
cultural heritage materials) is a research project funded
by Comunidad de Madrid and the European Union.
www.mipac-cm.es/
2
h
 ttps://play.google.com/store/apps/details?id=com.
norrispalmer.mipac
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ro-Álvarez, J.A. Rodrigo, and J.M. Menéndez. 2021.
Design and validation of tailored colour reference charts
for monitoring cultural heritage degradation. Heritage
Science 9(1): art. 41. https://doi.org/10.1186/S40494-
021-00511-6
Tétreault, J., E. Cano, M. van Bommel, D. Scott, M.
Dennis, M., M.-G. Barthés-Labrousse, L. Minel, and
L. Robbiola. 2003. Corrosion of copper and lead by
formaldehyde, formic and acetic acid vapours. Studies
in Conservation 48(4): 237–50. https://doi.org/10.1179/
sic.2003.48.4.237
Authors
Blanca Ramírez Barat obtained a BA in fine arts
(conservation), after which she focused on heritage
science, graduating with a degree in chemistry (UCM
University) and obtaining a PhD in materials science
and engineering (UC3M University). Since 2013 she has
worked at the CENIM-CSIC on the application of electro-
chemistry to the conservation and diagnosis of metallic
heritage. She has participated in several national and
European research projects, as well as different initiatives
related to heritage science, including the TechnoHeritage
network, the National Conservation Research Plan, the
CSIC Interdisciplinary Platform Open Heritage: Research
and Society, and the Spanish Node of the European
Research Infrastructure in Heritage Science (ERIHS.es).
María Teresa Molina has a BA in conservation and
restoration of cultural heritage and a MSc in science and
technology of architectural heritage from the University
of Granada. She has worked as an R+D+I technician
CORROSION DETECTION BY COLOR CHANGE USING CROWDSOURCED PHOTOGRAPHS. PRELIMINARY RESULTS OF THE MIPAC PROJECT 159

in the Department of Mineralogy and Petrology of the

University of Granada in topics such as the deterioration
of heritage materials by exposure to environmental and
atmospheric agents. Since 2019, she has been working on
her PhD thesis in materials science and engineering at the
CENIM-CSIC. Her work is focused on the conservation
of metals in scientific-technical heritage.

Emilio Cano is senior scientist at the CENIM-CSIC in

Madrid. He is head of the “Atmospheric Corrosion and
Cultural Heritage Conservation” (CAPAC) research
group, dedicated to studies of corrosion, the protec-
tion of metallic heritage, atmospheric corrosion, and
electrochemical techniques. He is the author of more
than 90 articles and 100 contributions to conferences.
He is a Fellow of the IIC and was assistant coordinator
of the ICOM-CC Metals Working Group (2012–2020).
He is a member of the coordination team of the CSIC
Interdisciplinary Platform “Open Heritage: Research and
Society” and National Coordinator of the Spanish Node
of the European Research Infrastructure for Heritage
Science (E-RIHS).
Reflectance Transformation Imaging Feature Maps for
Visual Documentation of Metal Objects

Amalia Siatou* Gaëtan Le Goïc Laura Brambilla

Haute Ecole Arc Conservation-
restauration (HE-Arc CR), HES-SO
University of Applied Sciences and
Arts Western Switzerland
Neuchâtel, Switzerland
amalia.siatou@he-ar.ch
Marvin Nurit
Imaging and Artificial Vision
Laboratory (ImViA), EA 7535,
University Burgundy-Franche-Comté
Dijon, France
marvin_nurit@etu.u-bourgogne.fr
Imaging and Artificial Vision
Laboratory (ImViA), EA 7535,
University Burgundy-Franche-Comté
Dijon, France
gaetan.le-goic@u-bourgogne.fr
Alamin Mansouri
Imaging and Artificial Vision
Laboratory (ImViA), EA 7535,
University Burgundy-Franche-Comté
Dijon, France
alamin.mansouri@u-bourgogne.fr
Haute Ecole Arc Conservation-restauration
(HE-Arc CR), HES-SO University of Applied
Sciences and Arts Western Switzerland
Neuchâtel, Switzerland
laura.brambilla@he-arc.ch
Christian Degrigny
Haute Ecole Arc Conservation-restauration
(HE-Arc CR), HES-SO University of Applied
Sciences and Arts Western Switzerland
Neuchâtel, Switzerland
christian.degrigny@he-arc.ch
*Author for correspondence

Abstract
Visual documentation plays a key role in cultural heritage
preservation, especially in condition assessment, recording,
and monitoring of objects. This research aims at detecting and
documenting surface changes on cultural heritage metal objects
by employing reflectance transformation imaging (RTI). The
objective is to use technological advances in the application of RTI
for automated visual documentation of historical metal surfaces.
The proposed methodology examines how new algorithms
developed to process raw RTI data can be applied to study surface
appearance attributes as a function of their angular reflectance.
Through visualization of geometric or statistical surface features,
global characterization of the appearance attributes and
isolation of information are possible. As an illustration of the
methodology developed, zinc printing plates exhibiting localized
corrosion were examined in terms of condition assessment and
surface cleaning monitoring. Data were acquired by employing
monochromatic acquisitions using a dome with fully calibrated
and motorized functions. Selected features of the surface
parameters were then visualized as feature maps. These maps
were compared to common RTI visualization methods based
on relighting and studying the surface normal. Examination
and interpretation of the results indicated that feature maps
can provide an enhanced visualization of surface information
in comparison to commonly used methods. Geometric maps
mainly contain information about the surface topography,
whereas statistical maps principally provide information related
to changes in the surface reflectance response and thus can
separate differences in the light reflection between a metal
substrate and its corrosion products. The combination of the
extracted information enhances the visualization of an object’s
condition and allows the creation of accurate cartographies.
Keywords
reflectance transformation imaging (RTI), condition
assessment, monitoring cleaning, surface documentation,
feature maps

Introduction
The need for conservation documentation is well defined
in terms of record keeping, monitoring, decision making,
and accessibility for managing and preserving tangible
cultural heritage (Moore 2001, Letellier 2007). Within the
general aspects of conservation documentation, condi-
tion assessment corresponds to recording the physical
state of an object, at a moment in time, in a planned and
methodological way (European Committee for Stand-
ardization 2019). It is common practice to accompany
written condition reports with visual documentation.
Visual and realistic representation of cultural heritage
objects is mainly achieved by means of imaging tech-
niques that are constantly gaining ground in the field
(Stanco 2011, Payne 2013, Bentkowska-Kafel 2017). To
this extent, this paper examines the use of reflectance
transformation imaging (RTI), a multi-light image
collection (MLIC) technique, as a visualization tool
for the condition assessment of historical metal objects
and its possible application in mapping conservation
treatments.
REFLECTANCE TRANSFORMATION IMAGING FEATURE MAPS FOR VISUAL DOCUMENTATION OF METAL OBJECTS
State of the art
RTI has been introduced as an easy-to-use, nonin-
vasive, portable, image-based technique that creates
photorealistic renderings of surface textures. The basis
of RTI lies in the work of Malzbender et al. (2001), who
created an image-based methodology using polynomial
texture mapping (PTM) in order to increase photoreal-
istic rendering of textured surfaces and overcome the
restrictions and complexities in the application of bump
mapping. Since then, RTI has become of interest in
cultural heritage-related applications, mostly due to the
free software made available by the nonprofit corporation
Cultural Heritage Imaging (2021).
In the field of cultural heritage, RTI is being used to
reveal the artistic and technological characteristics of
objects or artworks by enhancing epigraphs and reliefs on
different materials (Mudge 2008, Mudge 2010, Historic
England 2018, Mytum 2018). Gradually, the possibilities
of RTI, beyond its use as an object representation tool,
indicate its usefulness as a scientific tool. Seen from
different perspectives, various scientific teams have
developed methodologies or pipelines for documenting
not only object surfaces but also conservation treatments
(Kotula 2013, Manrique Tamayo 2013, Ono et al. 2017,
Boute 2018, Rosseti 2019) or for revealing underlying
information with the integrated use of spectral imaging
(Giachetti 2017, Ono 2017) and to map defects with clear
topographic changes (Manfredi 2014, Corregidor 2020).
Manfredi et al. (2013; 2014) were the first to introduce a
methodology for measuring changes by computing the
statistical limits of the surface and comparing the surface
normal before and after damage, therefore creating
damage maps. Corregidor et al. (2020) introduced an
image-processing methodology that combines RTI
specular enhancement and edge detection algorithms to
isolate and document topographic defects (i.e., scratches)
on a set of similar coins.
With regard to the literature on cultural heritage metal
objects, little study has been done on documenting the
condition of metal surfaces (Corregidor 2020) or moni-
toring conservation treatments (Kotula 2013, Rosseti
2019, Min 2021). In most cases, the ability of RTI as a tool
for enhancing details is validated. However, the benefit of
using RTI as a visual inspection tool for failure analysis
of industrial metal surfaces was analyzed by Coules et al.
(2019). In their paper, they demonstrate that even though
161
RTI cannot replace photogrammetric techniques, it can
provide invaluable information for the interpretation of
failure analysis.
Research focus
The current project proposes a new methodology based
on the evaluation of surface features visualized through
feature maps, with particular interest in documenting
surface information in an accurate and automated way.
The concept assumes that metal corrosion causes changes
in physical properties that also manifest as changes in
appearance, such as topographic alteration (material loss
or gain), texture differentiation (i.e., change in porosity,
crystal formation on the surface, localized corrosion
forms), color alteration (one of the most common char-
acteristics of metal corrosion), and loss of metal gloss.
Furthermore, documentation on cleaning treatments
was also examined, since it involved direct changes in
surface appearance.
Methodology
The experiment took place at the Imaging and Artificial
Vision Laboratory (ImViA) at the University of Burgundy
Franche-Comte in Dijon, France. It involved the use of a
dome-based system that provided controllable functions,
ensuring reproducibility of acquisitions and giving access
to different forms of data processing, i.e., surface texture,
generating maps or extracting 3D surface parameters,
and quantifying results.
Materials and methods
The system consisted of a custom-made dome equipped
with a single light source (cold white LED, 5000 K) that
was adjusted to a motorized system with the ability
to move in a circular axis and rotate at 360° and thus
covering a hemispherical space denominated in φ (eleva-
tion) and θ (azimuth) angles (Figure 1a). An industrial,
monochromatic camera with a CMOS sensor (Sony
IMX304, resolution 4112(H) × 3008 (V)) was placed at
the top of the dome and a motorized objective lens was
attached to the camera. A user interface allowed the
control and setting of experimental parameters.
The object under investigation was placed in the center
of the dome orthogonal to the camera, and a stack of
stereo-photometric images from different light positions
was acquired (Figure 1a). After capturing the images, the
162  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
appearance of the surfaces was modeled using custom-
made software. This software provided functions for
controlling the dome but was also equipped with visu-
alization tools and exploitable data formats.
Figure 1. (a) Simplified schematic representation of RTI acquisitions using
a dome system with one light source and (b) an image of the system used
Two visualization methods, providing different types
of information at pixel level, were evaluated (Figure 2).
The first involved fitting models, which are used to
provide continuous reconstruction of the angular light
and thus provide multi-light illumination of the exam-
ined surface. The methodological approach for fitting
models is well described in the literature (Malzbender
2001, Pitard 2017, Pintus 2018, Cultural Heritage Imaging
2021). Here, fitting models are examined as part of
the common approach for data visualization through
image relighting and extraction of the surface normal.
For this project, a fitting model called discrete modal
decomposition (DMD) was used, as it has shown more
accurate visual reconstruction on specular surfaces than
polynomial texture mapping (PTM) and hemispherical
harmonics (HSH) (Thomas 2019).
Figure 2. Schematic representation of the visualization of RTI-derived
information
The second approach was based on feature extraction
from the examined surface in the form of feature maps.
The features of an image are distinct or repeatable char-
acteristics/attributes that can be measured. For RTI, data
feature extraction is possible through the application
TECHNICAL STUDIES
of mathematical functions related to the geometric or
statistical attributes of a surface and is visualized through
feature maps. These maps correspond to the per-pixel
analysis of the surface in a global way (the entire surface
selected) and are able to characterize its topography/
texture and appearance.
Feature maps can be categorized as geometric and statis-
tical. In the former, information is derived from isolating
the directional data corresponding to normal map or
from exploiting the curvature properties (calculation
of the change rate of a curve from a straight line). In
the latter, the calculation is made by applying statistical
functions to the stack of multi-light data. This provides
information on the distribution, variability, or asymmetry
of the reflectance response of the examined surface
(Figure 3).
Figure 3. Categorization of geometric and statistical features
Application in a case study
Two aspects of conservation documentation were exam-
ined: condition assessments and documentation of
cleaning treatments. The condition assessment aims
at recording the visible changes on metal surfaces as a
result of corrosion phenomena. The documentation of
cleaning treatments aims at recording the changes to
the surface as a result of the treatment. The commonly
used approach of relighting and studying the surface
normal is compared to the proposed methodology of
using geometric and statistical feature maps.
The case of zinc printing plates (Figure 4) was selected.
These objects encompassed certain characteristic features
in terms of manufacturing and decoration, including
decorative engraving and different textures. In particular
they consisted of a zinc plate (identified by X-ray fluo-
rescence, analyses not presented in this paper) with a
mat surface finish and the characteristic grayish color of
zinc. They were engraved and the lower reliefs presented
a rougher texture covered by a dark layer, most probably
related to residues of ink from the printing process.
REFLECTANCE TRANSFORMATION IMAGING FEATURE MAPS FOR VISUAL DOCUMENTATION OF METAL OBJECTS
In regard to corrosion, they presented clearly visible
signs of localized corrosion in the form of white spots
scattered over the surface (Figure 4) that corresponded
to crystalline agglomerates of zinc carbonates (char-
acterized by Fourier transform infrared spectroscopy,
analyses not presented in this paper). These spots
created localized changes in the surface appearance,
observed as a white color with a rough texture and
crystalline topography that differed greatly from the
metal substrate.
Figure 4. Photograph of the object with (a) the characteristic white
corrosion spots and (b, c) different magnifications of the examined area
For the condition assessment, surface corrosion charac-
terization was studied at two different magnifications: one
corresponding to the general appearance of the surface
(global) and the other concentrated on one corrosion spot
(local). For the cleaning treatment, a similar surface was
studied before and after mechanical cleaning.
Results
Condition assessment
The selected object has different appearance properties
related to both manufacturing and decorative details, as
well as the presence of white corrosion spots (Figure 5a).
Relighting (Figure 5c) provided information on the
surface topography, manufacturing, and condition, which
were better depicted depending on the lighting angle. In
parallel, the surface normal (Figure 5b) was difficult to
interpret as it incorporated all of the topographic infor-
mation in a single visualization.
In the general observation of the surface, the geometric
maps (Figure 6a) were mostly able to characterize tech-
nological features related to the manufacturing and
decorative characteristics of the selected printing plate,
while defining the directionality of these features. For
example, the “Dz” map depicted areas parallel (white)
163
Figure 5. Condition assessment by common forms of visualization:
(a) image, (b) surface normal, (c) relighting
or perpendicular (black) to the viewpoint (positioning
of the camera) and therefore simulated the height differ-
ences on the surface. As regards local observations, the
corrosion products were accurately visualized in terms
of topography. The particular corrosion products did not
present any specific directionality and extended across
the top of the metal surface.
The statistical maps (Figure 6b) provided interesting
corrosion information. The results were similar for both
magnifications, but the higher magnification presented
more details on the extent of the corrosion products
on the metal surfaces. The characteristic white spots
were clearly recorded, since they presented completely
different reflectance responses from the metal substrate.
The corrosion reflectance response was characterized by
negative skewness and a low coefficient of variation (CoF)
that could be explained by the fact that these spots, in
relation to the surrounding metal surface, were white and
mat (negative skewness) but also presented lower vari-
ation in reflectivity (low CoF) for the different lighting
positions due to their non-specular texture. In parallel,
the manufacturing/decorative characteristics that create
different reflection responses were well depicted in the
statistical maps. For example, the dark areas of the lower
reliefs showed higher skewness and CoF due to the dark
color of the surface and the varying specular reflectivity
for the different light positions, respectively.
Figure 6. Condition assessment using geometric and statistical feature
maps under different magnifications
164  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Overall, the feature maps were able to separate infor-
mation and depict the characteristics of the surface in
terms of condition documentation. In certain cases,
especially for statistical feature maps, the visualization
can be enhanced by selecting the appropriate color
scale. In Figure 7, the difference in the visualization
between the grayscale and color scale is demonstrated.
For the color scale, a three-color transition from blue to
yellow to red was selected, illustrating lower to higher
values, respectively. In the particular case, the color
scale on the mean map depicts the white corrosion spots
varying from yellow to dark red, which corresponds to
lighter-colored areas. The green areas correspond to
the metal where the metallic grayish color was retained
and the blue areas to the lower level of the darker metal
background.
Figure 7. Enhancement of the visualization by selecting the appropriate
color map. Example of the mean feature map
Monitoring cleaning
A similar surface, from a different printing plate, was
cleaned mechanically with the aim to remove the most
friable corrosion products. The effect of the cleaning
process was documented with the proposed visualiza-
tion methods. Acquisitions before and after cleaning
were constant (same number of acquisitions and light
positions, same exposure time, same object position) to
ensure reproducibility of the results.
Surface normal and image relighting were able to docu-
ment the surface change (Figure 8). The surface normal
recorded the surface topography, but, as stated above,
the information provided was mixed in one single visu-
alization. With respect to relighting, the surface change
was visible, but no important information was extracted
from the different lighting angles.
TECHNICAL STUDIES
Figure 8. Documenting cleaning treatments: RTI relightable images at
the same lighting angles before (top) and after (bottom) cleaning
Both the representative geometric and statistical maps
showed the effect of cleaning in regard to surface changes
in topography and visual appearance, respectively
(Figure 9). The statistical maps, in particular, were better
able to document the reinstatement of the metal surface
and the extent of the remaining corrosion products. In
both mean and standard deviation maps, the areas with
higher values, representing the areas with corrosion prod-
ucts, showed values closer to that of the metal substrate
after cleaning (moving from red-yellow to light blue).
Furthermore, the remaining corrosion products had
lower values than prior to cleaning (shifting from red
to yellow), corresponding to partial surface cleaning in
the relevant areas.
Figure 9. Documenting cleaning treatments: geometric (left) and
statistical (right) feature maps before (top) and after (bottom) cleaning
Discussion and conclusion
Even though RTI has been used in the field of cultural
heritage for almost 20 years, there is still room for devel-
opment in many different aspects. Current developments
that can lead to the use of RTI as a documentation tool
are still at an experimental stage and require expertise to
apply and interpret the results. The proposed method-
ology, although still under development, is anticipated to
provide a user-friendly interface for visualization-based
conservation documentation. Nevertheless, expertise will
be required to interpret the results.
REFLECTANCE TRANSFORMATION IMAGING FEATURE MAPS FOR VISUAL DOCUMENTATION OF METAL OBJECTS
From the case study examined, it is evident that RTI
feature maps can provide more enhanced visualization
and isolation of information than common RTI relighting
and the observation of surface normal. These maps can
document technological features and reveal information
on corrosion phenomena that provoke alterations in
surface appearance and therefore automate surface condi-
tion mapping. When applied as a tool for documenting
conservation treatments, they can accurately record the
surface change and help monitor conservation treatments
by creating accurate cartographies.
As a general observation, geometric maps are linked to
information related to the directionality of the surface
and are thus able to easily isolate technological and
decorative characteristics. When the appropriate scale
is selected, corrosion products can be studied in terms
of topography and the alterations they can cause to the
metal substrate.
In parallel, statistical maps are directly related to the
surface reflectance response, allowing differences in
the appearance attributes to be distinguished between
corrosion products and metal surfaces. Further exam-
ination of the representation of the statistical maps
can lead to correlations in the behavior of the surface
and thus help to improve understanding of corrosion
formations or document the extent of a conservation
treatment.
The proposed methodology shows great potential for the
application of RTI data processing methodologies as a
tool for accurate and automated condition assessment
monitoring of conservation treatments in historical
metal objects.
Future work will involve quantifying the results and
isolating selected features based on second-order statis-
tical analysis and data segmentation, respectively. These
will provide access to more accurate surface documenta-
tion and automation of monitoring processes.
Acknowledgments
This research was conducted within the CHANGE
(Cultural Heritage Analysis for New Generations)
project, which has received funding from the European
Union’s Horizon 2020 research and innovation program
under the Marie Skłodowska-Curie grant agreement
No. 813789.
165
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Authors
Amalia Siatou is a professional conservator-restorer
with a master’s in chemistry and material science (2013).
Her studies and professional career have been devoted
to conservation-restoration practices, scientific analysis,
and evaluation of different cultural heritage materials.
Since 2019, she has been a research assistant at HE-Arc
CR and a PhD candidate at the ImViA Laboratory at the
University of Bourgogne.

Marvin Nurit is a PhD candidate in computer science

at the ImViA Laboratory working on the NAPS project
(ANR-17-CE10-0005).

Gaëtan Le Goïc is an assistant professor at the University

Burgundy-Franche-Comté and a member of the ImViA
Laboratory.

Alamin Mansouri has been a professor in computer

science and imaging at the University Burgundy-Franche-
Comté since 2006. He received his PhD in computer
vision in 2005 from the University of Burgundy. His
current research is focused on computational modelling
of visual perception through imaging.

Laura Brambilla has a PhD in chemical sciences from

the Università degli Studi di Milano, Italy. Since April
2013, she has been part of the R&D team at HE-Arc
CR, first as a scientific collaborator and, from 2017, as
a professor. She is currently project leader of various
different projects.

Christian Degrigny has a PhD in analytical chemistry

from the University of Paris IV on the stabilization of
submerged aluminum remains. He has since specialized
in the application of electrochemistry in conservation
science and the use of imaging techniques by conser-
vation professionals. He is currently a professor at
HE-Arc CR.
Revealing Degradation Patterns: Imaging Techniques
for the Study of Metal Soap Formation on Painted Metal
Objects
Silvia Russo*
Haute Ecole Arc Conservation-restauration (HE-Arc CR), HES-SO University of
Applied Sciences and Arts Western Switzerland
Laboratory of Technologies for Heritage Materials (LATHEMA), University of
Neuchâtel
Neuchâtel, Switzerland
silvia.russo@he-arc.ch
Laura Brambilla
Haute Ecole Arc Conservation-restauration (HE-Arc CR), HES-SO University of
Applied Sciences and Arts Western Switzerland
Neuchâtel, Switzerland
laura.brambilla@he-arc.ch
Abstract
In attempting to document the degradation processes
occurring on cultural heritage objects, imaging-based
analytical techniques present many advantages, as they
provide spatial and spectral information and allow the
simultaneous investigation of the chemical and morphological
characteristics of a sample. This study presents a protocol
based on chemical imaging – Fourier transform infrared
microspectroscopy (μ-FTIR) and hyperspectral imaging (HSI)
– aimed at monitoring the formation of metal soaps on
model metal coupons. Oil-painted metal supports are in fact
not immune to degradation due to metal soaps formation,
a phenomenon that affects all oil-painted surfaces from the
initial curing of the paint film. Copper and zinc sheets were
coated with cold-pressed linseed oil and artificially aged for one
Introduction
Metals, particularly copper, lead, iron and zinc, have
historically been common supports for painted artworks
due to their unique technical and aesthetic properties
in comparison to canvas and wood (Pavlopoulou and
Watkinson 2006, Terenzi et al. 2006). Some exam-
ples include oil-painted metal artworks popularised
during the 16th and 17th centuries by old masters like
Rembrandt and Rubens, and later in the 20th century by
contemporary artists such as Frida Kahlo, Frank Stella
and Alexander Calder. It is worth mentioning that the
concept of oil-painted metals is not limited to polychrome
metal objects but also encompasses metalwork artefacts
covered with waxes, lacquers and oils as protective or
finishing coatings (Hughes 1993).
Jean-Baptiste Thomas
Norwegian University of Science and Technology (NTNU)
Gjøvik, Norway
jean.b.thomas@ntnu.no
Edith Joseph
Haute Ecole Arc Conservation-restauration (HE-Arc CR), HES-SO University of
Applied Sciences and Arts Western Switzerland
Laboratory of Technologies for Heritage Materials (LATHEMA), University of
Neuchâtel
Neuchâtel, Switzerland
edith.joseph@he-arc.ch
*Author for correspondence
month in order to instigate the formation of metal soaps. Their
reaction was then monitored by means of µ-FTIR. The chemical
maps showed an increasing trend over time, elucidating some
aspects and differences in the mechanism of formation of
the organic salts for the two metal substrates. Additionally,
the samples were analysed using two hyperspectral cameras,
operating in the visible-near infrared and short-wave infrared
spectral range. The appropriateness of the two cameras in the
investigation of metal soaps, and the effect of the thickness of
the coating on the data obtained, is discussed here.
Keywords
metal soaps, metal carboxylates, imaging, painted metals,
metal conservation
Metal soaps are a class of water-insoluble organic salts
(carboxylates) that form ubiquitously on artworks
whenever a reactive metal ion is in close contact with
fatty acids, which typically come from an oil binder
(Hermans et al. 2016). Many scientific studies have
been conducted in the past couple of decades to inves-
tigate the technical aspects of the formation of such
compounds, from the initial chemical reaction (Baij et
al. 2018; Casadio et al. 2019, 47; Garrappa et al. 2020)
to the aggregation and migration mechanism of the
crystalline species towards the surface of the painting
(Herman 2016) and the subsequent implications for
the preservation of the object (Gabrieli et al. 2017,
Banti et al. 2018).
REVEALING DEGRADATION PATTERNS: IMAGING TECHNIQUES FOR THE STUDY OF METAL SOAP FORMATION ON PAINTED METAL OBJECTS 169

Even though it would be theoretically possible to understanding of the degradation pathways as the reac-
transfer the knowledge derived from such studies to tions progress. Specifically, artworks can be sequentially
any oil-painted object, different substrates present unique monitored by obtaining spectra of the same region of
physicochemical characteristics that must be taken into interest to generate a time series of chemical images.
consideration (Campos et al. 2016). When dealing with
Some considerations on the use of hyperspectral imaging
the formation of metal soaps within a traditional pictorial
(HSI) devices for the study of oil-painted metals are also
film, the analytical focus is centred on the interaction
presented. HSI techniques are a set of non-invasive,
between the metal ions of the mineral pigments and
non-destructive techniques based on the acquisition
the binder in which they are embedded (Casadio et al.
of separate images at narrow intervals of wavelengths
2019). However, the presence of a metal support acts as
(< 10 nm), called bands, that can then be analysed as
a competing source of metal ions, in which case another
a function of the chemical composition of an object
type of interaction must be identified between the paint
(Amigo 2020). Although HSI systems are not always
layer as a whole and the metal substrate. At a microscopic
readily available, they have proven successful in the
level, such organic-inorganic reactions occur between the
field of cultural heritage to identify pigments or binders,
fatty acids in the oil binder and the metal species present
or to monitor conservation treatments. Specifically,
in the support, and they are influenced by both internal
pigments have a strong characteristic signal in the
and external factors that affect the interface between the
visible and near-infrared range (VNIR, 400–1050 nm),
metal substrate and the oil paint. This adds a layer of
whereas binders typically have a strong spectral signa-
complexity to the study of the oil-metal system.
ture in the short-wave infrared spectral range (SWIR,
Applying the most common analytical techniques used 1050–2500 nm) that makes their identification possible
in the study of metal soaps found in paintings on canvas (Cucci et al. 2019, Amato et al. 2021).
would imply sampling and embedding in a suitable resin
The search for diagnostic signals of the presence of metal
as a cross-section (Kaszowska et al. 2013; Keune and
soaps in reflectance spectra acquired in the VNIR and
Boon 2013; Hermans et al. 2018; Casadio et al. 2019, 195;
SWIR spectral regions is described here. Such indicators
Ortiz Miranda et al. 2020). In the case of painted metals,
could manifest themselves in changes in the shape or
the paint alone would not give exhaustive information
intensity of the signal that could imply a chemical vari-
to shed light on the system’s complexity, as the reaction
ation due to the formation of metal soaps.
of interest occurs at the interface between the metal
and the paint layer (Pavlopoulou and Watkinson 2006).
Materials and methods
However, sampling the metal support together with the
paint raises both technical and ethical concerns, as it can Sample preparation
provoke irreversible damage.
Model samples were prepared for artificial ageing in trip-
The approach for a suitable elucidation of the degra- licates as 60 × 60 × 1 mm hair-brushed copper and zinc
dation processes occurring on such objects must then sheets. The hair-brushed finishing – an industrial process
involve the use of non-destructive techniques (NDT) which consists in utilising an abrasive material to create
for the investigation of the interface between the metal unidirectional lines giving a satin finish – was chosen
and the paint. A combination of well-chosen NDT can to mimic the artists’ common practice of scratching the
provide the in-depth information necessary to carry out surface of the metal prior to painting to increase the grip
conservation-restoration treatments (Cucci et al. 2019, of the paint on the metallic support. The samples were
Hennen Rodriguez et al. 2020). degreased with absolute ethanol (VWR Chemicals) and
coated with ~80 µL of cold-pressed linseed oil (Kremer
For this study, Fourier transform infrared microspec-
Pigmente). The linseed oil was applied on the metal
troscopy (µ-FTIR) was used to investigate the painted
surface with the aid of a rectangular painter’s spatula.
metal model samples. This analytical technique can be
used both to characterise metal soaps as well as generate
Coating thickness evaluation
chemical maps to understand the relative distribution of
the carboxylates (Gabrieli et al. 2017), allowing compar- The low affinity of oil and metal for one another did not
isons between different regions of an artwork and an allow homogeneous coatings to be obtained, despite the
170  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
standardisation of the samples’ preparation and coating
procedure. The samples presented evident differences
in coating thickness, a feature whose effect is intended
to be taken into consideration in this study. The inho-
mogeneities of the oil coating were measured using the
coating thickness gauge Surfix by Phynix, resulting in
ranges of thickness from 2 to 15 µm for the copper and
from 3 to 25 µm for the zinc samples.
Accelerated ageing
The coated samples were cured overnight at 80 °C then
artificially aged at 80 °C and 80% relative humidity in
a laboratory oven for 30 days. The triplets were kept
in a sealed box at constant relative humidity using a
glycerol-water emulsion (50% w/w) (Forney and Brandi
1992) and monitored by means of µ-FTIR at spaced time
intervals during 30 days. The samples were then left at
room temperature and relative humidity for an additional
11 months. The levels of relative humidity and tempera-
ture were monitored using a PeakTech 5185 datalogger
equipped with an immersion probe.
Fourier transform infrared microspectroscopy
(µ-FTIR)
Fourier transform infrared spectra were collected using
a Thermo Scientific Nicolet iN10 MX infrared micro-
scope equipped with a motorised stage. For each sample,
single scan spectra were acquired in reflectance mode
(650–4000 cm−1) with an aperture of 150 × 150 µm2,
step of 100 µm and at a resolution of 4 cm−1 on three
different areas (7500 × 1800 μm2). Spectra elaboration
was achieved with Omnic proprietary software and then
visualised using the ggplot2 package in the R free soft-
ware environment for statistical computing and graphics
(www.r-project.org/). Baseline, normalisation and atmos-
pheric corrections were performed to remove residual
signatures of atmospheric CO2 and water in the spectra.
Chemical heatmaps were generated in the spectral range
of 1525–1650 cm−1 to cover the main vibrational bands
corresponding to metal soaps (νaCOO−). The results were
comparable in all three areas analysed, hence only one
of the regions of interest will be discussed in this work.
Hyperspectral imaging (HSI)
Twelve-month-aged samples were analysed with push-
broom HySpex VNIR-1800 and SWIR-384 hyperspec-
tral cameras by Norsk Elektro Optikk. The acquisition
TECHNICAL STUDIES
geometry was standard at 45°/0° and the focus was set
at 30 cm, with a field of view of 16°, yielding a pixel size
of approximately 50 µm. The model samples and 99%
white diffuse reflectance standard (Spectralon) were
placed in-plane on a flat translational stage with mounted
broadband spectral coverage tungsten-halogen lamps at
45° and the camera at 90°. Acquisitions were performed
in the dark with the white standard playing the role of a
wide spectral range Lambertian reflector with uniform
response, to correct for the reflectance of the light source.
For the extraction of the spectra, an area of analysis
of 1000 × 1000 µm2 (20 × 20 px2) was chosen as a
good compromise between signal quality (S/N ratio)
and occurrence of representative regions of interest of
comparable size within the sample. The bundled OEM
software was used to implement dark current correction
and calibrate the sensor in the pre-processing stage of the
dataset. HyspexRadV2.0 software was used to convert
the raw data into radiance pixel values. The processing
of the data to obtain interpretable and comparable rela-
tive reflectance spectra was carried out using the ImageJ
open-source software. After re-slicing of the datacube at
the top avoiding interpolation, the data acquired both in
the VNIR and SWIR ranges were corrected for illumi-
nance, i.e. the dataset was divided by the radiance values
of the Spectralon white diffuse reflectance standard, after
stacking, re-slicing and adjusting its size to that of the
samples (Babini et al. 2021).
Results and discussion
Fourier transform infrared microspectroscopy
According to previous studies (Hermans et al. 2019
and 2021), several coordination geometries of the most
common zinc carboxylates can be detected by FTIR
spectroscopy in the range of 1525–1650 cm−1 (Table 1).
By observing this spectral region, the formation of metal
soaps at an early stage was monitored on the zinc and
copper samples during a period of 30 days (Figure 1). It
can be seen that the evolution over time of the intensity
of the signal of the characteristic νaCOO− vibrational
bands for the copper and zinc carboxylates increased.
Here, it was not possible to distinguish between different
amorphous and crystalline forms of copper and zinc
metal soaps, as only the signal of the general ionomer
structure is visible (Hermans et al. 2016). However, from
the qualitative monitoring using heatmaps, important
REVEALING DEGRADATION PATTERNS: IMAGING TECHNIQUES FOR THE STUDY OF METAL SOAP FORMATION ON PAINTED METAL OBJECTS 171

Table 1. Major asymmetric stretching vibrational bands for the different metal carboxylates and coordination geometries in the range of
1525–1650 cm−1

Zinc Copper Vibrational mode References

Palmitate 1539–1536 s 1586 s
Stearate 1540–1539 s 1586 s
Oleate 1547 vs, 1527 vs 1588–1584 vs Izzo et al. 2021;
Crystalline νas[COO−]
Azelate 1556–1535 vs 1588 vs Hermans et al. 2019 and 2021
Type A 1524 s, 1545 s, 1590 w
2D coordination polymer
Type B 1536 s
Oxo 1590 s
Amorphous νas[COO−] Izzo et al. 2021
Chain 1544 s, 1565 w, 1630 s
vs = very strong signal; s = strong signal; w = weak signal

Figure 2. Copper and zinc coupons coated with linseed oil and respective
analysed regions of interest (a, b). The dashed line separates areas
showing higher (darker, > 10 µm) and lower (lighter, < 10 µm) coating
thickness. The time series of µ-FTIR chemical images are obtained in the
range of 1525–1650 cm−1 after drying over night at 80 °C (c, d), 10 days
(e, f) and 30 days (g, h). Intensity range goes from red (maximum) to
blue (minimum). The scale bar indicates 1000 µm

It must be noted that the detection of metal soaps is also

Figure 1. FTIR spectra for linseed oil-coated (a) copper and (b) zinc
samples in the time intervals considered. The grey area indicates the
vibrational bands related to the metal carboxylates
features were observed (Figure 2): in both substrates
investigated, the intensity of the signal of the metal soaps
increased in the time window considered, confirming
what was observed by inspection of the point spectra.
Additionally, differences in the reactivity of the two
substrates could be highlighted, with zinc having higher
reactivity compared to copper. This can be seen in the
occurrence of red areas in the heatmaps (Figure 2c, 2d),
and it is supported by previous knowledge of the reac-
tivity of the two ions (Greenwood and Earnshaw 1997).
a function of the thickness of the oil, which could impede
their detection when values are higher. For this reason,
the metal soaps have a higher signal in thinner layers of
the coating (Figure 2a, 2b) for both substrates.
Additionally, due to the lack of distinct features on the
coated surfaces, the reproducibility of the selected areas of
analysis was not always achieved when monitoring over
time. In particular, the process of placing the samples
on the stage manually was bound to introduce errors
in consecutive analyses. This can be observed in the
resulting heatmaps.
Hyperspectral imaging
From the analysis of the dataset, it was not possible to
identify spectral features for the presence of metal soaps
in the VNIR and SWIR spectral ranges, since these did
not show characteristic signals in this range of wave-
172  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND TECHNICAL STUDIES

lengths. Nevertheless, from the analysis of the spectra,

relevant observations could be obtained, highlighting
differences in the substrate and coating responses in the
two ranges of wavelengths considered. In particular in
the VNIR spectral range, it was possible to identify the
characteristic reflectance spectra of the copper and zinc
bare metals (Sárosi et al. 2010). As the thickness of the
coating increased, the relative reflectance values, shape
and position of the peaks of the metal support changed.
For the copper substrate, the presence of the coating
influenced the shape of the signal and its intensity, but
it affected its position only marginally (Figure 3).

Figure 4. VNIR HSI analysis of a zinc sample coated with a non-

homogeneous layer of linseed oil. Average relative reflectance spectra
obtained from three 20 × 20 px2 areas for low (1–5 µm), medium (5–10
µm) and high (10–25 µm) coating thicknesses, and respective standard
deviations, are shown

drying oil was observed (Amato et al. 2021), with relative

reflectance values increasing with the thickness of the oil
coating (Figure 5).

The SWIR camera could therefore be a complementary

tool to the VNIR camera and could be employed for a
direct estimation of the thickness of the oil.

Figure 3. VNIR HSI analysis of a copper sample coated with a non-

homogeneous layer of linseed oil. Average relative reflectance spectra
obtained from three 20 × 20 px2 areas for low (1–5 µm), medium (5–10
µm) and high (10–25 µm) coating thicknesses, and respective standard
deviations, are shown

For the zinc, where the colour of the metal is significantly

different from that of the coating, a shift in the main peak
was visible, corresponding to the variation in colour of the
coating from yellowish to reddish (bathochromic shift)
as the thickness increases (Figure 4). This suggests that
VNIR hyperspectral imaging could be used to determine Figure 5. SWIR HSI analysis of the copper sample coated with a non-
the thickness of the oil coating indirectly. homogeneous layer of linseed oil (refer to Figure 3). Average relative
reflectance spectra obtained from the three 20 × 20 px2 areas for low
In the SWIR range, where the oil binder has a strong (1–5 µm), medium (5–10 µm) and high (10–25 µm) coating thicknesses,
signature signal, the characteristic spectrum of the and respective standard deviations, are shown
REVEALING DEGRADATION PATTERNS: IMAGING TECHNIQUES FOR THE STUDY OF METAL SOAP FORMATION ON PAINTED METAL OBJECTS
Conclusion
In this work, the question of whether the selected non-de-
structive imaging analytical techniques – namely µ-FTIR
and HSI – are suitable for the study of metal soaps on
painted metal objects was examined. In particular, the
focus of the work concerned the ability of such analyt-
ical techniques to allow monitoring of the formation of
metal soaps. Micro-FTIR proved to be determinant in
both the detection and the monitoring of metal soaps
on the copper and zinc model samples. In particular, it
was shown that metal soaps can be detected immediately
after the application of the oil coating. The intensity of
the monitored νCOO− vibrational bands corresponding
to the different metal soap forms increased in the time
frame considered. By utilising this technique, the differ-
ences in the reactivity of the two substrates could also
be highlighted.
The detection of metal soaps using HSI cameras in the
VNIR and SWIR spectral ranges was not successful
due to the absence of identifiable spectral features in
these regions. However, this technique raised ques-
tions with regard to the substrates and the thickness
of the oil coating that could be extended to different
applications in the field of cultural heritage, e.g. the
study of unpigmented oil-coated technical objects. For
the purpose of this paper, the focus was on qualitative
monitoring, but this could readily be extended to a full
statistical analysis.
In future research, the mid-wave infrared (MWIR)
range should be explored for the HSI analysis of metal
soaps, as MIR reflectance spectra are reported for these
compounds.
Acknowledgements
The authors would like to thank the team at the Norwe-
gian University of Science and Technology–Norwegian
Colour and Visual Computing Laboratory, particularly
the fellow PhD students Agnese Babini, Jan Cutajar and
Federico Grillini, for offering to acquire the hyperspectral
images when free circulation between countries was not
permitted.
This project has received funding from the Euro-
pean Union’s Horizon 2020 research and innovation
programme under the Marie Skłodowska-Curie grant
agreement No. 813789.
173
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Terenzi, M.G., F. Ferrucci, and M.L. Amadori. 2006.
Dipinti su rame: storia, tecnica, fenomeni di degrado,
diagnostica, indicazioni per la conservazione e il restauro,
2nd ed., coll. Collana i Talenti. Padua: Il Prato.
Authors
Silvia Russo has a BSc in chemistry from Sapienza
University of Rome (Italy, 2015) and an MSc in science
and technologies for the conservation and restoration
of cultural heritage (European Master Programme in
ARCHMAT (2018). She developed her expertise in the
study of metal objects and their degradation processes at
the Soprintendenza Archeologia, Belle Arti e Paesaggio
delle Marche (Italy, 2016), The British Museum (UK,
2017) and the University of L’Aquila (Italy, 2019). She
is currently an MSCA ITN-CHANGE Fellow (ESR11)
working on non-invasive analytical protocols to study
painted metal artefacts and detect early-stage degrada-
tion.
Laura Brambilla has a PhD in chemical sciences from
the Università degli studi di Milano, Italy. Since April
2013, she has been part of the R&D team at HE-Arc CR,
first as a scientific collaborator and then as a professor
from 2017. She is currently leader of various projects
and was one of the organisers of the ICOM-CC Metal
2019 conference.
Jean-Baptiste Thomas received his BSc in applied
physics (2004) and MSc in optics, image and vision
REVEALING DEGRADATION PATTERNS: IMAGING TECHNIQUES FOR THE STUDY OF METAL SOAP FORMATION ON PAINTED METAL OBJECTS 175

(2006) from the Université Jean Monnet in France. He

completed his PhD from the Université de Bourgogne
in 2009. Since 2010, he is been an associate professor at
the Université de Bourgogne. Between 2016 and 2021, he
was on sabbatical at NTNU as a researcher and then as
an associate professor. He has worked extensively on the
development of spectral imaging systems using spectral
filter array technology. Since 2016, he has worked on
understanding material appearance and measuring it by
using imaging systems.

Edith Joseph is an assistant professor at the University

of Neuchâtel and University of Applied Sciences Haute
Ecole Arc Conservation-Restauration in Neuchâtel, Swit-
zerland. She holds a PhD in environmental and heritage
chemistry from the University of Bologna, Italy. Her main
field of research is the application of green chemistry for
the preservation of artistic and archaeological objects. She
has published around 60 papers on analytical chemistry
and conservation science in international journals and
books.
Monitoring of Metal Sculptures and Their Environment in
Art Museums in Sweden
Stavroula Golfomitsou* Mariateresa Pullano
Department of Conservation, University Gothenburg Museum of Art
of Gothenburg Gothenburg, Sweden
Gothenburg, Sweden mariateresa.pullano@kultur.goteborg.se
stavroula.golfomitsou@gu.se
Malin Borin
Elyse Canosa Gothenburg Museum of Art
Swedish National Heritage Board Gothenburg, Sweden
Visby, Sweden Malin.Borin@kultur.goteborg.se
elyse.canosa@raa.se
Abstract
During recent discussions related to carbon emission, there has
been little consideration of how such measures might impact
cultural heritage collections. This paper examines the efforts to
monitor the conditions of selected metal sculptures from Moderna
Museet in Stockholm and the Gothenburg Museum of Art in
Gothenburg, Sweden. The selected sculptures, which included
significant artworks by Picasso, Fautrier, and others, differed in
their surface characteristics and were displayed under different
environmental conditions. Our aim was to link the environment
and microenvironment of these artworks to the condition of the
metal alloys, in order to manage and prevent potential corrosion.
The methods used included pollutant monitoring using passive
Introduction
Artworks made of metal alloys have a prominent place
in many museum collections. In Sweden, those on open
display include works from artists such as Henry Moore,
Degas, Rodin, and Picasso. The corrosion of metal alloys
is often inevitable, even indoors. Metal sculptures are
often displayed along with artworks made of organic
materials that are considered sensitive, and climatic
parameters are adjusted to levels appropriate to these
objects. These choices may adversely impact metals; for
example, higher humidity could increase the corrosion
rate of metallic sculptures. Although a number of studies
have determined the corrosion rates of alloys exposed
outdoors, the long-term effects of indoor environments
have been less well studied.
Sweden has an ambitious strategic plan to achieve zero
net emissions of greenhouse gases by 2045 (Ministry
of the Infrastructure 2020). Implementation includes
an action plan for cultural heritage. Museums should
Eva Nygårds Karin Hermerén
Gothenburg Museum of Art Moderna Museet
Gothenburg, Sweden Stockholm, Sweden
eva.nygards@kultur.goteborg.se k.hermeren@modernamuseet.se
Michaela Florescu *Author for correspondence
Moderna Museet
Stockholm, Sweden
m.florescu@modernamuseet.se
sampling devices and X-ray fluorescence. Elemental analysis
showed the presence of sulfur and chlorine as well as selective
zinc corrosion. Among the detected pollutants was formic acid.
All tools were used noninvasively on site. If these same processes
are used intermittently but consistently over the coming years,
when combined with visual documentation they will shed light
on how display environments change over time and how a
particular environment can impact a collection.
Keywords
pollutants, corrosion, air quality monitoring, contemporary art,
Sweden, X-ray fluorescence (XRF)
actively work to reduce their carbon footprint and the
use of heating, ventilation, and air-conditioning (HVAC)
systems, which can contribute to high greenhouse gas
emissions. Although there is ongoing research to develop
low-carbon emission systems, it may well take years
before museums can afford to replace older systems. The
need to reduce carbon emissions has been addressed by
museum professionals, and conservation can contribute
by allowing greater fluctuations in humidity and temper-
ature (see National Museum Directors’ Council 2014, IIC
and ICOM-CC 2014). However, there is little knowledge
on the tolerance threshold of the materials on display,
and these measures could lead to irreparable damage.
A determination of the impact of local environmental
conditions on Swedish collections becomes paramount
to ensure the longevity of the artworks on display while
working toward developing environmentally sustainable
strategies.
MONITORING OF METAL SCULPTURES AND THEIR ENVIRONMENT IN ART MUSEUMS IN SWEDEN
This paper discusses issues regarding the metal alloy
artworks displayed in two Swedish museums using an
analytical approach to characterize the alloys and their
surrounding environments. The focus is primarily on
the development of a methodology aimed at preventing
corrosion phenomena. As the project is currently in its
early stages, it has concentrated on the choice of artworks
and a characterization of their environment. Analyses of
the alloy composition were prioritized over determina-
tions of the corrosion products and were carried out in
situ. The results, combined with visual documentation,
aided in: (i) identifying synergistic relationships between
metal substrate corrosion and the deterioration of surface
coatings; (ii) linking the object’s history to current
conditions; (iii) correlating atmospheric environmental
conditions to degradation pathways; and (iv) comparing
artworks by the same artists or of similar composition
displayed in different environments. The project will
also provide museums with information about their
ambient environment that will inform future climate
and air-quality decisions.
Study locations
The selected artworks included those made of copper
and iron alloys and displayed under different conditions
in two different museums located in urban-coastal
environments: Moderna Museet in Stockholm and the
Gothenburg Museum of Art in Gothenburg.
Moderna Museet
Moderna Museet is a Swedish government-funded
museum responsible for the national collection of
modern and contemporary art. Opened in 1958, the
museum has one of Europe’s finest and most well-known
collections of 20th- and 21st-century art, comprising
more than 130,000 works in various media, including
some 1,800 sculptures and installations. Originally
dominated by three categories—Swedish and Nordic art,
French-oriented modernism, and American art from the
1950s and 1960s—the collection has been extended to
include key international artworks, in line with current
societal issues.
Moderna Museet’s building dates to 1998 and was reno-
vated in 2004. It is situated on Skeppsholmen, a small
island in the center of Stockholm. Exhibition halls for
the permanent collection cover 2,226 m2, divided into
19 rooms, grouped in three blocks and a corridor and
177
all located on the main entrance floor. The building is
divided into three controlled climatic zones—the exhibi-
tion area, the temporary exhibition space, and the storage
space—with the latter on the lowest floor of the building.
The air-conditioning system is remotely controlled. In
the exhibition area, the relative humidity (RH) varies
yearly between 47 and 53% and the temperature between
18 and 22°C. The maximum 24 h variation in RH and
temperature is ± 3% and ± 2°C. There is currently no
monitoring or control of pollutants.
Metals are present in a variety of forms and representing
all families of alloys, from traditional (ferrous and copper
alloys, lead, silver) to modern (aluminum, stainless
steel, and metallic coatings such as nickel and chrome).
In some artworks, metals are the sole or main material
and in others they have been used in combination with
other inorganic (other metals, concrete, stone, glass,
ceramic) or organic (wood, textiles, synthetic materials,
paints, leather, straw and plant fibers, food) materials.
These composite artworks can be difficult to preserve,
particularly as Moderna Museet encourages a playful and
experimental approach to displaying its art.
Gothenburg Museum of Art
The Gothenburg Museum of Art building was inaugu-
rated in 1923 and was partially extended to gain more
exhibition space in 1968, with a new entrance added
in 1996. The collection includes Western art from the
15th century until today, with an emphasis on Nordic
art. The museum owns a unique collection specialized
in Nordic art from the turn of the 20th century. The
70,000 artworks collection comprises 4,300 paintings, 900
sculptures, installations, and multimedia, around 61,000
works of art on paper, 900 photographs, and some 2,300
children’s book illustrations.
The museum has a history of climate issues. It was built
with poor insulation and included a souterrain construc-
tion that exposes it to extra moisture. In 1996, the new
entrance, connected to the Sculpture Hall by an open
staircase, resulted in higher particle levels.
The climate system was installed in 2008 and includes
separate systems for high-security exhibition rooms and
the collection. Some of the rooms housing the collection
contain north-facing walls and no radiators, while in
others there are south-facing windows and radiators.
For this reason, the climate is kept at level A, with a
178  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND TECHNICAL STUDIES

RH of 50% ± 15% and a temperature that is set to 20°C

but can range from 18°C in winter to 24°C in summer.
In 2008, air filters were installed that currently include
class F9 filters.

The historical climate data are limited, as only single

meters were used. Periodic data show a RH range of
30 to over 70%, with repeated mold issues until 2008.
In the exhibition rooms relevant to this study’s selected
sculptures, there are now fewer humidity issues.

Artworks
The artworks selected for this study are highly important
Figure 2. Jean
to the museums’ collections and their preservation is of
Fautrier, La
particular concern. Grandetete,
1943, 33 cm,
Moderna Museet patinated copper
 alloy, wood
The selected objects include a group of cast bronze sculp-
tures from Pablo Picasso (Femme aux bras croisés, 1948;
Nu, 1945; Femme debout, 1948; Le Bras, 1959) (Figure 1),
Jean Fautrier (La Grande Tête, 1943) (Figures 2, 3), and
Germaine Richier (L’Hydre, 1954). Additionally, analysis
and observations were performed on a steel and stainless
steel sculpture by a young Swedish artist, Hanny Kamali
(Freddie Gray, 2019) (Figures 4, 5).

The cast bronze sculptures are in one of the exhibition

rooms while the steel and stainless steel sculpture is

Figure 3. Jean Fautrier, La Grandetete, detail of a regularly monitored

area

Figure 1. Pablo Figure 4. Hanni

Picasso, Le Kamaly, Freddie
Bras, 1959, Gray, 2016–2018,
58 × 18 × 16 cm, 235 × 170 × 190 cm,
patinated copper steel and stainless
 alloy  steel
MONITORING OF METAL SCULPTURES AND THEIR ENVIRONMENT IN ART MUSEUMS IN SWEDEN 179

Figure 6. Pablo Picasso, Madame Fernande Olivier, 1906, 35.7 × 24.8 ×

Figure 5. Hanni
24.4 cm, panitated copper alloy
Kamaly, Freddie
Gray, detail of a
 corroded area

displayed in the corridor leading to the exhibition rooms.

This corridor is exposed to a high level of visitor traffic
and is close to the main museum entrance. The sculptures
are dusted regularly.

Gothenburg Museum of Art

The two bronze sculptures analyzed were Pablo Picasso’s
Madame Fernande Olivier (Figure 6), acquired in 1951,
and Marino Marini’s Rider, acquired in 1952 (Figure 7).
With a combination of distinct facial features and a more
unfinished and abstract part, Picasso’s Madame Fernande
Olivier foreshadows an important shift in the artist’s
oeuvre, from his Rose Period (1904–1906) to his Cubist
phase. The sculpture dates from 1906 and was made after
the Gósol period, but it is uncertain when it was cast.
The sculpture is likely one of the early sets of casts signed
by the artist. Subsequent unsigned casts were made in
1959. In the acquisition record, the sculpture is described
as bronze, with a dark-brown patina. Picasso used gauze
or net in the still wet plaster to achieve the porous texture
in the metal surface.
The Italian sculptor Marino Marini, one of modernism’s
foreground figures, referenced Etruscan heritage and
classic art in his works. Rider, from 1945, was made in
connection with his time spent in Switzerland and was
inspired by a 13th-century equestrian sculpture in the
cathedral of Bamberg, Bavaria. The monumental form
in combination with the treatment of the surface, using
scratches, chisels, and crayons, gives the sculpture a
timeless appearance that seems to refer to archaeo-
logical antique finds. In Basel’s National-Zeitung, an
Figure 7. Marino Marini, Rider, 1952, 108 × 96 × 37 cm, copper alloy
article described Marini’s working methods as casting
and molding at the same time, reworking the raw cast
with sculptor’s tools and color, and then using plaster
techniques, bringing the opaque, neutral, white mass
seemingly to life. The result is an immediate and tension-
filled effect that makes a deep impression on the viewer
(Kuhn 1944). These details are reflected in Rider, the
surface of which has traces of the sand from the casting
and hints of gold, blue, and red.
Both sculptures have been on permanent display for
almost 70 years, Rider in the Sculpture Hall, located at
the top of the staircase, where levels of particulates are
high, and Madame Fernande Olivier in the French Gallery
on the 6th floor, where the environment is more stable.
Methods
The composition and condition of the sculptures were
investigated using visual observation and X-ray fluo-
rescence (XRF). Pollutant levels were measured in two
different areas of each museum, each of which contains
at least one of the sculptures discussed. The areas were
180  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
selected because their displayed objects have suffered
corrosion or due to their corrosion potential. At Moderna
Museet, air quality was measured in the corridor leading
to the exhibition rooms (containing Hanny Kamali’s
Freddie Gray) and in the exhibition room containing the
Picasso, Fautrier, and Richier sculptures. The corridor
is near the main entrance of the building while the
exhibition room is shielded by walls. At the Gothenburg
Museum of Art, air quality was measured in the Sculp-
ture Hall containing Marini’s Rider and in the French
Gallery on the 6th floor. It should be noted that yearly
visitor traffic is higher in Moderna Museet than in the
Gothenburg Museum of Art.
Pollutant monitoring
The intermittent monitoring of pollutants allows a
better understanding of the microenvironments in these
museums. Monitoring has thus far been performed using
passive sampling devices from the Swedish Environ-
mental Research Institute (IVL). The devices are compact
plastic cylinders approximately 3 cm in diameter and
1 cm thick and containing adsorbent materials. They
require no pumps and allow for the diffusive capture
of pollutants through a mesh on the top of the device.
As they are quiet, small, and unobtrusive, these passive
sampling devices are ideal for museum environments.
Their exposure times can last between a few hours and
several weeks. Longer exposure times allow for lower
limits of detection, which is necessary for cultural
heritage environments, where low levels of pollutants
over time can cause collection damage. The samplers
used in this study collect acid gases, namely acetic acid
(CH3COOH), formic acid (HCOOH), sulfur dioxide
(SO2), and hydrochloric acid (HCl), and were exposed
for 4 weeks (8 September–7 October 2021, at the Goth-
enburg Museum of Art; 18 October–3 November 2021,
at Moderna Museet). The samplers were either placed
directly on a flat surface (e.g., ground, platform) with
the mesh facing up or were adhered vertically to a wall
using putty. After exposure, the samplers were returned
to the IVL for analysis using ion chromatography. The
detection limits for each measured pollutant over a
4-week exposure time are given in Table 1.
Compositional analysis of the artworks (XRF)
The elemental composition of the selected sculptures was
determined using XRF, which provided information on
TECHNICAL STUDIES
Table 1. Detection limits of pollutants measured by passive sampling
devices
Pollutant Detection limit (μg/m3)
CH3COOH 1.0
HCOOH 1.0
SO2 0.2
HCl 0.3
both the original materials used to create each sculpture
and the identification of possible corrosion products
resulting from atmospheric pollutant exposure. The
XRF device consisted of an XG Elio portable, noncon-
tact XRF spectrometer with a rhodium tube. For each
measurement, a voltage of 40 keV, a current of 20 μA, and
a measurement time of 40 s were applied. The head of
the spectrometer was placed close to the surface and the
measurement was made with the aid of alignment lasers.
The medium between the object and XRF head was air
(no light detection element was possible). At least five
different points were measured on each sculpture, with
each point measured in duplicate or triplicate.
Results
Climate in Stockholm and Gothenburg
Climate data were collected by the authors from the
Stockholms Luft- och Bulleranalys (SLB) (www.slb.nu/
slbanalys/) for Stockholm and the Swedish Meteorolog-
ical and Hydrological Institute (SMHI) (www.smhi.se/q/
Stockholm/2673730) for Gothenburg. The climate in
both cities is considered mild. Average winter temper-
atures annually vary from −14 to 5°C (coldest month:
February) and average summer temperatures from 6 to
19°C (hottest month: August). It rains year-round but the
intensity and the amount vary, with May and September
as the wettest months and April as the driest month. The
largest deviation occurs during the winter, although in
some years a large deviation can also occur in summer.
The average RH is very high, averaging between 60 and
85%, with lower levels in the summer but with greater
fluctuations.
Both Stockholm and Gothenburg are port cities and
therefore receive a large volume of shipping traffic. Based
on pollutant data collected from a weather station near
the Gothenburg Museum of Art for the past 10 years,
average nitrogen dioxide (NO2) levels in this area, with
the exception of 2020, were 30.9 ± 6.6 μg/m3, which is
higher than the suggested concentration range for general
MONITORING OF METAL SCULPTURES AND THEIR ENVIRONMENT IN ART MUSEUMS IN SWEDEN
cultural heritage collections of 3.8–19.1 μg/m3 (Grzywacz
2006). In 2020, because of the COVID pandemic, the
levels declined to an average of 17.94 μg/m3. Outdoor
annual PM10 levels have been relatively constant, even in
2020, with an average of 18.9 ± 2.3 μg/m3 (SMHI 2021).
According to data from the past 10 years, NO2 levels
in Stockholm have fluctuated, with annual averages of
12 ± 11 μg/m3 (SMHI 2021, SLB 2021). Concentrations
are highest in February and March (highest measured
value: 113 μg/m3) and lowest during the summer months
(lowest measured value: below sensor detection levels).
Conversely, ozone concentrations are highest between
May and August (highest measured value: 145 μg/m3) and
lowest during the winter months (lowest measured value
0.2 μg/m3), with a 10-year average of 51.4 ± 19.5 μg/m3.
Average SO2 levels in both cities over the last 10 years
have been low (0.4–1.5, with a winter average maximum
of 2.9 μg/m3). However, SO2 levels have been steadily
declining, with a dramatic decrease over the last 30 years
due to environmental regulations, good public transport,
and the widespread use of bicycles. This is consistent
with many European and North and South American
countries, where SO2 levels have similarly decreased
since the 1970s (Klimont et al. 2013).
Indoor air quality
Data from the IVL passive samplers exposed for 4 weeks
showed that the indoor concentrations of SO2, acetic
acid, and HCl were below the instrument’s detection
limits. While the levels of formic acid were detectable,
they were still below the suggested ranges for sensitive
cultural heritage collections (Table 2). In general, the
indoor air quality measured between 8 September and
7 October 2021 was good. However, the passive sampling
Table 2. Pollutants measured by passive sampling devices at the
Gothenburg Museum of Art, 9 September–7 October 2021. All values
are in μg/m3
Suggested Suggested
Compound GBG GBG range for range for
measured location 1 location 2 sensitive general
collectionsA collectionsA
SO2
< 0.2 < 0.2 0.11–1.1 1.1–5.3
HCOOH 6.4 6.4 < 9.6 9.6–38.2
CH COOH
3
<1.0 < 1.0 < 12.5 99.6–697.2
HCl < 0.3 < 0.3 NA NA
A: Data from Grzywacz (2006), converted from ppb to μg/m3
NA: Not applicable, no current data found in the literature
181
devices placed in Moderna Museet were, unfortunately,
unexpectedly removed during the original measurement
period and were not recovered. New samplers were placed
on 18 October 2021, but the data could not be analyzed
in time for this publication.
Thus, as a comparison, in 2019 Canosa and Norrehed
(2019) measured indoor pollutants at the Nationalmu-
seum, located near Moderna Museet. These measure-
ments, performed during a period of renovation (between
18 January and 15 February 2019), showed indoor
average values of < 0.2 μg/m3 for SO2, 14.7–42.3 μg/m3
for acetic acid, 28.4–36.2 μg/m3 for formic acid, and
< 1.0–1.5 μg/m3 for ozone. The high concentrations may
have been the result of the renovation environment and
the use of fresh construction and decoration materials
that were off-gassing.
X-ray fluorescence
Figures 8 and 9 show representative spectra of each
artwork. All of the artworks are composed of bronze
(evidenced by the presence of copper and low amounts
of tin) containing zinc and iron. Additionally, all objects
were determined to contain low amounts of copper
corrosion products, based on the presence of sulfur and
chlorine peaks. Traces of chromium were detected in the
Richier sculpture (MR), Fautrier sculpture (MF), and
Moderna Museet Picasso sculpture (MP), and traces of
nickel, silicon, and potentially titanium in the leaded
bronze sculpture by Marini (GM). Unlabeled peaks are
Figure 8. XRF spectra of the analyzed sculptures. MR: Moderna Museet,
Richier; MF: Moderna Museet, Fautrier; MP: Moderna Museet, Picasso;
GP: Gothenburg Museum of Art, Picasso; GM: Gothenburg Museum of
Art, Marini
182  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Figure 9. Details of the XRF peaks observed in the spectra from Figure
8. The left side shows the peaks found in the energy range of 1.5–8 keV
and the tin Ka peak at 22–28 keV
from the rhodium target in the XRF or from argon in
the surrounding atmosphere.
The XRF spectra from three different measurement
points on the Marini sculpture at the Gothenburg
Museum of Art are shown in Figure 10. According to
the spectra, areas showing white surface accretions
contain increased relative amounts of zinc, tin, and iron,
indicative of the selective corrosion of zinc (i.e., dezinci-
fication). Additionally, the XRF spectra for the Kamali
sculpture at Moderna Museet showed the presence of two
different iron alloys: a galvanized stainless steel threaded
rod bar that is attached to a body of plain steel (Figure 5).
Figure 10. XRF of different areas of Marino Marini’s Rider. (A) left hip of
the horse, dark green patina; (B) left side of the human torso; (C) left side
of the human torso in an area with significant white accretions
Discussion
Different surface finishes during a sculpture’s manufac-
ture may result in different corrosion rates. Conserva-
tion also impacts corrosion, but sufficient information
regarding previous treatments of the studied objects is
TECHNICAL STUDIES
lacking. Each artwork displays different patinas, ranging
from uniform, highly polished, and homogeneous to
non-uniform and rough, due partially to their manufac-
turing and finishes and partly to the selective corrosion
that has developed over their lifetime.
Corrosion rates are often linked to the type and level
of pollutants as well as to temperature and humidity.
Copper- and iron-based alloys are susceptible to corro-
sion under conditions such as those found in both
Moderna Museet and the Gothenburg Museum of Art.
The high levels and wide fluctuations of humidity in
combination with NO2, SO2, O3, HCl, Cl2, reduced sulfur
compounds, and organic acids could result in increased
rates of corrosion (Leygraf et al. 2016, 87). Therefore,
the monitoring of environmental parameters, such as
those discussed here, can help conservators determine
whether action should be taken to prevent corrosion.
The cost of monitoring pollutants is lower than that
of conservation treatments, and intermittent meas-
urements may suffice. As conservation moves towards
preventive measures, pollutant monitoring could be a
significant step in this direction. As demonstrated by
the sculptures included in this study, leaded bronzes
such as used in the Marino Marini sculpture can
corrode in the presence of organic acid gases, including
those of acetic acid and formic acid (Grzywacz and
Tennent 1994, Tétreault et al. 2003, Grzywacz 2006).
Copper alloys can corrode in the presence of common
atmospheric gases, especially sulfur dioxide and chlo-
rine-containing compounds (e.g., HCl and Cl2) (Rice
et al. 1981), both of which will be high given the prox-
imity of both museums to the sea and to port traffic.
While the pollutant concentrations measured in this
first monitoring campaign were lower than suggested
for sensitive collections (see Table 2), they may fluc-
tuate, both seasonally and over time. Additionally, the
environmental data collected (SLB 2021, SMHI 2021)
showed a significant decrease in pollutants during the
pandemic. Therefore, future measurement campaigns
will be performed.
COVID reduced the exposure of the air quality samplers,
as a number of museums in Sweden remained closed for a
significant period of time and, once opened, their visitor
numbers were much lower. Exposure levels increased
once the museums were back to relative normalcy, with
the first samplers exposed in September, albeit before
governmental restrictions were lifted (on 29 September
MONITORING OF METAL SCULPTURES AND THEIR ENVIRONMENT IN ART MUSEUMS IN SWEDEN
2021). The next set of samplers will be placed in late
December and then in the spring and summer.
In the next steps of the project, high-definition photo-
graphs of the selected areas will be made under consistent
lighting conditions. Fourier transform infrared (FTIR)
spectroscopy using contactless nondestructive reflection
will be employed in situ to detect traces of varnish or
wax used in the past. Other analytical methods, such
as Raman spectroscopy, could be used to determine the
composition of newly formed corrosion products (espe-
cially those representing active corrosion).
Conclusion
As museums align with wider environmental goals and
conservation treatments become less frequent than in the
past, measures aimed at preventing corrosion become
essential tools in the conservation of metal sculptures.
Environmental monitoring, including the monitoring of
humidity, temperature, and pollutants, can be a signifi-
cant indicator of potential corrosion and other forms of
deterioration. Related areas of research include descrip-
tors based on high-definition imaging. Most museums
monitor RH and temperature but not pollutants. This
project explores practicable methods and novel, low-cost
tools, such as passive samplers, to develop protocols for
monitoring artworks vulnerable to corrosion and other
forms of environmental damage.
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decade of global anthropogenic sulfur dioxide: 2000–2011
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Kunstmuseum. National-Zeitung 12, December 1944.
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Graedel. 2016. Atmospheric corrosion, 2nd ed. Hoboken,
NJ: John Wiley & Sons.
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Integrated National Energy and Climate Plan. https://
ec.europa.eu/energy/sites/ener/files/documents/se_
final_necp_main_en.pdf (accessed 15 October 2021).
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Environmental sustainability – Reducing museums’ carbon
footprint. Bizot Green Protocol. Available at www.national-
museums.org.uk/what-we-do/contributing-sector/
environmental-conditions/ (accessed 10 October 2021).
Rice, D.W., P. Peterson, E.B. Rigby, P.B.P. Phipps, R.J.
Cappell, and R. Tremoureux. 1981. Atmospheric corro-
sion of copper and silver. Journal of The Electrochemical
Society 128(2): 275–84.
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slb.nu/slbanalys/ (accessed 1 October 2021).
Swedish Meteorological and Hydrological Insti-
t u t e ( S M H I ) . 2 0 2 1 . w w w. s m h i . s e / q / S t o c k -
holm/2673730 (accessed 1 October 2021).
Tétreault, J.,  E. Cano, M. van Bommel, D.A. Scott,
M. Dennis, M.-G. Barthés-Labrousse, L. Minel, and
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sic.2003.48.4.237
Authors
Stavroula Golfomitsou (BA, PhD, FIIC) is senior
lecturer at the Department of Conservation, University
of Gothenburg, Sweden. Previously, she was a lecturer in
conservation studies at UCL Qatar, where she set up and
coordinated the MSc program in Conservation Studies.
Discovery of a 12th-Century Enamelled Reliquary Pendant:
Elemental Analysis and Content Visualisation Using Prompt
Gamma Neutron Activation Analysis and Neutron Tomography
Matthias Heinzel* Eschly Kluge
Leibniz Research Institute Institute for Nuclear Physics (IKP),
for Archaeology, Römisch- University of Cologne
Germanisches Zentralmuseum Köln, Germany
Mainz (RGZM) ekluge@ikp.uni-koeln.de
Mainz, Germany www.ikp.uni-koeln.de/
matthias.heinzel@rgzm.de
https://web.rgzm.de/ Dorothee Kemper
German Society for Studies in Art
History
Berlin, Germany
dorothee.kemper@gmx.net
www.dvfk-berlin.de
Abstract
In October 2008, a heavily corroded pendant was found during
an excavation campaign in the historic district of Mainz,
Germany, in an ancient dump. The reliquary pendant, made
of gilded copper, is in the shape of a quatrefoil, also referred
to as a phylacterion, and dates from the late 12th century.
Its front and verso were enamelled using the technique of
émail champlevé and its several compartments include figural
representations. The side section is also gilded and enamelled
with cross-hatched decoration. Two different techniques were
applied in the analysis of the pendant’s surface. An elemental
analysis was done using micro-X-ray fluorescence, and the glass
and pigments of the enamels were investigated using Raman
spectroscopy. The carbonaceous content of five reliquary
packages became visible after neutron imaging, performed
at the Research Neutron Source Heinz Maier-Leibnitz
(FRM II), Technical University of Munich in Garching, Germany.
A combination of a position-sensitive prompt gamma-ray
neutron activation analysis and neutron tomography was used
to reveal the reliquary’s internal structures and contents. The
Introduction
A heavily corroded reliquary pendant was found at an
ancient dump in October 2008, in the historic district
of Mainz, Germany. The dump was rectangular, approx-
imately 3 × 3 m in size, and had been backfilled in the
mid-14th century. The pendant was already relatively
old before it ended up in the dump, where it stayed for
over 600 years.
The interdisciplinary analysis of the pendant included
art-historical, material-scientific and manufacturing
perspectives aimed at reconstructing the pendant’s manu-
Burkhard Schillinger Christian Stieghorst
Heinz Maier-Leibnitz Zentrum Heinz Maier-Leibnitz Zentrum
(MLZ), Technical University of (MLZ), Technical University of
Munich (TUM) Munich (TUM)
Garching, Germany Garching, Germany
burkhard.schillinger@frm2.tum.de christian.stieghorst@frm2.tum.de
https://mlz-garching.de/ https://mlz-garching.de/
*Author for correspondence
latter consisted of small packages of tiny particles of bone
covered by textile and wrapped with a thin thread to keep
them together. Neutron imaging allowed exact measurements
of the textiles and bones. The construction of the container
and especially the closure mechanism were also clearly visible.
With the aid of infrared spectroscopy, a small sample of wax
was identified as beeswax. The analysis of a small fragment of
fibre which had survived in the pendant’s suspension eyelet
revealed that it was made of silk. This object is one of only
four known phylacteria of this type from the late 12th- and
early 13th-century Hildesheim workshop in Lower Saxony.
The other three are housed in Boston, Rome and Halberstadt.
This reliquary pendant is a rare example of an object found in
context from controlled archaeological excavations.
Keywords
reliquary, phylacterion, neutron imaging, prompt gamma-ray
neutron activation imaging (PGAI), (micro-X-ray fluorescence)
μ-XRF, émail champlevé, Hildesheim
Figure 1. Pendant before its restoration and radiography of its side
and front (photograph by Matthias Heinzel, radiographs by Stephan
Patscher, RGZM)
DISCOVERY OF A 12TH-CENTURY ENAMELLED RELIQUARY PENDANT: ELEMENTAL ANALYSIS AND CONTENT VISUALISATION 185

facture, the composition of its enamels, the iconography

and the possible origin. Neutron tomography in combi-
nation with position-sensitive prompt gamma neutron
activation imaging (PGAI-NT) was applied to the object
for elemental analysis and content visualisation.

Condition and conservation treatment

The pendant was covered with a 3- to 5-mm-thick layer of
green and blue copper corrosion products with embedded
soil constituents. An initial radiograph of the pendant
performed at the Leibniz Research Institute for Archae-
ology (RGZM) revealed the exact shape of the quatrefoil
and several figural representations (Figure 1). The copper Figure 2. Digital microscopy: one of the five fibre fragments from the
eyelet, as seen at 200× magnification (by Matthias Heinzel with a
corrosion products were removed mechanically using Keyence VHX-6000 digital microscope)
diamond-tipped grinding tools and fine mechanical instru-
ments. During this process, the original enamel and gilded
copper surface were uncovered. As the entire base material
was already heavily mineralised, the gilding had detached
from the base metal in many areas or lay exposed on top.

In addition, some areas of the enamel were chipped

or brittle and the entire object was relatively unstable.
During the restoration process, conducted in 2009 in
the workshop of the Directorate of State Archaeology in
Mainz, exposed areas were stabilised with epoxy resin
(Araldite 20/20) to avoid a loss of substance. The epoxy
resin was of high transparency, with extensive non-yel-
lowing properties, high adhesive strength, and the same
light refraction as glass. Due to its low viscosity, it is very
well suited for infiltration bonding. At the time of the
restoration, 13 years ago, it was one of the best avail-
able options and thus far no change is discernible. The
stabilisation had no influence on any of the subsequent
analytical methods. During the discovery, a cord-like
fragment of fibre was found inside the pendant’s suspen-
sion eyelet. The surrounding copper corrosion products
preserved this fragment, due to their biocidal effect. This
1.5-mm-long fragment could not be preserved in situ and
was separately packaged for further analysis (Figure 2).
After its restoration, the pendant had the following
dimensions: length 67 mm (with bail), 57 mm without
bail; width 57 mm, and thickness 11–12 mm. The
suspension is ~10 mm in diameter. The object’s total
mass is 70.5 g. Conservation work on the pendant
required ~500 hours in total. The restored pendant was
kept in storage at the Directorate of State Archaeology
in Mainz until the end of 2016, when the first author
started a new job at the RGZM. In 2017, research on
Figure 3. Front, side and verso of the pendant after restoration
(photographs by Sabine Steidl, RGZM)
the pendant began when it was shown to art historian
Dr Dorothee Kemper during a conference in Hildesheim
on the famous Welandus or Henry reliquary from the
Louvre in Paris. She immediately recognised the special
nature of the Mainz reliquary pendant and encouraged
further exploration.
Description
The rare pendant, also known as a phylacterion, is quat-
refoil shaped with a central square (Kemper 2020). It is
made of gilded copper. An eyelet is visible at the top,
suggesting that the object was worn around the neck on
a ribbon or chain. This object consists of a container and
a closure which are held together by a visible rivet. The
front and verso were enamelled using the technique of
émail champlevé and are decorated with several figural
representations (Figure 3). All figures carry a nimbus
and are raised from the background, engraved and
gilded. The background fields, the halos, the frame of
the central field and the internal drawings of the figures
are enamelled. The colour spectrum of the enamelled
186  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
areas is very narrow and varies on the front and verso.
The square field on the front is green and framed by blue
semicircles, with the halo of the central figure being blue
and the halos of the surrounding representations being
white. On the back side, the colours are reversed: the
square field is blue and the semicircle fields are turquoise
green, whereby the halo of the central figure is white and
the halos of the surrounding figures are blue.
The representations in the upper semicircle segment of
both sides, where the riveting of the two components is
located, were constructed with the placement of the rivet
having been taken into account, such that the figures on
the front and verso tilt their heads to the right to make
room for the rivet. The side section of the pendant is
cross-hatched, except the closure. The lozenges are gilded
and the lines are enamelled.
Optical examination
High-resolution digital photos were taken for documen-
tation and further research. The cord-like fragment,
consisting of five thread fragments, from the area of
the suspension eyelet was examined in photos obtained
using a Keyence digital microscope with reflected and
transmitted light. During the restoration process, a soft,
waxy substance was discovered on the side containing a
representation of Mary, in the upper semicircle segment
with the rivet. In this area, where the closure is also
located, the surface of the pendant is heavily damaged,
most likely due to the strong degradation that occurred
during its time in the ground. A sample of this waxy
substance was taken for analysis.
Transmitted light microscopy of the fibre sample revealed
the fibre to be silk. The cord consisted of at least five
strands of thread, each of them z-twisted. It is the first
evidence of material on which such pendants were most
likely carried.
Technological studies
A radiograph (front and side) was made to gain insights
into the construction of the pendant. Non-destructive
and non-invasive methods, specifically, micro-X-ray
fluorescence (μ-XRF) and Raman spectroscopy, were
combined to obtain information on the composition of
the metals and enamels (type of glass, colourants and
opacifiers). The waxy substance was investigated by
infrared spectroscopy (FTIR).
TECHNICAL STUDIES
Results of the μ-XRF (in weight %)
• Substrate metal is copper: Cu 99.2%/Pb 0.4%/
Ag 0.2%/Sn 0.2%
• Gilding was applied using fire gilding: approx.
Au 83%/Hg 17%
The pendant consists of pure copper, with only traces of
other elements, most likely reflecting impurities from
the ore that was used. Fire gilding was evidenced by the
high content of mercury.
There are four different opaque enamel colours on this
object: white, blue, green and turquoise green. Due to
its fragility, the enamel was measured under normal
atmosphere and not in a vacuum, as is usual for glass
and enamel. Thus, a quantitative determination of the
glass composition was not possible, although it can be
concluded that all colours were made from soda glass
and the green glass is a leaded glass.
The other three enamel colours contain lead, with a
few percent of lead oxide. Calcium antimonate was the
opacifying agent in the opaque enamels (white, blue and
turquoise). The antimony content of the green glass is
too low to have created opaque enamel. The colours
of the enamels were derived as follows: blue by copper
and cobalt, green by copper and lead, and turquoise by
copper. The turquoise enamel also contains tin and zinc.
Presumably, a bronze alloy that was on hand was added
here instead of pure copper, a common procedure and
indicative that the goldsmith used what he had at hand.
Results of FTIR of the waxy substance
Infrared spectroscopy clearly identified the waxy
substance as beeswax (Figure 4).
Figure 4. FTIR spectra of beeswax (top) and a sample of the waxy
substance from the reliquary pendant
DISCOVERY OF A 12TH-CENTURY ENAMELLED RELIQUARY PENDANT: ELEMENTAL ANALYSIS AND CONTENT VISUALISATION
The construction of the quatrefoil pendant suggested that
it contained relics, but these were not initially visible on
the X-rays taken at the RGZM. In X-ray images, organic
and inorganic materials, such as textiles and bones, are
optically ‘outshone’ by the surrounding metal and enamel
and are thus not recognisable.
For X-ray-complementary, non-destructive structural
and elemental analyses, the reliquary was investigated
at the research reactor FRM-II of the Heinz Maier-Lei-
bnitz Institute of the Technical University of Munich at
Garching, using NT of different spatial resolution and
PS-PGAA. The absorption behaviour of neutrons is
nearly opposite of that of X-rays. Free of electrical charge,
neutrons penetrate deeper into matter, specifically metals.
Conversely, their stronger absorption by hydrogen results
in a high imaging contrast in biological material. NT was
used to specifically visualise the structure of the organic
content and allowed the identification of five distinctive
packages (Figure 5). The investigation methods have
no implications for possible carbon dating and DNA
extraction. However, the latter are not possible because
the reliquary pendant cannot be opened without causing
its destruction.
In general, reliquary packages of the Middle Ages
consisted of bone fragments wrapped in linen or silk.
In most cases these fragments were claimed to have
Figure 5. Neutron tomography of the pendant with its five reliquary
packages
187
stemmed from worshiped saints. To secure the fragments
within the textile, thin threads were wrapped around the
woven textile wraps. Some packets were more sack-like,
with one thread closing it on top. Usually, such packages
were labelled with the specific saint’s name, written on
attached parchment strips known as authentic or cedula.
However, in the present case, no signs of parchment strips
were seen on the NT images. It cannot be ruled out that,
after being buried for more than 600 years, any parch-
ments underwent either partial or complete decay. Since
the reliquary’s riveting is strong and tight, the subsequent
removal of the strips is unlikely, as opening the reliquary
would have required great force, of which there are no
signs. It may be that a list of the reliquaries contained in
this pendant was stored separately.
With the aid of NT and the highly valued interpreta-
tions of the reconstructions, the structural properties
of the reliquaries could be determined in detail. For
specimens showing high grey-value contrasts, it was
possible to measure the thread spacing or density, with
a mean square error of ± 0.3 threads. Since the wrapped
reliquaries were stuffed into the pendant from the top,
most of their fabric is heavily warped. Thus, many threads
within the observable fabric parts were either extremely
stretched apart or compressed, which in some specimens
hindered determinations of the horizontal and vertical
thread densities (Figure 6).
Figure 6. Detailed structures of the reliquary packages (textile and
splinters) as seen on a NT-slice
188  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND TECHNICAL STUDIES

Details of the five reliquary packages along the vertical
symmetry axis of the pendant from top to bottom include
the following:
1. Packaging: a very fine, loosely lying outer textile
(vertical and horizontal thread spacing of 0.33 mm
and 0.26 mm; vertical and horizontal thread densi-
ties of 30/cm and 39/cm), with an estimated spatial
volume of ~2 cm3, encloses a relatively tight-fitting
and coarsely threaded textile, whose nominal thread
characteristics could not be determined. Contents:
an irregular tetrahedral-like splinter with maximum
dimensions of 7.2 × 5.3 × 5.1 mm.
The thinly threaded, denser textile of bags 1, 2, 3 and 5 is
most likely silk, and the thicker, less dense textile of bag
4 and within bag 1 is probably linen. In the NT recon-
structions, all structural components of the pendant were
clearly visualised. This allowed the complex construction
of the closure (later shown to be opaque to X-rays) to
be investigated in detail. The chiselled immersions of
the émail champlevé were clearly visible in the NT slices
(Figure 7).

2. Packaging: a loosely packed thinner textile (vertical

and horizontal thread spacing of 0.35 mm and
0.30 mm; vertical and horizontal thread density of
29/cm and 33.9/cm) with an estimated volume of
~6 cm3. Contents: two fragment plates which appear
to be of bone cortex and adjacent bone sponge tissue.
Maximum dimensions: one is 15 × 8.8 × 8.6 mm, and
the other 2.77 × 1.8 × 2.4 mm.

3. Packaging: loose bundle of fine textile (thread

spacing of ~0.34 mm or 39.5 threads per cm)
with an estimated volume of 2 cm3. The bundle is
wrapped with a single string. Contents: four small
Figure 7. Chiselled and engraved immersions of the émail champlevé
plates within the upper part. Maximum dimen- seen on the cross-sectional NT-slice
sions: 1. 10.8 × 1.0 × 7.0 mm; 2. 4.6 × 0.7 × 1.8 mm;
3. 2.6 × 0.5 × 1.0 mm; 4. 3.4 × 0.8 × 2.7 mm. The elemental compositions were determined using
PS-PGAA, in which two depth layers with 14 measure-
4. Packaging: tightly folded, thick textile (vertical and
ment positions each and an additional inter-layer and
horizontal thread spacing of 0.4 mm or 25 threads per
inter-row position at the object’s closure were analysed
cm) wrapped with a string. Estimated volume: ~3 cm3.
(Figure 8). The chosen rasterization covered all reliquary
Contents: some small and many very tiny fragments.
bags, with a total of 21 measurement positions (along the
Maximum dimensions of the most prominent frag-
pendant’s vertical axis): eight other measurements served
ments: 1. 2.2 × 0.9 × 2.5 mm; 2. 3.1 × 0.8 × 1.8 mm;
as the lateral reference. PGAI-NT is the combination of
3. 2.6 × 1.1 × 1.8 mm.
PS-PGAA imaging and NT.
5. Packaging: loosely packed bag of thinner textile
The PGAA results tensor is visualised in three dimen-
(thread spacing ~0.34 mm or 29.5/cm thread density)
sions via voxels embedded in the reconstructed object
and an estimated volume of ~4 cm3. Contents: two to
three crossed fragment plates. Maximum dimensions:
1. 4.0 × 0.6 × 5.0 mm; 2. 2.3 × 1.2 × 7.4 mm. Three to
four objects other than bone fragments are unevenly
distributed within the bag. Compared to the observed
bone fragments, those objects are highly homoge-
neous, spherically symmetrical, with much smoother
surfaces and a mean diameter of ~1.3 mm. Their grey
values, however, are identical to that of the bone frag-
ments. Their nature and material remain unknown. Figure 8. Reliquary PGAI-NT positions with 29 measurement points
DISCOVERY OF A 12TH-CENTURY ENAMELLED RELIQUARY PENDANT: ELEMENTAL ANALYSIS AND CONTENT VISUALISATION
volume on NT. The different elements are represented by
means of different colours and their relative abundance
is encoded via different colour intensities (Explanatory
notes: E. Kluge et al., www.ati.ac.at/~saagas26/css/files/
SAAGAS_26_paper_22.pdf, accessed 30 June 2020) . In
the analysis of the pendant, the elemental composition
of six positions was noteworthy. Compared to the refer-
ence positions and surface materials, these positions
contained significant amounts of hydrogen, calcium and
potassium. Manganese and iron were also found at a few
points (Figure 9).
Figure 9. PGAI-NT of the elements calcium, hydrogen, potassium/iron
and oxygen (from left to right)
The additional hydrogen content along the vertical axis
supported the presence of biological material. The rela-
tively high hydrogen content at the closure fits well with
the identified beeswax within this area. The increased
calcium content along the vertical axis together with
the amounts of hydrogen found was a strong elemental
indication of the presence of bone material. Some of the
hydrogen may have stemmed from the textiles. Based
on the structural and elemental analyses obtained with
PGAI-NT, it is extremely likely that the objects within
bags 2, 4 and 5 are indeed biological bone material. The
plate in package 2 is also likely to be bone, based on
the visually prominent sponge structures in the cortex
tissue. As the same certainty cannot be applied to the
contents of bags 1 and 3, these objects were labelled
simply as fragments. In the analysis of the components
of the pendant’s frontal and verso plates, the results of
the PGAA coincided, as expected, with those of X-ray
fluorescence spectroscopy.
Manufacturing technique
The pendant consists of a bottom and a top sheet
of copper, each ~1.5–2.4 mm thick. The frame is
made of four equally sized circle segments, formed
of ~1.9-mm-thick and 8-mm-wide copper sheets. A
rhombic copper peg is located in the intersections of each
petal and forms the corners of the central square frame.
All of these components are soldered together, forming
the quatrefoil shape (Figure 10).
189
Figure 10. Exploded drawing of the construction components (drawing
by Vera Kassühlke, RGZM)
The closure was made separately and consists of a
rectangular, ~10-mm-long frame made by bending a
1.1-mm-thick copper sheet. The frame was then firmly
soldered to a lid made from an ~1.6-mm-thick copper
sheet. The lid is slightly larger than the opening, so that
it overlaps. In addition, there is a sturdy eyelet, made
of 4 mm copper wire, with an oval cross-section on the
outside of the cover plate. The wire ends of the eyelet,
forged into narrow sheet-metal strips, lead through the
centre of the lid into the inside of the frame. The eyelet,
including the sheet-metal strips, is soldered to the cover
plate. The entire closure element is constructed like a
drawer that fits exactly into the existing opening of the
container. A rivet pin connects this closure element to the
main container. Like all other components, the rivet pin
is made of copper. It has a round cross-section of 2.5 mm.
Decoration
The container is enamelled and gilded; the closure area,
the figural depictions and the outlines are gilded. The
side area is cross-hatched and also gilded and enamelled.
The manufacturing process of the pictorial surfaces is
as follows: After the hollows were completed they were
filled with the appropriately coloured enamel powders
and then heated. This process was most likely repeated
several times until all hollows were sufficiently filled with
enamel. The entire surface was then polished (Brepohl
1999). The thickness of the enamel varies between 0.5
190  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
and 0.9 mm. Next, almost all of the raised metal areas,
i.e., the figural representations and outlines of the front
and verso, as well as the diamond areas of the lateral
cross-hatched section, were fire-gilded and polished.
The areas of the closure that would later be visible on the
outside were also fire-gilded. Finally, the relic packages
were placed inside and the container was tightly closed
with the aid of the rivet. The beeswax found in the area
of the closure could have served as a sealing compound
to additionally secure the closure of the reliquary and/
or to firmly connect the container with the closure and
thus prevent it from wobbling.
Historical classification
Based on several criteria, the Mainz phylacterion can
be assigned to a group of smaller, enamelled quatrefoil
phylacteria from the second half of the 12th century
(Kemper 2020). These phylacteria, now kept in Boston,
Rome and Halberstadt, have approximately the same
dimensions, basic shape, manufacturing technique,
pictorial motifs, colour spectra and internal division
(Boston, Museum of Fine Arts, Inv. no. 55.466; Rome,
Vatican Museums, Hall of Addresses, Inv. no. 64548;
Halberstadt, Dommuseum, Inv. no. 27). The pictorial
motifs of this group are limited to themes of Christ, Mary
and the Crucifixion (with accompanying figures). They
vary slightly in design and type but all are characterised
by a generally widespread iconography that did not have
to convey any specific references to the relic content, the
place of origin/destination, or the bearer. With these char-
acteristics, they coincide with productions of Hildesheim
enamel workshops from around the mid-12th to the
mid-13th century, where items for liturgical or religious
use were serially produced.
Conclusion
The quatrefoil shaped reliquary pendant dates to the
last third of the 12th century and most likely came
from a workshop in Hildesheim, Lower Saxony. This is
supported by its shape and by other characteristics found
in comparable objects. The object presented here is one
of only four phylacteria of this type known today from
the Hildesheim workshop; the other three are housed in
Halberstadt, Boston and Rome. This artefact was made
to contain reliquary packages, which after completion
of the container were inserted and the reliquary then
tightly closed. Through different modes of analysis, the
TECHNICAL STUDIES
pendant was shown to be made of gilded copper and was
enamelled using the technique of émail champlevé. The
four different enamel colourswere analysed by μ-XRF and
Raman spectroscopy. Examination of a thread fragment
from the area of the suspension eyelet revealed silk, thus
providing the first evidence of the material on which such
pendants were most likely carried. A sample of a waxy
substance could be identified as beeswax by infrared
spectroscopy. NT was used to visualise the contents of
five relic packages and measurements of the textiles and
individual splinters were obtained. The material thickness
of the metal parts and the enamel fields was similarly
determined. PS-PGAA allowed an elemental analysis of
the pendant’s contents. This reliquary pendant is a rare
example of such an object from a controlled excavation.
It was only through the collaboration of archaeologists,
art historians, chemists, neutron researchers, a nuclear
physicist, restorers and goldsmiths that it was possible
to arrive at these detailed results.
Analytical details/methods
• Micro-XRF was conducted by Ms Sonngard Hart-
mann, RGZM. Instrument: Eagle III spectrometer
(Röntgenanalytik, Taunusstein), rhodium source,
maximal power at 40 kV and 1 mA, 25 μm titan filter,
beam diameter 0.3 mm, vacuum, the surface was
analysed under clean conditions but without further
surface preparation.
• Raman spectroscopy was conducted by Dr Marlène
Aubin, RGZM. Instrument: LabRam HR800 (Horiba
Jobin Yvon company), laser 532 nm, 1800 lines/mm
grating, 50 × long focal lens objective.
• FTIR-microscopy was conducted by Ms Sonngard
Hartmann and Mr Matthias Heinzel, RGZM. Instru-
ment: Thermo Scientific FTIR spectrometer. Measured
with an ATR crystal (diamond).
• NT was conducted by Dr Burkhard Schillinger at
FRM II, Garching, TUM. Instrument: ANTARES
(https://mlz-garching.de/antares) (27 October 2021).
• PS-PGAA was conducted by Mr Eschly Kluge and
Dr Christian Stieghorst at FRM II, Garching, TUM.
Instrument: PGAA (https://mlz-garching.de/pgaa)
(27 October 2021).
References
Brepohl, E. 1999. Theophilus Presbyter und das mittelalter-
liche Handwerk, Buch III, Kap. LIIII, 136-140. Köln:
Bölhau.
DISCOVERY OF A 12TH-CENTURY ENAMELLED RELIQUARY PENDANT: ELEMENTAL ANALYSIS AND CONTENT VISUALISATION 191

Kemper, D. 2020. Die Hildesheimer Emailarbeiten des

12. und 13. Jahrhunderts. Regensburg: Schnell & Steiner.

Author
Matthias Heinzel is a conservator responsible for the
precious-metal conservation workshop at the Leibniz
Research Institute for Archaeology, Römisch-German-
isches Zentralmuseum Mainz, Germany. He is a trained
goldsmith and a conservator of archaeological objects.
ANALYTICAL INVESTIGATIONS
Sulfur, the ‘Enemy of Copper’: Replication of Sulfurous
Efflorescence on Copper-based Heritage Materials with
Elemental Sulfur
Charlotte F. Kuhn-Wawrzinek Thomas Schleid
TEMA GmbH Institute for Inorganic Chemistry, University of Stuttgart
Kusterdingen, Germany Stuttgart, Germany
charlotte.kuhn-wawrzinek@temagmbh.de thomas.schleid@iac.uni-stuttgart.de

Gerhard Eggert* *Author for correspondence

State Academy of Art and Design
Stuttgart, Germany
gerhard.eggert@abk-stuttgart.de

Abstract
Copper containing visible three-dimensional sulfurous
efflorescence is known in Europe as ‘black spots’ and in the
USA as ‘brown fuzzies’. These are found on many heritage
materials containing copper exposed to traces of sulfurous
gases. A systematic investigation was carried out to get a
better understanding of the different factors that influence the
underlying corrosion process. The low sublimation pressure
of sulfur in closed containers was utilised to generate typical
efflorescence on copper as well as copper alloys with different
surface properties at varying relative humidity (RH) and
temperature. The stability of chalcocite and covellite, often found
as corrosion products in ‘black spots’, was investigated by exposing
powder samples to different RH. Laboratory experiments were
complemented by surveying more than 300 affected objects
from 11 different collections. The laboratory-grown ‘black spots’,
powder samples and corroded objects were studied using light
microscopy and scanning electron microscopy (SEM) and their
composition – crystalline copper sulfides, oxides and (rarer)
sulfates, and amorphous material – was detected and analysed
using Raman microscopy, energy-dispersive X-ray (EDX) analysis
and X-ray powder diffraction (XRPD). For the first time, typical
‘black spot’ corrosion was reproduced in laboratory experiments.
The laboratory results aligned well with analysis of ‘black spot’
corrosion samples from objects. A systematic correlation
between colour, morphology and chemical composition of the
efflorescence was found and the systematic influence of the
parameters of RH, temperature, alloy type and surface properties
was proven. The stability of covellite and chalcocite decreases
with increasing RH, which increases the corrosive effect of
covellite on metallic copper when in direct contact.
Keywords
anilite, black spots, chalcocite, copper sulfide, covellite,
efflorescence, elemental sulfur, spionkopite

Introduction
The Latin word sulp(h)ur is related to the Sanskrit
s(h)ulbari, a composite of shulba (copper) and ari
(enemy) (Böhtlingk and Roth 1875, col. 269; Monier-Wil-
liams 1899, 1084; Vira 1950, XVI, XXI). The name ‘enemy
of copper’ might preserve ancient chemical knowledge
on the reactivity of sulfur with copper, which is the
background for our study.

The characteristic feature of ‘black spots’ is their striking

three-dimensional growth. Weichert et al. (2004) defined
their morphological nomenclature as ‘trees, bunches and
cauliflower’. They can easily be rubbed off an object’s
surface due to their loose cohesion. Contrary to what
the common term ‘black spots’ suggests, they do not Figure 1. ‘Black spots’ and ‘brown fuzzies’ in the eye of a classical Zeus
only appear in black but also brown, grey and irides- figure
SULFUR, THE ‘ENEMY OF COPPER’: REPLICATION OF SULFUROUS EFFLORESCENCE ON COPPER-BASED HERITAGE MATERIALS WITH ELEMENTAL SULFUR 195

cent colours. In the USA, the term ‘brown fuzzies’ is products and the source of the pollutant. The forma-
commonly used to describe the phenomenon (Eggert tion of sulfurous efflorescence needs volatile sulfur
2021) (Figure 1). sources. There is no proof at all in the literature that the
ubiquitous pollutant sulfur dioxide can produce sulfide
Conservator Gustav Rosenberg (1878–1941) of the
phases, but it might have a synergistic role in corrosion
National Museum of Denmark first described black
processes. Instead, gases containing reduced sulfur (i.e.
spots on bronzes in 1913 in his unpublished working
sulfur with oxidation number −II, −I or 0) have been
notes (Madsen 1985). The first public mention of black
considered in the literature: hydrogen sulfide (H2S),
spots was in a recorded conference discussion remark by
carbonyl sulfide (COS), carbon disulfide (CS2), dimethyl
Werner Wimmel in 1972 (Kirchner 1973, 47). Unpub-
sulfide (CH3SCH3), dimethyl disulfide (CH3SSCH3) and
lished microprobe analyses from 1973 in the archives
elemental sulfur (references in Kuhn-Wawrzinek 2020,
of Antikenmuseum Berlin (Peltz 2021, 541 ff.) detected
22). Cases where the emitting material has been identified
copper, sulfur and possibly oxygen and assumed the
are quite rare, mostly rubber vulcanised with sulfur or
existence of copper sulfide. In the first article on the
wool (emitting, e.g., COS) used in display cases. They can
subject, Madsen (1977) detected covellite by X-ray
easily be identified by the Oddy test or the iodine-azide
powder diffraction (XRPD) and assumed it was due to a
test (Thickett and Lee 2004). Objects from anaerobic
microbiological attack, since a cladosporium fungus was
sites may contain elemental sulfur or unstable sulfides
found on a bronze. Later, this was refuted by Oddy and
(e.g. pyrite) and are known to cause efflorescence (Eggert
Meeks (1982) and Eggert and Sobottka-Braun (1999).
and Sobottka-Braun 1999). Some brands of plasticine are
Black spots have been observed on a wide range of objects formulated with elemental sulfur and may cause black
of different dating, provenance and material composition. spots when used as mounting material (Eggert 2006).
Weichert et al. (2004) and Eggert et al. (2004) reported
With the aim of reproducing the efflorescence in its
black spot efflorescence on copper alloys (including
varying morphologies, a systematic laboratory study
pewter with only 1% Cu), corrosion products, minerals
was designed (Kuhn-Wawrzinek 2020) to investigate the
and pigments. The sulfurous efflorescence consists of
influence of the parameters of time, RH, temperature,
either various crystalline sulfides and rarer sulfates as
copper alloy types, surface finish and minerals on the
oxidation products, or they are amorphous. Although
corrosion process. To ensure that the results from the
they were first discovered in conservation over a century
laboratory experiments could be translated into practice,
ago, no systematic investigations into the corrosion
the morphologies and chemical composition of labora-
process and the stability of the corrosion products
tory-grown corrosion were compared to original objects
have yet been undertaken, as it has not been possible
and samples. Additional experiments were designed to
to reproduce the corrosion products with analogous
investigate the stability and corrosivity of typical black-
morphologies in the laboratory so far.
spot corrosion products on copper to gain information
Thermodynamically, copper sulfides are not stable in on whether and how affected objects should be treated.
the presence of oxygen, therefore sulfates are preferred
(Gow et al. 2016, figs. 1–6). Copper sulfides can also Experimental
transform into other stoichiometries (Ramdohr 1980).
Experiments with metal coupons
Pewter samples (1%–10% Cu) were exposed to hydrogen
sulfide as part of the work of Weichert et al. (2004) and Metal coupons of pure copper, as well as the copper
initially showed only a little tarnish. After 12 years of alloys CuSn8 and CuZn10, with a 2 cm edge length were
storage in polyethylene (PE) bags without the presence exposed in desiccators in the presence of elemental sulfur
of an external sulfur source in our office in Stuttgart, at different temperatures and RH.
they were re-examined and showed significant amounts
To run more than 200 experiments with different param-
of brown efflorescence – a clear indication that black
eter combinations over considerable time (up to 60 weeks)
spots are not stable.
excluded the use of climatised gassing cabinets (e.g. using
Most previous publications present individual case hydrogen or carbonyl sulfide as a sulfur source). As the
studies and focus on the identification of the corrosion pollutant concentration is adjusted by the sublimation
196  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
pressure of sulfur (1.38 ppb at 20 °C, 16.98 ppb at 40 °C),
it naturally resembles values that can also be expected in
practice. For a slow corrosion process, no depletion of
reactants in the chamber is to be expected. Gas diffusion
is fast enough and no constant gas stream with a definite
stream of pollutant is needed.
To adjust RH, saturated solutions of salts (analytical grade)
in beakers were used according to Greenspan (1977):
NaOH for 9%, MgCl2∙6H2O for 33%, Mg(NO3)2∙6H2O
for 54% and KNO3 for 95% at 20 °C (the values were
slightly lower for 40 °C).
For experiments at 20 °C, the desiccators were placed in
a temperature-controlled laboratory. For experiments at
40 °C, the desiccators were placed in a heating cabinet.
Temperatures as well as RH were measured with a data-
logger and found to be constant in a range of ± 2 °C and
± 3%, respectively.
Metal coupons were lightly abraded using a glass bristle
brush then cleaned with demineralised water followed
by acetone and air drying.
In one test series, surfaces of copper coupons were sprin-
kled with powders of malachite (Cu2(OH)2CO3), cuprite
(Cu2O) and tenorite (CuO) (10 mg each) to study their
stability and influence on copper corrosion.
A further series included copper coupons that were
cleaned and heated before the experiment to form a
uniform oxide layer on the surface to investigate its
protective properties.
All test series were run for 30 weeks. Additional series
were run with coupons at 20 °C for 45 and 60 weeks due
to their slower corrosion rate.
Blind tests were run for every series without the pres-
ence of elemental sulfur. Test series were carried out in
triplicate to check for reproducibility.
Stability of copper sulfides
Powder samples of pure covellite, chalcocite and copper
were exposed in closed containers at 20 °C and at different
RH levels of 33, 54, 75 and 95% to examine their stability
depending on RH. Additionally, 1:1 mixtures of covellite
with copper and chalcocite with copper were exposed
to find out whether the sulfides had a corrosive effect
on copper. Another experiment exposed covellite or
chalcocite to copper in the same container without being
ANALYTICAL INVESTIGATIONS
in direct contact to find out if the sulfides generated
corrosive gases that affected the pure copper.
All test series were run for 32 weeks and samples were
analysed after 1, 2, 4, 8, 16 and 32 weeks.
Synthesised chalcocite and covellite as end products of
the series of sulfides were chosen for the study.
To adjust RH in closed containers, saturated salt solutions
were used as described above, using NaCl for 75% RH.
Investigation of museum samples
To check the relevance of laboratory results, they
were compared with black spots that had occurred
in collections. With public calls for samples and the
support of many colleagues, it was possible to docu-
ment and sample more than 300 affected objects in
eleven museums (Kuhn-Wawrzinek 2020) in Göttingen,
Frankfurt, Nuremberg, Cologne, Leipzig (Germany),
Lund (Sweden), Samos (Greece), Zurich (Switzerland),
Amsterdam (The Netherlands), Thorsminde (Denmark)
and Fremantle (Australia).
Analytical methods
Scanning electron microscopy (SEM; Zeiss EVO 60) was
used to visualise the efflorescence with high magnifica-
tion and depth resolution. Combined with energy-dis-
persive X-ray analysis (SEM-EDX; Bruker X Flash 6130
detector), elemental information could be obtained.
Micro-Raman spectra of efflorescence as well as single
particles in powder samples were recorded using a
Renishaw inVia Raman spectrometer (grating 1800 L/mm,
resolution 1 cm−1, He-Ne laser (632.8 nm)) equipped with
a Leica DMLM microscope and a RenCam CCD detector.
Sulfides low in copper (up to spionkopite, Table 1) contain
disulfide units which can easily be detected by their
intensive stretching vibration in the Raman spectrum.
Sulfates as oxidation products can be recognised by the
typical S–O vibrations of the anion.
Selected corrosion samples from objects and laboratory
experiments as well as the test series with powder samples
were analysed by XRPD (Stadi P diffractometer with PSD
detector, Mo Kα radiation with a Ge monochromator) for
their composition of crystalline phases. Beside covellite
(CuS) and chalcocite (Cu2S), a number of other copper
sulfides with Cu to S ratios in between have been differ-
SULFUR, THE ‘ENEMY OF COPPER’: REPLICATION OF SULFUROUS EFFLORESCENCE ON COPPER-BASED HERITAGE MATERIALS WITH ELEMENTAL SULFUR 197

entiated in the last decades as minerals (Table 1) and can

now be distinguished by precision XRPD.

Table 1. Copper sulfide minerals and their composition

Mineral name Formula Cu:S ratio

Chalcocite1 Cu2S 2.00:1
Djurleite 1
Cu31S16 1.94:1
Roxbyite Cu58S32 1.81:1
Digenite1 Cu9S5 1.80:1
Anilite 2
Cu7S4 1.75:1
Geerite Cu8S5 1.60:1
Spionkopite 2
Cu39S28 1.39:1
Yarrowite 1
Cu9S8 1.13:1
Covellite1 CuS 1.00:1 Figure 2.
1
Identified in the literature in black spots Spionkopite on
2
Newly identified in this study in black spots Cu at 9% RH and
40 °C after 30
 weeks
Corrosion rates on metal coupons were qualitatively esti-
mated by a visual assessment of the amount of corrosion
product formed. Conversion in powder samples could
be estimated semi-quantitatively by comparing their
XRPD data.

Materials from collections that were suspected to be the

source of a sulfurous pollutant were tested using the
Oddy test.

Results and discussion of laboratory

experiments

Experiments with metal coupons

Figure 3.
RH is the decisive factor influencing which compounds
Yarrowite (and
form on copper as well as the tested alloys. possibly covellite)
on Cu at 33% RH
At lower RH, sulfides lower in copper were detected on and 40 °C after 30
copper coupons.  weeks

At 40 °C, only spionkopite was detected at 9% RH

(Figure 2), yarrowite (and possibly covellite) at 33% RH
(Figure 3) and both anilite and spionkopite at 54% RH
(Figure 4).
Between 9 and 54% RH, the corrosion rate increased
slightly. Corrosion was quite evenly distributed over the
surface but more prevalent at the edge of the coupon,
which is an expected reaction with gas phase trans-
port of a reactant. Covellite, yarrowite and spionkopite
formed (blue-)black platelets. Anilite occurred in net-like
branched structures which appeared as brown to grey
efflorescence under low magnification.
At 40 °C and 95% RH, a thicker cuprite layer initially
formed and caused a less evenly distributed growth of
the sulfurous efflorescence, which predominated along
the edges of the coupons. Djurleite was the primary
product and formed a very fine light-brown bush-like
efflorescence which could easily be recognised as needles
and dendrites in the SEM (Figure 5a, 5b). The finer the
dendritic units, the lighter the macroscopic colour.
Over time, djurleite transformed into tenorite (CuO) and
copper sulfides with disulfide bonds, as could be detected
at the top of the thickening needles. This process could
198  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND ANALYTICAL INVESTIGATIONS

bushes. Green and colourless particles could be differen-

tiated on the surfaces of the efflorescence by microscopic
investigation, due to sulfate-producing oxidation.

Experiments at 20 °C showed similar results, but the

vapour pressure of sulfur is lower, and the corrosion
rate is, of course, significantly lower. At 20 °C and 95%
RH, the transformation of djurleite to sulfates was not
observed within 30 weeks.

Bronze (8% Sn) and brass (10% Zn) showed similar

results to pure copper, with a slight tendency towards
sulfides lower in copper. The amount of corrosion prod-
ucts formed was lower and the crystal size was smaller.
Figure 4. Anilite They were less homogeneously distributed over the metal
and spionkopite surface and tended more towards net-like intergrowth. At
on Cu at 54% RH
and 40 °C after 30
95% RH, tiny green spots of brochantite (Cu4(OH)6(SO4))
 weeks occurred on the brass. Oxidation of djurleite to sulfates
seemed to be faster on brass; the bushy efflorescence
turned mainly grey within 30 weeks at 40 °C. No corro-
sion products containing tin or zinc were detected.

Powders of malachite (Cu2(OH)2CO3), cuprite (Cu2O)

and tenorite (CuO) that were sprinkled on copper
coupons proved to be more stable than the metal itself
when exposed to sulfur vapours. Severe conditions (40 °C,
95% RH, 30 weeks) produced some brown discolouration
on the malachite and cuprite powders, which showed
tenorite as well as a disulfide vibration in the Raman
spectrum. The tenorite remained stable.

Figure 5. Heating a copper coupon prior to the experiment to

Corrosion on create a uniform oxidation layer of tenorite and cuprite
Cu at 95% RH
caused a very limited and spotty growth of the sulfurous
and 40 °C after
30 weeks: (a) efflorescence at 54% RH and both temperatures. Under
bushes along these conditions, the oxidation layer had protective
the edge of a properties allowing the sulfurous corrosion to form only
coupon, (b) light-
at defect points. At 95% RH and both temperatures, the
brown bushes of
djurleite, (c) dark- sulfurous efflorescence was also less evenly distributed
brown bushes than in experiments without prior oxidation of the
of djurleite coupons’ surface. However, the protective ability of the
with secondary
reaction to
oxidation layer was less effective at the higher RH.
tenorite and
All experiments showed good reproducibility. Three
sulfur-rich copper
sulfides at the morphological types of efflorescence could be differ-
 needle tops entiated by macroscopic and microscopic examination.
The morphologically characteristic growth of copper
also be observed macroscopically and microscopically as sulfides could be traced back to motifs within their
a darkening of the efflorescence’s colour by the formation crystal structures: sulfides low in copper with disulfide
of black particles (Figure 5a, 5c). During further expo- units (covellite (CuS), yarrowite (Cu1.13S) and spionkopite
sure, this turned into an overall greyish aspect of the (Cu1.39S)) appeared as plate-like crystals of (blue-)black
SULFUR, THE ‘ENEMY OF COPPER’: REPLICATION OF SULFUROUS EFFLORESCENCE ON COPPER-BASED HERITAGE MATERIALS WITH ELEMENTAL SULFUR 199

colour. Covellite formed two-dimensional hexagonal

layers which favoured platelet growth. Anilite (Cu1.75S)
and digenite (Cu1.8S) formed branched net structures
which appeared as brown to grey efflorescence. In the
copper rich sulfides, djurleite (Cu1.94S) and chalcocite
(Cu2S), Cu-S layers were interrupted. The resulting
one-dimensional bands favoured needle and dendritic
growth. Such efflorescence occurred in very fine light-
brown bushes (needles and dendrites in the SEM).

Stability of copper sulfides

Figure 6. Roman
No changes could be detected on pure copper samples at fibula with dark-
all RH levels over 32 weeks. The presence of chalcocite brown bushes
and very dark to
or covellite without direct contact also had no impact on iridescent surface
the stability of the copper powder. due to secondary
reactions on
Only at 95% RH did covellite develop some sulfates copper-rich
(Raman: chalcanthite (Cu(SO4)∙5H2O) and antlerite copper sulfides:
(Cu3(OH)4SO4)). The conversion rate was very slow and (a) fibula,
(b) iridescent
the amount of sulfates was below the detection limit for area, (c) SEM
XRPD after 32 weeks. micrograph
showing bushes
Pure chalcocite reacted from 33% RH onwards to with a dense layer
djurleite (XRPD) and tenorite (Raman) which could be of secondary
observed in the formation of a dark tarnish on the particle reaction products
on the bushes’
surfaces. The reaction rate increased significantly with surface

increasing RH.

In mixtures, chalcocite had no effect on copper powder

when in direct contact at any RH level, whereas covel-
lite did react with copper powder. The reaction rate
increased significantly with increasing RH, forming
cuprite (Raman, XRPD) and brochantite (Raman).
Investigation of museum samples
Efflorescence found on museum objects can roughly be
divided into three categories similar to those found in
the laboratory experiments. Sometimes different forms
are found side by side on the same object.
Among the objects studied, 205 exhibited brown, bush-
like efflorescence often intergrown to larger areas and
sometimes with (blue-)black or iridescent spots. Light-
brown bushes consisted of very fine dendritic units,
while darker-brown bushes had coarser particles at the
top. In very dark, black or iridescent areas, a continuous
layer had formed on the bushes’ surface (Figure 6). The
light-brown efflorescence looked similar to that found
in laboratory experiments at 95% RH (Figure 7) and
was also identified as chalcocite or djurleite. Darker
particles or layers on top of the bush-like formations
were identified as tenorite and sulfides with disulfide
units (Raman). In one corrosion sample, the copper
sulfate antlerite was detected as well as djurleite (XRPD).
Eighty-nine objects had blue-black efflorescence
consisting of plate-like units (Figure 8). They consisted
of sulfur-rich sulfides (disulfide vibration in the Raman
spectrum), as found in corrosion from laboratory exper-
iments at 9 and 33% RH. In one sample, antlerite was
detected, indicating oxidation to basic sulfate.
Sixty-five objects had brown to grey efflorescence,
showing quite coarse dendritic to net-like structures
under the microscope. They showed no vibrations in
the Raman spectrum, while XRPD pointed to spionko-
pite and digenite. Fine plate-like units in between the
dendrites consisted of disulfides (Figure 9). All in all, this
corrosion was similar to the products formed at 54% RH
in the laboratory.
200  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND ANALYTICAL INVESTIGATIONS

Figure 9. Grey
efflorescence on
a candelabrum
with dendritic-
branched
structure: (a) grey
Figure 7. Light-
efflorescence, (b)
brown bushes
SEM micrograph
on a metal
fragment with
 of efflorescence
characteristic
dendritic
structures: (a)
detail, (b) SEM growth of efflorescence found on museum objects.
micrograph of The systematic influence of the RH, temperature, alloy
light-brown composition and surface condition parameters on the
bush, (c) SEM
micrograph of
corrosion process could be proven.
dendritic units in
RH was the decisive factor in growing the different
 light-brown bush
morphologies of brown, grey or blue-black efflorescence
which consist of different compounds with different
Cu:S ratios.

The initially formed sulfides can undergo secondary

reactions and thereby promote further corrosion of the
metal itself, especially at high RH.

Based on the results, guidance for best practice is as

follows:
• Remove copper sulfides from objects whenever
possible.
• Store copper-containing objects at low temperature
Figure 8. Blue-black efflorescence at cracks in the corrosion layer of a and low RH.
bronze sword • Test storage and display materials for sulfur emissions
(Oddy or iodine-azide test) and look for other sources
Conclusion and outlook of sulfur.

The sublimation pressure of up to 17 ppb at 40 °C was Despite extensive experimental effort, open questions
sufficient to grow significant amounts of sulfur-induced still remain. The methodology developed in this work
efflorescence on copper-containing alloys and copper can now be used to study further issues related to the
in 30–60 weeks, making it possible to simulate the slow black-spot corrosion process.
SULFUR, THE ‘ENEMY OF COPPER’: REPLICATION OF SULFUROUS EFFLORESCENCE ON COPPER-BASED HERITAGE MATERIALS WITH ELEMENTAL SULFUR
More research is needed on remedial conservation like
the protective effect of lacquer coatings, which need to
be flawless or spots can often grow in the defects.
The authors came across cases where silver rich in
copper formed mixed silver-copper sulfides with similar
dendritic morphologies. But what about other alloys such
as lead, a common compound in ancient copper alloys?
And what is the nature of the amorphous material in the
spots which cannot be identified by XRPD? In the Raman
spectra, no evidence was found for any intermediate
S–O compound between sulfide (S2−) and sulfate (SO42−).
Much more sophisticated analytical methods will be
needed to study the oxidation state of sulfur (e.g. X-ray
absorption near-edge spectroscopy (XANES)).
While black spots and brown fuzzies are certainly infre-
quent, they are present today in museums around the
world. Conservators must be aware of them so that the
‘enemy of copper’ can be identified and prevented.
Acknowledgements
The authors would like to thank Baden-Württemberg
for providing Charlotte F. Kuhn-Wawrzinek with a
graduate stipend, Christoph Krekel for providing access
to Raman and SEM-EDX, Rainer Niewa for providing
access to XRPD and Uwe Peltz for indicating useful
earlier research.
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Authors
Charlotte F. Kuhn-Wawrzinek has a degree in objects’
conservation (2010) and a PhD (2020) from the Stuttgart
State Academy of Art and Design. She has worked as a
conservator, conservation scientist and lecturer focusing
on the preservation and corrosion of metal artefacts,
historic pigments and chemistry in conservation. Since
2016, she has worked in various strategic roles in the IT
industry.

Gerhard Eggert has a degree in chemistry (1982)

and a PhD (1986) from the University of Bonn, where
he conducted experimental work in electrochemistry.
Between 1985 and 1998 he was head of the Conserva-
tion Department at Rheinisches Landesmuseum Bonn,
dealing mainly with archaeological finds. From 1998
to 2019 he was Chair of Objects’ Conservation at the
Stuttgart State Academy of Art and Design. His research
interests include the manufacture, degradation and
conservation of inorganic objects.

Thomas Schleid has a degree in chemistry (1984) and

a PhD (1988) from the Justus Liebig University, Gießen,
where he conducted experimental work in inorganic
chemistry. In 1993, he obtained a postdoctoral quali-
fication in inorganic chemistry from the University of
Hanover. Since 1995, he has been Chair of Inorganic
Solid State Chemistry, University of Stuttgart and director
of the Institute of Inorganic Chemistry, with research
interests in multi-anionic solid-state rare-earth metal
compounds.
The Role of Patina on Archaeological Copper Alloy Coins in
the Outbreak and Progression of Bronze Disease
Johanna C. Thunberg* Nicola J. Emmerson
Cardiff University Cardiff University
Cardiff, UK Cardiff, UK
thunbergjc@cardiff.ac.uk emmersonnj@cardiff.ac.uk
David E. Watkinson Zoltan Kis
Cardiff University Centre for Energy Research
Cardiff, UK Budapest, Hungary
watkinson@cardiff.ac.uk kis.zoltan@energia.mta.hu
Abstract
Archaeological copper alloy objects form unique corrosion
structures according to their manufacture and burial
environment. Categorisation has identified protective Type I
structures and chloride-containing Type II structures which may
lead to bronze disease. Using visual examination to determine
which of these exist on objects dictates conservation decisions;
unfortunately, there is limited evidence linking surface features
directly to corrosion risk. In this study, the chloride content
of 39 archaeological copper alloy coins was determined non-
destructively using prompt gamma-ray activation analysis. Their
surfaces were examined through Raman spectroscopy, reflective
Introduction
Archaeological copper alloy objects often occur in large
numbers in heritage collections. The primary concern
with these objects is the onset of bronze disease. This
is an active, chloride-driven corrosion process that can
result in the complete destruction of an object (Scott
2002). Bronze disease develops from cuprous chloride
(CuCl), which forms adjacent to the metal core during
burial when chloride ions interact with cuprous ions (1)
(Wang et al. 2006):
Cu+ + Cl− → CuCl + e−  (1)
If pH < 5, cuprous oxide (Cu2O) can also form CuCl
through (2) (Grayburn et al. 2015):
Cu2O + 2H+ + 2Cl ←→ 2CuCl + H2O(2)
In a post-excavation environment, CuCl can interact
with atmospheric oxygen and moisture to form copper
trihydroxychloride isomers (Cu2(OH)3Cl) (3) (Dowsett
et al. 2012):
4CuCl + O2 + 4H2O → 2Cu2(OH)3Cl + 2H+ + Cl−(3)
Ildikó Harsányi Mark Lewis
Centre for Energy Research National Roman Legion Museum
Budapest, Hungary Caerleon, UK
harsanyi.ildiko@energia.mta.hu mark.lewis@museumwales.ac.uk
Zsolt Kasztovszky *Author for correspondence
Centre for Energy Research
Budapest, Hungary
kasztovszky.zsolt@energia.mta.hu
transformation imaging and visually using descriptors reflecting
Type I, Type II and ‘bronze disease’ surfaces. When subjected
to high relative humidity, none of the coins exhibited bronze
disease despite containing chlorides and showing characteristics
of Type II structures and bronze disease. The results highlight the
difficulty of determining risk and taking informed decisions for
the management of archaeological copper alloy objects.
Keywords
bronze disease, corrosion monitoring, management, decision-
making, conservation, characterisation
The rapid and voluminous growth of Cu2(OH)3Cl can
disrupt overlying corrosion layers, destroying surface
details and forming a disfiguring growth on the surface.
The ability of the process to continuously form CuCl (4)
means that the destruction will continue until the supply
of oxygen, atmospheric moisture or copper is supressed
(MacLeod 1981).
2HCl + 2Cu → 2CuCl + H2(4)
As a result of the significant risks to objects suffering
from bronze disease, conservation efforts are focused on
preventing post-excavation processes from occurring.
Management of archaeological copper alloys
The tools to evaluate the risk of bronze disease within
practical or ethical remits are limited. Thorough inves-
tigation of the burial and post-excavation environments,
and the nature of the alloy, manufacturing processes
and corrosion stratigraphy can inform conservation
204  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
strategies, but this information is rarely available. The
location of CuCl next to the metal surface means that
it cannot be identified without destructive sampling.
Due to the complex formation of corrosion products,
surface analysis offers limited insight unless Cu2(OH)3Cl
is detected, yet at this point the object is likely to have
already incurred damage. In practice, visual inspection is
often employed for assessing the condition of copper alloy
objects. The success of visual inspection is dependent on
factors such as understanding of corrosion processes,
experience, colour perception and method of assessment.
Guidance to identify corrosion risk can standardise and
improve the accuracy of assessments.
Archaeological copper alloys display complex corro-
sion profiles as a result of extrinsic factors, such as the
chemo-physical properties of the burial environment, and
intrinsic factors, such as the nature of the alloy and manu-
facturing processes (Ingo et al. 2019, Leygraf et al. 2019).
The appearance of copper alloy objects can therefore differ
widely. Despite this, it has been suggested that copper alloys
can fall within two types of corrosion structures that create
distinguishable features, commonly recognised as Type I
and Type II structures (Robbiola et al. 1998). A literature
review of conservation and archaeometallurgical publica-
tions identified over 50 sources applying Type I or Type II
structures to characterise objects, suggesting they are often
used for this reason. A Type I structure has a two-layered
profile that replicates the metal surface (‘original surface’)
without a significant change in volume. A Type II structure
is defined by a porous, three-layer profile rich in chloride
ions next to the metal and containing no detail from the
original surface. As a result of their corrosion history,
Type I and Type II structures could display features that
are visually distinguishable by their textures and colours.
Being able to separate these surfaces by appearance is
potentially important for conservation practice, as a Type I
structure is believed to have protective properties, while
a Type II structure is thought unstable due to its chloride
content and by allowing ion transport (Payer et al. 1995,
Robbiola et al. 1998).
Examination of guidelines and literature reveals the
existence of jargon in conservation practice to describe
archaeological copper alloy surfaces and bronze disease,
with many terms overlapping or being closely connected
to the terminology used by Robbiola et al. (1998) to
define Type I and Type II patinas (e.g. Wadsak et al.
2000, Constantinides et al. 2002, Bozzini et al. 2017,
ANALYTICAL INVESTIGATIONS
Cosano et al. 2018). Table 1 demonstrates the descriptors
most frequently encountered in literature to describe
Type I and Type II patinas, alongside descriptors used
to identify bronze disease (Table 1). Several descriptors
to identify bronze disease overlap those with a Type II
patina, indicating that these may be linked.
While the terminology around archaeological copper
alloys is well established, the link between the descrip-
tors in Table 1 and the stability of an object has not been
investigated in detail. When copper alloy objects in
the Burrell collection were examined in a recent study,
only 6 of the 64 objects suspected to suffer from bronze
disease after visual inspection were shown to be actively
corroding (Bryan 2021). This suggests that the accuracy
of descriptors currently used in practice to identify
objects affected by bronze disease is low.
As object appearance informs conservation deci-
sion-making, it is critical to have a good understanding
of the information that can be determined visually from
corroded surfaces. This pilot-study explores the link
between existing vocabulary to describe copper alloy
objects and the outbreak of bronze disease.
Aim and objectives
This study aims to investigate the relationship between
the appearance of archaeological copper alloy objects,
the presence of chlorides and the risk of bronze disease.
This is achieved by:
• characterising the surfaces of 39 Roman archaeological
copper alloy coins by visual and instrumental analysis;
• establishing the chloride content of the coins by
prompt gamma-ray activation analysis (PGAA);
• exposing the coins to high humidity environments
understood to trigger bronze disease and monitoring
corrosion using reflectance transformation imaging
(RTI) and oxygen consumption.
Method
In this study, 39 archaeological copper alloy coins
(IP01–IP40) were examined (Figure 1). These were
metal detectorist finds donated to Cardiff University
Conservation Department for research. The coins varied
between 6 and 27 mm in diameter and weighed between
0.88 and 4.96 g. X-radiography demonstrated that all
of the coins had a metallic core. The detection site and
context are unknown, and the coins are therefore deemed
THE ROLE OF PATINA ON ARCHAEOLOGICAL COPPER ALLOY COINS IN THE OUTBREAK AND PROGRESSION OF BRONZE DISEASE 205

Table 1. Example of descriptors used in literature to characterise archaeological copper alloys

Type I Type II Bronze disease

Smooth Powdery Powdery
Even Buboes Dusty
Uniform/monochrome Warts Patches
Shiny Limpets Flakes
Lustrous Coarse/rough Blisters
Hard Pits Warts
Dense Crevices Pustules
Pleasant effect Crust Mounds
Coherent Loss of material (incl. spalling, breakup of overlying layers) Loss of material
Adherent Local outbreaks/attack Voluminous
Compact Patches Local outbreaks/attack
Texture

Detail from original surface Polychrome Spots

Spots Cracking
Cracking Non-adhering, loose
Soft Pits
Non-adhering, loose
Underweight
Lamellar plates
Flakes/delamination
Holes
Porous
Hard to nearly hard
No detail from original surface
Green Green Green
Red Light green Blue-green
Brown Light blue Pale green
Colour

Grey Bright green Bright green

Blue Blue-green Light green
Black
Red
Brown

Figure 1. Images of all coins

examined. Images are not
to scale. Length of diameter
at widest point is given in
 mm in parentheses
206  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
of low archaeological value. The coins were mechanically
cleaned to remove soil products.
Establishing chloride content
The bulk chloride content of the coins was determined
non-destructively using PGAA at Budapest Neutron
Centre, Hungary. PGAA can detect bulk chloride through
irradiation from a cold-neutron beam which detects
characteristic gamma-photons emitted in (n, γ) reac-
tions. The neutrons can penetrate several centimetres
into a material, facilitating determination of the bulk
concentration of elements in small objects. The distribu-
tion of chlorides was mapped in three coins (IP05, IP39
and IP40) using the NIPS-NORMA (neutron-induced
prompt gamma-ray spectroscopy and neutron optics and
radiography for material analysis) station.
Surface examination
All coins were recorded using a Broncolor Scope D50
RTI dome equipped with 48 white (5000 K ± 75 K) LED
lights. Images were processed using Truvis Authentica
software. Images were captured with a Nikon D5600 with
a Nikon AF-S Micro-Nikkor 105 mm lens.
Raman spectroscopy was employed to characterise
surface corrosion products with a B&W Tek iRaman
Plus equipped with a 785 nm (resolution ~3.5 cm−1
max 30 mW) and 532 nm (resolution ~4.5 cm−1 max
340 mW) probe at ×50 magnification (laser spot size
42 µm). Integration time ranged from 2 to 60 sec and 1
to 100 acquisitions. Laser intensity ranged from 1 to 5%
of maximum laser output. Twenty spectra of each coin
were taken at sites of different colours and textures to
account for the surface heterogeneity of the coins.
Three trained conservators with practical experience
of working with archaeological copper alloys examined
the surface of each coin at ×4 magnification under a
Just Normlicht XL colour viewing light with a D65 LED
light source (colour temperature of 6500 K) at a 70 cm
working distance. The descriptors in Table 1 were used
to characterise the surface of each coin during exami-
nation. All descriptors that were applicable to describe
the surface of the coins were selected.
Corrosion monitoring
Coins IP01–IP40 were subjected to a saturated humidity
environment and monitored for any physical signs of
ANALYTICAL INVESTIGATIONS
active corrosion for 37 days. A 100% relative humidity
(RH) environment was created by enclosing three beakers
with cotton wool saturated with water (total 450 mL) in
a Stewart Gastronorm 13l polypropylene box.
The oxygen consumption of five coins containing the
highest chloride content (IP05, IP11, IP39, IP20 and
IP40) was measured individually to produce a quanti-
tative measure of their corrosion rates. The method has
been reported in detail in an open access publication
(Emmerson et al. 2021).
A 250 mL Mason Ball jar was used to create an airtight
environment for oxygen measurements containing
a two-point PreSens GmbH SP-PSt3-NAU-D5-YOP
ruthenium oxygen sensor spot adhered to the interior
wall using Radio Spares RTV silicone rubber compound.
Every vessel was assigned a Madgetech RHTemp101A
datalogger (± 1.1% RH at 80% RH) to monitor the
internal RH. Silica gel (160 g) conditioned to 80% RH
was enclosed in the vessel to maintain a high humidity
environment for the test duration. A relative humidity
of 80% RH was chosen as a suitable environment to
detect activity related to bronze disease as this is known
to produce rapid corrosion rates (Thickett 2016). A
PreSens GmbH POF-L2.5-1SMA 505 nm fibre sensor
connected to a Fibox 4 oxygen meter was used as the
luminescence source. The coins were monitored for their
oxygen consumption for 44 days.
To investigate the protective properties of corrosion
structures, coins IP05, IP11, IP20, IP39 and IP40 were
thereafter scored through the corrosion profile and down
to the metal surface using a scalpel, revealing the full
corrosion profile of the coin and potentially exposing
chloride sites (Figure 2). Their oxygen consumption was
recorded for 140 days. Detailed mapping of chlorides
using NIPS-NORMA on IP05, IP11 and IP39 determined
the location of scoring down the middle of the obverse
and reverse of the coins (Figure 2). All coins were visually
assessed at the end of oxygen consumption to control
for any changes.
Results
PGAA/NIPS-NORMA analysis
The chloride content in all of the coins is expressed as a
ratio of chloride to copper in elemental weight. All of the
coins (IP01–IP40) contained chloride, demonstrating a
copper to chloride ratio between 2.65 × 10−4 and 1.46 × 10−2
THE ROLE OF PATINA ON ARCHAEOLOGICAL COPPER ALLOY COINS IN THE OUTBREAK AND PROGRESSION OF BRONZE DISEASE 207

(Figure 3). Neutron imaging of IP05, IP11 and IP39

demonstrated that chloride was localised within the coin.

Surface examination
During examination, different descriptors were
employed by each observer to characterise a coin. No
two coins had identical sets of descriptors, and descrip-
tors for Type I, Type II and bronze disease were used
to describe each coin (Figure 3). The five coins with
the highest chloride/copper ratio (IP05, IP11, IP20,
IP39, IP40) and those with the lowest chloride/copper
ratio (IP01, IP24, IP25, IP30, IP36) were characterised
by many overlapping descriptors, with no apparent
distinguishing features to suggest one set would contain
more chlorides (Figure 4).
Figure 2. IP05, IP11, IP20, IP39 and IP40 after scoring on the obverse
and reverse Eighteen coins displayed some preservation of the orig-
inal surface detail. These were both within the range of
the highest (IP05, IP20, IP39, IP40) and lowest (IP01,
IP25) chloride-containing coins, demonstrating no

Figure 3. The number of Type I patina, Type II patina and bronze disease Figure 4. Descriptors used for the coins containing the lowest chloride
characteristics identified in each coin by at least one of the three assessors. content (IP01, IP24, IP25, IP30 and IP36) and highest chloride content
The chloride/copper ratio of each coin as measured by PGAA is included (IP05, IP11, IP20, IP39 and IP40)
208  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND ANALYTICAL INVESTIGATIONS

obvious relationship between the preservation of the Corrosion monitoring

original surface detail and chloride content (Figure 3).
Some descriptors were used consistently throughout
the dataset, whereas some were never used to describe
surface features (Table 2).
Table 2. Descriptors applied to all coin surfaces and descriptors not
used to characterise coin surfaces
None of the coins showed signs of active corrosion after
exposure to 100% RH. Coins IP05, IP11, IP39, IP20 and
IP40 did not consume any oxygen during exposure to
80% RH. Scoring the coins to damage the patina did not
affect their oxygen consumption rate, and the coins did
not develop any visible signs of bronze disease.

Descriptors used for all coins Descriptors not used Discussion

Hard Porous
Dense Dusty Establishing the presence of chloride cannot indicate
Coherent Warts whether bronze disease will occur. None of the coins
Adherent Pustules investigated developed new signs of active corrosion
Buboes when subjected to environments known to promote the
Limpets process, despite a known chloride content. Compro-
Holes mising the patina and exposing chloride sites in five of
Pleasant effect the coins with the highest chloride content (IP05, IP11,
IP39 and IP40) did not result in the breakout of bronze
Detection of corrosion compounds using Raman spec-
disease. This makes it unlikely that any CuCl was exposed
troscopy was difficult, probably due to poor crystallinity
during the study.
of the corrosion products and significant fluorescence
masking the Raman signal. Raman detected the presence It is possible that the chlorides mapped by PGAA and
of malachite (Cu2CO3(OH)2) and cerussite (PbCO3) NIPS-NORMA are not present as CuCl but located
(Figure 5). Soil components included quartz, calcite, elsewhere in the corrosion products. Copper trihy-
feldspar and the TiO2 isomers rutile and anatase. droxychlorides (Cu2(OH)3Cl) may already be present
in the patina, and other copper chloride compounds,
such as connellite (Cu 19 Cl 4 (SO 4 )(OH) 32 ∙3(H 2 O)),
sampleite (NaCaCu5(PO4)4Cl∙5(H2O)) and calumetite
(Cu(OH, Cl)2∙2(H2O)), have been found on archaeological
copper alloys (Scott 2002, Giovanelli et al. 2010, Muros
and Scott 2018). Other alloying chloride compounds have
been identified, such as mendipite (Pb3Cl2O2), pyromor-
phite (Pb(PO4)3Cl) and laurionite (PbCl(OH)) in leaded
copper alloys (Ingo et al. 2006, Bernard and Joiret 2009,
Mezzi et al. 2012) and AgCl in silvered coins (Fabrizi
et al. 2019). None of these compounds were identified
using Raman spectroscopy, but due to the heterogeneity
of the surface, poor crystallinity of compounds and the
limit of laser penetration, these compounds could still be
present. Chlorides could also be present as a soil product
and integrated on the surface. A second, follow-up study
will examine the coins in more detail to locate chlorides
throughout the corrosion profiles.

Surface examination
The surface examination of each coin using descriptors
Figure 5. Raman spectra of (a) malachite (Cu2CO3(OH)2) and (b) cerussite highlights the subjectivity of visual examination and the
(PbCO3) difficulty of standardising vocabulary to guide object
THE ROLE OF PATINA ON ARCHAEOLOGICAL COPPER ALLOY COINS IN THE OUTBREAK AND PROGRESSION OF BRONZE DISEASE
inspection. Several challenges occurred during exam-
ination resulting in an unclear relationship between
surface features and chloride content, further limiting
the ability to correlate the appearance of objects to risk.
These challenges included:
• Interpretation of key descriptors
A range of descriptors were not used by assessors due
to the lack of references illustrating the descriptors,
making them difficult to interpret. Others lacked a
contrasting reference point, such as ‘soft’ or ‘under-
weight’. The challenge of using descriptors to char-
acterise a surface is demonstrated in the range of
terminology used by the assessors to characterise the
same objects.
• Applicability of descriptors for each object
Interpretation of object surfaces is further compli-
cated by the presence of Type I, Type II and bronze
disease descriptors on all examined surfaces. While
this reflects the heterogeneity of archaeological copper
alloy surfaces, it suggests that there is a limit to the
usefulness of these descriptors for determining risk.
This is illustrated in Figure 6, which shows the simi-
larity of a stable surface (IP03) and the surface of a
coin from a different sample set on which active bronze
disease has been recorded.
Figure 6. IP03 (∅ 10.6 mm) and an actively corroding coin (∅ 25.9 mm)
from outside this sample set showing similarity of surface features
• Insufficient terminology to reflect the complexity of
some surfaces
Despite the range of terminology used to distinguish
Type I, Type II and bronze disease surfaces, the
descriptors did not reflect the complexity of each coin.
In particular, colour may not be a reliable indicator
owing to the colourant properties of Cu(II), which
may produce a range of products similar in colour
(Leygraf et al. 2019), as illustrated in Figure 6.
209
Implications for conservation practice
Identifying chloride in archaeological copper alloy corro-
sion structures is not a determining factor in identifying
risk of bronze disease. Consequently, visual examination
and identification of surface features that are suggestive
of a chloride-containing corrosion structure may not
be a reliable indicator that bronze disease will occur.
Complexity of surfaces, ambiguity in interpretation of
descriptors and the occurrence of multiple features on
the surface of one object will further complicate deci-
sion-making.
Some key features that were not used by the assessors in
this study could be indicators of bronze disease (Table 2)
but may only provide retrospective evidence for ongoing
active corrosion when damage has already occurred,
rather than detect risk. As the outbreak of bronze disease
may not occur immediately after excavation, active
bronze disease can proceed unhindered unless objects are
monitored regularly. Conversely, the cautious approach
of bulk treatment or environmental control of objects
(possibly unnecessarily) to mitigate the risk of bronze
disease can be costly in time, materials and potential
exposure to harmful materials and may also result in
unwanted surface alterations.
Conclusion
• This study highlights the limitations of using visual
examination and surface analysis to determine whether
an object is at risk of developing bronze disease, which
normally dictates management policy and treatment
decisions.
• Using written guidance for visual analysis is complex,
and it is difficult to determine the success of using
descriptors.
• Some terminology may be more useful for determining
the risk of active bronze disease, but a more precise
language is necessary to determine risk.
• Non-destructive analysis techniques to determine the
presence of chlorides are of limited use in assigning
risk, as they do not serve as an indicator for bronze
disease.
• The cost-benefit rationale for treatment or imple-
menting environmental control is affected when
corrosion risk cannot be evidenced.
• Ongoing monitoring to detect changes in copper
alloys on display or in storage is an important but
often monumental task.
210  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
The sample set of coins are of similar size, dimension
and corrosion thicknesses and cannot provide a complete
picture of the different corrosion surfaces associated
with bronze disease. A further larger-scale study will
include objects of different shapes and contexts to gain
a more complete understanding of appearance/bronze
disease relationships. A follow-up study is underway to
determine the chloride location throughout the corrosion
profiles of the coins.
Acknowledgements
The authors wish to thank the AHRC-funded SWW DTP
consortium and IPERION CH for supporting this project.
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September 2016, eds. R. Menon, C. Chemello, and A.
Pandya, 180–7. New Delhi: International Council of
Museums-Committee for Conservation (ICOM-CC) and
Indira Gandhi National Centre for the Arts (IGNCA).
Wadsak, M., I. Constantinides, G. Vittiglio, A. Adriaens,
K. Janssens, M. Schreiner, F.C. Adams, P. Brunella, and M.
Wuttmann. 2000. Multianalytical study of patina formed
on archaeological metal objects from Bliesbruck-Rein-
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Wang, J., C. Xu, and G. Lv. 2006. Formation processes
of CuCl and regenerated Cu crystals on bronze surfaces
in neutral and acidic media. Applied Surface Science
252(18): 6294–303.

Authors
Johanna C. Thunberg teaches conservation and is
undertaking a PhD at Cardiff University. Her research
focuses on storage protocols for archaeological metals
and identification of instability in copper alloy artefacts.

David E. Watkinson teaches and researches conser-

vation at Cardiff University. His work on the corrosion
rate of iron underpins the preservation of Brunel’s iron
steamship SS Great Britain.

Nicola J. Emmerson lectures in conservation science

at Cardiff University and researches the management
of corrosion prevention strategies for metallic cultural
heritage artefacts.

Zoltan Kis is a senior fellow scientist at the Centre for

Energy Research, specialising in gamma spectroscopy,
PGAA and imaging.

Ildikó Harsányi is a researcher at the Centre for Energy

Research. She has published extensively on the use of
PGAA to examine archaeological materials.
Non-Invasive Analysis: The Mirage and the Reality
Peter Northover
University of Oxford (retired)
Abingdon, Oxfordshire, UK
peter.northover@retired.ox.ac.uk
Abstract
This paper aims to seek a balance between non-invasive and
sample-based analyses. To do so, it presents three case studies:
a medieval sculpture, the Pisa Griffin; copper fastenings from
wooden warships from the time of the Napoleonic Wars; and
a study of the bronze artefacts from a Late Bronze Age village
in England that had been destroyed by fire. In the first case,
a correct understanding of the Griffin could not be obtained
without taking metal samples, and for the copper it was non-
invasive neutron diffraction that amplified the conclusions
Introduction
The central premise of this paper is that contained within
the material of every metal artefact is a wealth of infor-
mation for the archaeologist, the historian, the curator,
the conservator, and the metallurgist. Everything that
has happened to it since the metal left the furnace can
leave traces which can be recovered by an appropriate
metallographic method. Traces of one event may over-
write another but, very often, a very complete biography
is possible, one that is enhanced when it is linked to the
documentary record, and that can have a telling impact
on both scholarship and broader outreach.
At the start of, and throughout, any project, be it a single
museum or gallery exhibit, or the assemblage of metal-
work from an excavation, there should be a conversation
among all these parties to review all the possibilities. Two
questions have to be addressed. The first is how much of
that information needs to be retrieved, bearing in mind
that if the artefact is correctly conserved, unrecovered
information will still be retained. The second question
is how to do this, and the cry is always for non-invasive
analysis, which can be difficult since the information
is distributed throughout the artefact. Non-sampling
methods of compositional analysis, even using heavy,
high-energy particles such as 3 MeV protons (proton
induced X-ray emission (PIXE)), have limited depth
from metallographic samples. In the final example, non-
invasive analysis would have completed the picture but was
not practical at the time. The two approaches should be explored
together and an appropriate analysis strategy reached without
preconceptions.
Keywords
non-invasive analysis, macrostructure, microstructure,
sampling, metallography, interpretation
penetration and, with the exception of some proton
instruments, are more or less blind to surface and
sub-surface alterations such as corrosion, oxidation, and
plating; obtaining a composition unaffected by these
factors requires some intervention.
The composition of a metal artefact only tells part of
its story: macro- and microstructure are as important.
These pose another problem, since observation of
the microstructures of metals requires a flat, polished
surface, either on a cut sample or in situ on an object
(or on a thin foil for the rare occasions when transmis-
sion electron microscopy (TEM) might be relevant to a
project). A cut sample is also often the most effective and
efficient way of displaying the complexities of corrosion
to both the archaeologist and the conservator, and this
is especially true for archaeological material. Advances
in computed tomography (CT) have great potential in
this area as micro-CT can map inclusions and corrosion
in three dimensions in suitable sections, but expense
is always an issue. Other whole-object techniques for
composition and structure do exist, especially those
using neutron beams, but they are limited in resolu-
tion and can be extremely time consuming. They are,
though, still the best way of addressing some important
questions over whole objects.
NON-INVASIVE ANALYSIS: THE MIRAGE AND THE REALITY 213

Case studies
Three case studies are presented to demonstrate different
combinations of non- and minimally invasive approaches
to characterisation. In the first two the mix has evolved
over the continuing life of the projects, greatly extending
the scope of the initial conversations. The third project is
of much shorter duration to a planned design and is now
in the course of publication. All three projects provide
scope for further development, the only limitation being
funding. The projects are:
• the Pisa Griffin, a medieval piece of public art, where
much could be done non-invasively but sampling was
essential to solve certain problems;
Figure 1. 3D scan of the Pisa Griffin
• copper fastenings from Royal Navy wooden warships
from the late 18th and early 19th centuries, where
12th century. Its early history is unknown and the first
most questions could be answered from small samples,
direct evidence of its presence in Pisa is not until the 15th
although there was one major aspect which required
century, by which time it was mounted on the apex of the
a non-invasive solution;
east pediment of Pisa Cathedral. It is reasonable, though,
• the metalwork from the pile-dwelling Late Bronze Age
to believe that it was placed there when the cathedral was
village at Must Farm, near Peterborough, England,
completed in the early 12th century. How it came to Pisa
which was destroyed by fire a few months after it was
is also unknown, but acquisition during a Pisan raid on
built, c. 850 BC. For the questions asked, the project
Almeria in 1089 or on the Balearic Islands in 1113–15 is
was completely dependent on metallographic samples;
the one opportunity for extensive non-invasive anal- very possible. A date of this order is supported by a radi-
ysis, the mapping of sulfide corrosion, was not practical ocarbon date from organic material found in one wing
within the budget. (Calcagnile 2018); it should be pointed out that the wings
are separate castings riveted in place and are not a pair.
The first two projects evolved from a rather basic design
over an extended period of time, and they are still The relevance of the Griffin to the discussion in this paper
evolving with the incorporation of new techniques as lies in its present location and access to it. The Griffin was
so much is still unknown. The third used a much more removed from the cathedral roof in 1828 and exhibited in
detailed design based on previous experience of Bronze the Camposanto, protected from the rain but still exposed
Age metalwork assemblages. In all cases, electron probe to a marine atmosphere. In 1986 the Griffin and its tall
microanalysis (EPMA) with wavelength dispersive spec- plinth were moved to the new Opera del Duomo Museum.
trometry (WDS) and optical metallography formed the In its present position, access along one side is difficult.
analytical core of the project. Another consideration is a large crack originating from a
cold shut in its back, which gave great cause for concern
The Pisa Griffin after the Griffin was transported to an exhibition in Doha
in 2008. The decision was made not to move it again, which
The Pisa Griffin is a large copper alloy figure of a griffin,
prevented its transport for radiography or a CT scan. In
a mythical beast with the head, breast, and wings of an
addition, it was also decided that it was not possible to
eagle and the body of a lion, and all analysed components
take radiographs in situ safely. Thus, to understand the
were cast in a copper-tin-zinc alloy with a modest lead
construction and condition of the Griffin, it was necessary
content of 1%–2%. The Griffin measures 1.07 m in height
to depend on photography, endoscopy, and a 3D scan of the
and 0.90 m in length (Figure 1). It has been the subject of
exterior and as much of the interior as could be reached.
extensive research over a long period, culminating in a
symposium in 2013, published in 2018 (Contadini 2018). When compositional analysis was first agreed in the early
It was most probably cast in Al-Andalus (Andalusia), in 1990s, portable analytical techniques such as X-ray fluo-
Moorish Spain, at the end of the 11th or beginning of the rescence (XRF) or laser-induced breakdown spectroscopy
214  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND ANALYTICAL INVESTIGATIONS

(LIBS) were not available. Sampling was permitted in five

locations: a sample was cut from the finning inside the
body via a ventral opening and two were drilled from
Figure 3.
each wing. The remaining two samples were drilled from Metallography
a copper alloy vessel that had been discovered cast into of sample
the interior of the body, with the aim of determining from the
interior of the
whether it was cast integrally with the body or as a retrofit
Griffin (field of
(Figure 2). It is proposed that the vessel was part of an view: 100 µm)

apparatus for producing sound, in other words to make
the beast roar (Camber and Contadini 2018).

Figure 4a. Plot of tin against zinc for Pisa Griffin samples

Figure 2. The vessel in the interior of the Griffin

Pisa is close to the sea and metallography of the cut sample

(Figure 3) clearly showed the effects of centuries of expo-
sure. Here, EPMA allows the selection of corrosion-free
areas for analysis coupled with detection limits down
to 100 ppm for impurities and trace elements. Eighteen
elements were analysed, typically over 30 × 50 µm rasters,
with bivariate plots made for a number of element pairs,
for example tin vs zinc (Figure 4a) and iron vs antimony
(Figure 4b) (Northover 2018). From these data it is clear
that the two wings are not a pair and that they and the Figure 4b. Plot of iron against antimony for Pisa Griffin samples
vessel differ from the alloy of the body, showing that the
vessel was not cast integrally with the body.

The interior of the body and the vessel were later analysed
by both XRF and LIBS on uncleaned surfaces (Loren-
zetti et al. 2018). The results for the principal alloying
elements, zinc, and tin (Figure 4c) were broadly similar
for the body but probably reflect segregation in a large
casting, with the EPMA sample from the interior coming
from metal penetrating a crack in the core and solidifying
before the other areas analysed. Differences will also
arise from varying and, in the case of XRF and LIBS,
unknown effects of corrosion. For the vessel there was a
large difference: the drilled EPMA samples had corroded Figure 4c. Comparative analyses of tin and zinc for the Pisa Griffin
NON-INVASIVE ANALYSIS: THE MIRAGE AND THE REALITY 215

material discarded, and higher zinc contents and lower

tin contents relative to the corroded surface are to be
expected (Figure 4c). Also, in the EPMA data the impu-
rity pattern in the body with, for example, a lower iron
and higher antimony concentration confirms its differ-
entiation from the vessel. We must conclude that, when
understanding the composition and construction of an
object is crucial to understanding its history, appropriate
sample-based analysis is essential.
Figure 5a. Copper bolt from HMS Impregnable

Copper fastenings
The beginning of this project was a post-excavation
study of copper bolts from the wrecks of two Royal Navy
ships, the 96-gun HMS Impregnable (completed 1786,
lost 1799) and the frigate HMS Pomone (completed
1895, lost 1811). Cut samples were taken for optical
metallography and EPMA (Figures 5a–c) (Northover
et al. 2015), with part of the work on Pomone being tele-
vised. It quickly became apparent that the copper used
by the Royal Navy was very uniform in character, with
arsenic, bismuth, silver, and lead being the principal
Figure 5b. Detail of bolt showing Government broad arrow and Forbes
impurities, and all the bismuth and part of the arsenic works stamp
being present as oxide inclusions. The copper came
from mines in Cornwall and on the island of Anglesey
in north-west Wales, the same copper that was used for
the British copper coinage from 1797 and exported to
the Philadelphia Mint in the United States of America
for striking ‘Liberty Head’ cents. It also became apparent
that the generally accepted history of the use of copper
fastenings by the Royal Navy was wrong. The outcome
has been continuing work to understand the metallurgy
of the bolts and to correlate this with documentary
research to create a better history.

From the first voyage in 1761–63 of HMS Alarm, the first

Royal Navy vessel to be copper sheathed as a protection
against the shipworm (Teredo navalis), the galvanic corro-
sion caused by the contact between copper sheathing
and iron fastenings in seawater was recognised. As an
experiment, the 14-gun HMS Swallow, built in 1769, was
ordered to be copper fastened; despite its loss in 1776, the
experiment was deemed a success and, at the beginning of
1777, six vessels up to 32 guns were ordered to be copper
fastened. The bolts were forged with a trip hammer and a
swage and were delivered by William Forbes, the Navy’s
copper contractor. Miraculously, when Forbes retired
in 1793 he took his business archive with him, and it
is now preserved by Falkirk Community Archives in
Figure 5c. Microstructure of copper bolt from Impregnable
Scotland and housed in the mansion Forbes built for his
retirement. In conjunction with Admiralty records, this
previously unexplored archive offers us a very complete
paper trail for this history.
From 1777 onwards, the size of vessels that it was deemed
to be safe to bolt with copper increased until, in 1783,
it was ordered that all new construction, including the
largest battleships, should be copper fastened. This was
quickly followed by the order to re-fasten all existing
iron-fastened ships with copper. To achieve this, the
216  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
production of copper bolts had to be rapidly expanded
and, since forging was too slow, rolling mills with grooved
rolls were introduced and three separate patents for hot
and cold rolling taken out in 1783.
Characterisation of the copper continued to be by
EPMA and optical microscopy followed up by other
techniques in order to answer questions raised by the
metallography. In particular, it was necessary to explain
microstructures which showed elongated grains, but no
slip traces or deformation twins could be etched. The
suggestion was made that electron backscatter diffrac-
tion (EBSD) could assist (Northover and Northover
2012); fortuitously, the routine of polishing and etching
used for the metallography proved to be the ideal
Figure 6a. Drawing from specification of William Collins’s patent No.
1388, 2 October 1783 (image from Sheffield City Library)
Figure 6b. Wire texture data from a Collins bolt
ANALYTICAL INVESTIGATIONS
preparation for EBSD as well. One of the first results
was to identify a wire texture in a bolt from Pomone,
implying that it had been produced following William
Collins’s patent of 1783, which used grooved rolls to
grip a copper bar to pull it through a die (Figure 6a–b).
(Texture describes the distribution of preferred orienta-
tions of grains produced when metal is worked and heat
treated, with different textures correlated with different
processes.) Thus, although it was not possible to assign
a bolt to a source by its composition, some at least could
be linked with a maker through their texture.
Copper bolts were produced in a large range of sizes, up
to 60 mm in diameter and 4 m or more in length and, as
noted above, produced by forging, rolling, or drawing,
or, indeed, a combination of these processes. Add to this
the stresses incurred in driving the bolts, the workings of
a ship’s hull at sea, and the breaking up of the hull when
wrecked, all of which add complexity to the pattern of
textures in a bolt. To map this using cut samples would
be unnecessarily destructive, but the same results can
be achieved using neutron diffraction techniques. This
work is being carried out at the ENGIN-X beamline at
the ISIS neutron source at Harwell, England. A complete
bolt, held by a robot, can be moved through a range of
positions and orientations with crystallographic data
collected at each location; the analysed volume at each
step might be a 4 mm cube. Copper is a good absorber
of neutrons and so there is a limit to the path length
through the copper that can usefully be used; data
collection is slow, and it may take 24 hours per bolt. A
bolt from HMS Impregnable in position in the Cyberman
robot is shown in Figure 7a and typical texture results in
Figure 7b (Malamud et al. 2016, Malamud et al. 2017).
Despite this slow rate, neutron diffraction is seen as the
only realistic approach.
So far only bolts produced after the introduction of
rolling/drawing in 1783 have been studied, but a bolt
from HMS Crocodile, one of a batch of six copper-fas-
tened ships ordered in 1777, and certain to be forged, is
now available. Work will also be done on bolts used by
the merchant fleet and those used on French ships of the
same period, mainly using technology exported from
Britain; an application for beam time will be available
shortly (to date, all applications for this project have been
successful). Where good cross-sections of bolts are avail-
able, micro-hardness maps can also be made but, so far,
they have proved challenging to interpret and correlate
NON-INVASIVE ANALYSIS: THE MIRAGE AND THE REALITY
Figure 7a. Bolt
from Impregnable
at ENGIN-X

Figure 7b. Typical texture data from ENGIN-X
with the texture data. One precious asset is that two sister
ships of Pomone are still afloat, HMS Trincomalee and
HMS Unicorn. Remarkably, Unicorn was never taken into
service and, apart from being towed from the Thames to
Dundee in Scotland, it has never been to sea. It is to be
hoped that we can access some of the bolts and so exclude
some variables from our texture studies.
Must Farm
The post-excavation project design for the metallurgical
study of the bronze artefacts from the Late Bronze Age
217
pile-dwelling settlement at Must Farm had several objec-
tives, namely, to determine:
• the alloys used and possible correlations with the
types of object;
• the impurity patterns and the evidence they provide
for the origins of the metal;
• the results of lead isotope analysis of selected pieces;
• the quality of manufacture;
• given the short period of occupation, whether there
was any evidence that particular tools or weapons
were new, or if these had been brought to the site by
the settlers;
• the nature of a container of scrap metal;
• the condition of the objects on the day of the fire;
• the impact of the fire on each object and how this
correlated with the forensic investigation of the fire;
and
• the different states of corrosion of the bronze and their
relationship with the different environments in which
they were left after the fire.
It was agreed that all objects, where their condition
allowed, would be analysed by EPMA on cut samples,
which would then be available for metallography.
Sampling and sample preparation used the same methods
as for the two projects already described; samples for
lead isotope analysis were drilled from within the cut
made with the saw.
The significance of the site lies in the way in which it
was abandoned with a full range of domestic equip-
ment – bronze, ceramic, wood, and other materials
were left behind, meaning we can learn what the typical
possessions of a household were. It should be noted that
potentially ‘elite’ objects such as swords and sheet bronze
vessels were present only as fragments, suggesting that the
settlement itself was not of particularly high status. Also
of great importance is the exact dating of the site through
dendrochronology and radiocarbon to the middle of
the 9th century BC, because such precise dates for Late
Bronze Age metalwork in Britain are scarce.
The selection of alloys was typical for the British Late
Bronze Age, with leaded bronze for cast objects and
unleaded bronze for sheet, the lead often being residual
from scrap bronze. Tin contents were mainly 7%–11%
with a few around 3% tin, and some specialist tools such
as chisels with 12% tin or more. The impurity patterns
were those common in eastern England at the time
(arsenic, antimony, nickel, and silver), with much of the
218  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND ANALYTICAL INVESTIGATIONS

metal imported from the Continent and lead added in

England. The scrap bronze found in a wooden container
had just the same characteristics and was, presumably,
from objects broken in use, or just found, and collected
to exchange for new bronze. None of the Must Farm finds
appeared new to the site.

The metallographic study was keenly awaited: previous

studies of fire-damaged ancient metalwork were from
cremations and none from an extensive fire such as that
which engulfed Must Farm. The author has developed
a system for tabulating metallographic data so as to give
a simple overview of an assemblage and to allow some
Figure 8a. Partially melted medium tin leaded bronze bucket fitting
variables to be treated quantitatively. The system was
(scale bar: 20 µm)
pioneered for a large metalworker’s hoard from Arbedo,
Ticino, Switzerland (Northover 1998), and extended to
fire-damaged bronze from the Late Bronze Age/Early
Iron Age cemetery at Bischofshofen-Pestfriedhof, Austria
(Northover 2009), and a Late Bronze Age weapon assem-
blage in Norfolk (Bridgford and Northover 2020). This
was also done for Must Farm and it was found that the
most severely heat-affected microstructures correlated
strongly with the hotspots found in the forensic study of
the fire. Although the excavation is now in the course of
publication, there is still more work to be done, especially
with understanding partially melted structures (e.g.
Figures 8a–b). Sadly, the detailed analysis and micros-
copy needed cannot be funded even from a generous Figure 8b. Partially melted and quenched low tin bronze from cast bronze
excavation budget. vessel (scale bar: 50 µm)

All the analysis from Must Farm so far has been carried
out on cut samples; a typical sample size is 2–3 mm across,
although useful results can be obtained from a sample of
less than 1 mm diameter. Nonetheless, there is one area
where a non-invasive, surface analysis would have been
of great benefit, and that is in mapping the occurrence of
sulfide corrosion, given the areas of waterlogged, anaer-
obic conditions across the site. Not every bronze need
be analysed, only sufficient to characterise the different
types of patina so that sulfide corrosion can be identi-
fied visually and mapped photographically. Because the
sulfur K X-ray lines are of low energy, the most effective Figure 9. An example of the patination of bronze tools from Must Farm
approach would be either XRF or PIXE with a helium
flush or, for preference, a vacuum chamber. If such an Discussion
experiment were funded it would offer a requirement and
To achieve the greatest benefit from the input of the
a boon to conservators, the requirement being to ensure
as accurately as possible the surface appearance and the metallurgist to the study and interpretation of the arte-
boon to offer a simple approach to understanding objects facts discussed in each of these case studies, it is very clear
with sulfide corrosion. that the optimum approach to such study is a combina-
NON-INVASIVE ANALYSIS: THE MIRAGE AND THE REALITY
tion of non-invasive and sample-based analyses. We must
now consider how this impacts the decision-making of
the conservator and curator.
Perhaps an antipathy to sampling has stemmed from
scholars in the past advocating samples that were unnec-
essarily large. It may be true that the bigger the sample,
the greater the possible return in information, but there
is a law of diminishing returns. Perhaps those analysing
ancient metalwork did themselves a disservice by a
concentration on provenance using drilled samples such
that asking for a metallographic sample was seen as a step
too far. It might also be said that the information to be
obtained from the present-day range of metallographic
techniques was never adequately explained. This is where
the conversations advocated in the introduction are so
important, and where the metallurgical input must be
supported by a demonstration of typical sample sizes
and sites, and the range of information to be gained from
combining current metallographic techniques, not least
the pattern and extent of the corrosion.
It can be argued that invasive sampling, however minimal,
can be avoided because methods still being developed
will allow essential data to be collected non-invasively.
This is unlikely, but even if it were not, there are still
two constraints: the laws of physics and cost. An impor-
tant consequence of the former is a lack of resolution,
both spatial and spectral, and extended time scales for
collecting data. In contrast, a cut sample can provide a
quantitative analysis for, say, 18 elements at a detection
limit down to 100 g/g and optical micrographs for GBP
50 per sample, with multiple samples each day. The same
sample can then be preserved for future use, for example
for stable isotope analysis by laser ablation inductively
coupled plasma mass spectrometry, eliminating the need
for further analysis.
From the non-invasive perspective, making CT and 3D
scans more accessible to museums and archaeology would
be enormously helpful, especially in imaging the mechan-
ical state of an object (as with the Griffin), mapping
corrosion and particle distributions, and guiding sample
selection. Neutron imaging and diffraction methods are
also powerful, as seen in the discussion of the copper
bolts, but none of these can contribute the compositional
data at the level required to inform the conservator, the
curator, the archaeologist, and the metallurgist. This
brings us back to the start of these arguments: the need
for a proper definition of what is required by each party
219
to the project and of the methods needed to obtain it,
with no a priori assumptions about the use of either
analytical approach. The outcome must be an appropriate
balance between non-invasive and invasive techniques,
however minimalist the latter might be. Those should be
the keywords in the future: appropriate analysis.
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Author
Peter Northover was born in Oxford and grew up in
the Isle of Wight. He read metallurgy at the University
of Oxford, having worked at the metallurgy lab of West-
land Aircraft at Cowes, Isle of Wight, between school
and university. He graduated in 1970 and went on to a
DPhil in metallurgy with a thesis on stress corrosion and
hydrogen embrittlement in controlled transformation
stainless steels. Since 1974 he has pursued the applications
of metallurgy in archaeology, specialising in non-ferrous
metals, producing well over 200 publications. Since
retiring from the University of Oxford in 2014 he has
specialised in copper and copper alloys of the industrial
revolution, especially for ships and railways.
An Analytical Study of the Corrosion Behavior and
Microstructural Properties of a Group of Copper Alloy
Artifacts from the Khirbet Yajuz Archaeological Site, Jordan
Ahmad N. Abu-Baker*
Department of Conservation and Management of Cultural Resources, Faculty
of Archaeology and Anthropology, Yarmouk University
Irbid, Jordan
ahmad.abubaker@yu.edu.jo
Abstract
In this study, the composition, corrosion, and microstructure
of a group of four copper alloy artifacts excavated from the
Byzantine cemetery at the Khirbet Yajuz archaeological site,
Jordan, were investigated. Scanning electron microscopy
coupled with energy-dispersive X-ray spectroscopy (SEM-
EDX) analyses of a necklace, a bracelet, a paten, and a spatula
showed that they were made of quaternary copper-zinc-
tin-lead alloys. X-ray diffraction (XRD) analysis revealed the
presence of cuprite (Cu2O), cornetite (Cu3PO4(OH)3), sampleite
(NaCaCu 5(PO 4) 4Cl·5H 2O), spencerite (Zn 4(PO 4) 2(OH) 2·3H 2O),
pyromorphite (Pb 5(PO 4) 3Cl)), malachite (CuCO 3·Cu(OH) 2),
atacamite/paratacamite (α- and γ-Cu2(OH)3Cl), and cotunnite
(PbCl2) as the corrosion products. SEM-EDX and EDX elemental
mapping were conducted to determine the corrosion
stratigraphy and elemental distribution in the corrosion
layers and original alloy. The metallographic examination
showed various degrees of working and heat treatment in
Introduction
Archaeological copper alloy artifacts form an important
part of cultural heritage collections. Analytical investi-
gation of these artifacts is essential to understand their
chemical, physical, and mechanical characteristics. Iden-
tification of their corrosion products and the processes
involved in their formation can shed light on the archae-
ological context and determine the preservation state
and conservation needs. The conservation literature
includes several studies that investigated archaeological
copper alloy artifacts and identified their composition
and corrosion characteristics using various analytical
techniques (Fabrizi et al. 1989, Abu-Baker 2008, Ingo
et al. 2010, Oudbashi et al. 2016, Papadopoulou et al.
2016, Abu-Baker and Al-Qudah 2017, Fan et al. 2020,
Abu-Baker et al. 2021). The results of those studies
have helped to demonstrate the link between long-term
Lutfi A. Khalil
Department of Cultural Resources Management and Conservation, Faculty of
Archaeology and Tourism, The University of Jordan
Amman, Jordan
lakhalil@ju.edu.jo
*Author for correspondence
the manufacture of the artifacts. The uncommon presence
of phosphate corrosion products was attributed to the
phosphate species released by the hydrolysis of hydroxyapatite
(Ca 5(PO 4) 3OH) from the skeletal materials in the adjacent
bodies buried in the cemetery. The resulting formation of
insoluble phosphate corrosion products on the surface of
the artifacts improved their stability and reduced the risk of
activating the cuprous chlorides present in the internal pits
and the dezincification of these artifacts in the uncontrolled
environment of their storage area. The conservation options
for the artifacts include direct intervention using corrosion
inhibitors as well as preventive conservation measures, such
as by controlling the relative humidity.
Keywords
Khirbet Yajuz, copper alloy, corrosion, microstructure, copper
phosphates, zinc phosphates, lead phosphates
corrosion processes, the exposure conditions (e.g., burial,
exhibition, or storage), and metallurgical aspects of the
studied artifacts. The diverse range of corrosion mecha-
nisms and products associated with copper alloy artifacts
emphasizes the importance of comprehensive analytical
investigation to elucidate the particular characteristics of
the artifacts with respect to their context, which in turn
will allow a determination of their conservation needs.
As an example, a multi-analytical investigation of a group
of four copper alloy artifacts excavated from the graves
of the Byzantine cemetery at the Khirbet Yajuz archae-
ological site in Jordan were investigated. The aim was to
identify the composition, corrosion, and microstructural
properties of the artifacts and thus their archaeological
context and corrosion processes in order to develop
appropriate preservation and conservation strategies.
222  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Figure 1. The copper alloy artifacts under investigation: (a) necklace, (b) bracelet, (c) paten, and (d) spatula
Materials and methods
The artifacts that were the focus of this study consisted
of a necklace, a bracelet, a paten, and a spatula. They are
representative of dozens of similar artifacts excavated
from the Khirbet Yajuz archaeological site, which is
located on a hill situated about 11 km northwest of the
center of Amman, Jordan. The site was inhabited in
the Roman, Byzantine, Umayyad, and Abbasid periods,
as indicated by the architectural and material finds
discovered during excavations (Khalil 1998). The arti-
facts are heterogeneously corroded, broken, and have
missing parts (Figure 1). They have yet to be analytically
assessed since their discovery and placement in the
storage area of the University of Jordan Archaeological
Museum (UJAM) in Amman some 25 years ago. The
fluctuating relative humidity and other corrosive agents
in the uncontrolled environment of the storage area
have had an adverse effect on the chemical stability and
physical integrity of the artifacts. It is expected that the
analytical investigation will enable their preservation
and conservation.
Scanning electron microscopy (SEM) coupled with ener-
gy-dispersive X-ray spectroscopy (EDX) spot analysis
and X-ray elemental mapping were used to study the
corrosion stratigraphy and elemental distribution in the
original alloys and corrosion layers. One cross-section
was taken from each artifact and prepared according to
the procedure described in Abu-Baker et al. (2021). A
FEI-Quanta 600 scanning electron microscope coupled
with an energy-dispersive X-ray spectroscopy analyzer
was used for this analysis. Wet mode at 0.5 Torr H2O and
an electron beam of 30 kV were employed. The samples
were gold-coated before their analysis to avoid charging
effects at the corroded edges of the cross-sections.
ANALYTICAL INVESTIGATIONS
The corrosion products of the artifacts were analyzed by
X-ray diffraction (XRD) analysis using a Rigaku ultima
IV X-ray diffractometer operating at 40 kV and 40 mA.
A small amount of the corrosion products was scratched
off from the surface of each artifact, then mixed and
dispersed in ethanol and spread on a microscopic glass
slide. After evaporation of the ethanol, the slide was
placed in the XRD instrument for analysis. The X-ray
was generated from an anticathode copper (Cu) tube
with a wavelength CuKα= 1.54178 Å. The analysis range
was 5°–95° 2θ and the scan speed was 3° per minute.
The embedded cross-sections were also examined using
an Optika IM-3MET inverted metallurgical microscope
to investigate their corrosion profile. They were then
etched with alcoholic ferric chloride to investigate their
microstructures using bright-field and cross-polarized
light microscopy (PLM) to determine the respective
manufacturing techniques (Scott 1992, 72). The photo-
micrographs were taken using an Optika C-P8 digital
camera attachment.
Results and discussion
Alloy compositions and microstructures
SEM-EDX analysis of the necklace’s internal alloy showed
a quaternary Cu-Zn-Sn-Pb alloy. The SEM image and
EDX elemental mapping showed a homogeneous distri-
bution of Zn and Sn in the Cu-rich α-phase, with Pb
appearing as separate globules randomly distributed in
the alloy (Figure 2a). On the PLM image of the etched
internal alloy of the necklace, recrystallized equiaxed
α-grains together with annealing twins and white lead
globules were seen (Figure 2b). The repeated cycles of
working and annealing were finished by an annealing
process, as indicated by the presence of straight annealing
AN ANALYTICAL STUDY OF THE CORROSION BEHAVIOR AND MICROSTRUCTURAL PROPERTIES OF A GROUP OF COPPER ALLOY ARTIFACTS FROM THE KHIRBET YAJUZ ARCHAEOLOGICAL SITE, JORDAN
twins; however, coring in the copper-rich α-phase was
not completely removed by the annealing process (Scott
and Schwab 2019, 154).
According to the SEM-EDX analysis, the bracelet’s
internal alloy is a quaternary Cu-Zn-Sn-Pb alloy. The
SEM image showed air porosity and white lead globules,
Figure 2. SEM-EDX, EDX elemental mapping (a), and PLM (b) of the
internal alloy of the necklace
223
also apparent on the EDX elemental mapping image. The
zinc and tin had completely solubilized in the copper,
resulting in their homogeneous distribution in the
alloy (Figure 3a). The PLM image of the etched internal
alloy showed recrystallized equiaxed α-grains and white
lead globules (Figure 3b). The small grains suggested
repeated cycles of working and annealing and a final
Figure 3. SEM-EDX, EDX elemental mapping (a), and PLM (b) of the
internal alloy of the bracelet
224  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND ANALYTICAL INVESTIGATIONS

annealing process, as indicated by the presence of straight Corrosion characteristics

annealing twins; however, as in the necklace, coring in
XRD analysis
the copper-rich α-phase was not completely removed
by the annealing process (Scott and Schwab 2019, 154). The XRD analysis of the four artifacts revealed
SEM-EDX analysis of the paten’s internal alloy was cuprite (Cu 2 O) and copper phosphate minerals,
consistent with a quaternary Cu-Sn-Zn-Pb alloy. The such as cornetite (Cu 3(PO 4)(OH) 3) and sampleite
EDX elemental mapping images showed the even distri- (NaCaCu5(PO4)4Cl·5H2O), as the main corrosion prod-
bution of zinc and tin in the copper matrix, with a small
amount of lead present as elongated, chloride-corroded
globules (Figure 4a). The bright-field image of the
etched internal alloy revealed a partially recrystallized
microstructure with some annealing twins and lead
globules; however, coring remained from the cast alloy,
which together with the weakly defined grain structure
indicated that the paten had not been extensively worked
or annealed. The presence of slip lines and intergran-
ular cracks suggested cold working, probably to finish
the surface decorations, without sufficient annealing
(Figure 4b) (Scott and Schwab 2019, 154).
The SEM-EDX analysis of the spatula’s internal alloy
indicated a quaternary Cu-Zn-Sn-Pb alloy. The SEM
image together with EDX elemental mapping showed
spherical and elongated lead globules distributed in the
alloy, and zinc and tin that were completely solubilized in
the copper and distributed homogeneously (Figure 5a).
The partially recrystallized grains appearing under
bright-field illumination suggested that the cast artifact
had been annealed for a short time at high temperature
or for a longer time at a moderate temperature. The
presence of slightly curved annealing twins and a series
of slip lines indicated cold working without sufficient
annealing, to give the artifact its final shape (Figure 5b)
(Giannossa et al. 2013; Scott and Schwab 2019, 154).
The four artifacts are made of quaternary Cu-Zn-Sn-Pb
alloys. As decorative and cosmetic objects, the presence
of large amounts of zinc, particularly in the necklace and
bracelet, give the alloy an attractive golden color. In the
3rd century AD, quaternary Cu-Zn-Sn-Pb alloy (modern
leaded gunmetal) was used regularly and was made by
mixing pure brass, freshly made using a cementation
process, with scrap bronze, which decreased the amount
of zinc from 22%–28% to around 13% and added tin
into the composition of the alloy. Lead was either added
deliberately to reduce the melting point and improve the
fluidity and casting properties of the alloy or due to the
use of copper ores containing lead minerals. The small
amount of tin increased the hardness and durability of Figure 4. SEM-EDX, EDX elemental mapping (a), and bright-field image
the alloy (Craddock 1978, Thornton 2007). (b) of the internal alloy of the paten
AN ANALYTICAL STUDY OF THE CORROSION BEHAVIOR AND MICROSTRUCTURAL PROPERTIES OF A GROUP OF COPPER ALLOY ARTIFACTS FROM THE KHIRBET YAJUZ ARCHAEOLOGICAL SITE, JORDAN
ucts. Significant amounts of the zinc hydroxy phosphate
mineral spencerite (Zn4(PO4)2(OH)2·3H2O) were detected
on the necklace, bracelet, and paten, and the lead minerals
pyromorphite (Pb5(PO4)3Cl) and cotunnite (PbCl2) on
the spatula. The basic copper chlorides atacamite/parat-
acamite (α/γ-Cu2(OH)3Cl) are also present in significant
amounts on the bracelet and the spatula, while malachite
Figure 5. SEM-EDX, EDX elemental mapping (a), and bright-field image
(b) of the internal alloy of the spatula
225
Figure 6. XRD analysis of the corrosion products: (a) necklace, (b) bracelet,
(c) paten, and (d) spatula
(CuCO3·Cu(OH)2) is a minor corrosion product found
on all of the artifacts (Figure 6).
Cuprite is the first corrosion product to form in the pres-
ence of oxygen and moisture, and the predominant oxide
of copper that appears over a wide range of conditions
(Scott 2002, 82). Malachite forms over cuprite, due to the
dissolution and precipitation of the oxide as copper(II)
salts; its presence indicates a high carbonate content
at a pH of 7.5 or higher (Eary 1999). The presence of
atacamite/paratacamite and the absence of nantokite
(CuCl) in the XRD results suggested that the initially
formed nantokite in the burial soil underwent oxidative
hydrolysis, with the formation of atacamite/paratacamite
under the uncontrolled storage conditions. The artifacts
have either been stabilized by this reaction or are in a
metastable state if nantokite is present deeper in the alloy
such that it was not collected in the samples obtained
for XRD analysis (Scott 1990). SEM-EDX analysis of
the cross-sections will help to distinguish between these
possibilities.
Cornetite (Cu 3(PO 4)(OH) 3) was identified on four
artifacts and sampleite (NaCaCu5(PO4)4Cl·5H2O) on
three. The phosphoric species causing the formation of
these copper minerals in the burial environment was
hydroxyapatite (Ca5(PO4)3OH), which is the main inor-
ganic material of bones and teeth. The decomposition
of the adjacent buried bodies in the graves where the
artifacts were found resulted in the release of phosphate
ions, which induced the formation of copper phosphate
minerals. The reaction leading to the formation of
cornetite by cupric ions in contact with hydroxyapatite
and ground water is shown in Equation (1):
226  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND ANALYTICAL INVESTIGATIONS

Ca5(PO4)3OH + 6Cu2+ + 5H2O → 5Ca2+ + and faster than Cu+1 ions, which have an ionic radius
2Cu3(PO4)(OH)3 + H2PO4− + 3 H+  (1) of 0.096 nm (Ravichandran and Rajendran 2005, Ingo
et al. 2010, Papadopoulou et al. 2016). The PLM of the
According to the equation, H2PO4− and H+ resulting
unetched cross-section shows the blue-green corrosion
from this reaction will cause the formation of cornetite
layer, which mainly contains cornetite and sampleite,
(or other copper hydroxy phosphate minerals). The
over a thin white band that is probably the spencerite
presence of sampleite can be attributed to the soluble
sodium and chloride ions in the ground water of the
burial environment, which react with the cupric and
phosphate ions to form this mineral (Fabrizi et al. 1989;
Bruckner et al. 1993; Scott 2002, 243; Fan et al. 2020). The
hydrogen phosphate ions resulting from the hydrolysis
of hydroxyapatite also react with the released zinc ions
and form spencerite (Zn4(PO4)2(OH)2·3H2O) (Chen et al.
2016). The formation of compact zinc phosphate minerals
hindered Cu(I) dissolution and improved the corrosion
resistance of the alloy (Yohai et al. 2011).

Pyromorphite (Pb5(PO4)3Cl) is a stable lead mineral

found in a wide range of geochemical environments.
The Pb(H2PO4)2 and PbHPO4 formed by the reaction
of Pb2+ with the H2PO4− and HPO42− ions resulting from
the hydrolysis of hydroxyapatite can be converted to
pyromorphite at pH values above 2.7 and 4.7, respectively
(Nriagu 1973, Fan et al. 2020). In addition to pyromor-
phite, the XRD analysis revealed cotunnite (PbCl2) in
the spatula. Cotunnite is a stable lead corrosion product
under acidic and high-chloride-containing microenvi-
ronments (Selwyn 2004, 122).

SEM-EDX, EDX mapping, and PLM

SEM-EDX analysis and EDX elemental mapping of the

necklace’s corroded edge showed an external layer that
mainly contains Cu, with variable amounts of P, C, O,
Zn, Pb, Sn, Cl, and Fe (Figure 7a, area a). Accordingly,
cornetite and sampleite predominate, while the layer
in Figure 7 marked (b) is richer in Zn, indicative of the
presence of spencerite, and the thin band marked (c)
contains Cu, C, and O, i.e., the elements of malachite
detected in the XRD analysis. The internal layer marked
(d) has a higher O content, attributable to the presence of
cuprite, while the EDX results of the white area marked
(e) are consistent with lead or lead minerals. Finally, the
internal corrosion pits marked (f) are zinc depleted and
rich in Cu and Cl, which suggests a dissolution of the
more anodic metal, zinc, from the alloy and the pres-
ence of cuprous chloride corrosion cells. The corrosion
process is controlled by diffusion such that anodic Zn+2 Figure 7. SEM-EDX, EDX elemental mapping (a) and PLM (b) of the
ions, with an ionic radius of 0.070 nm, diffuse easier corroded edge of the necklace
AN ANALYTICAL STUDY OF THE CORROSION BEHAVIOR AND MICROSTRUCTURAL PROPERTIES OF A GROUP OF COPPER ALLOY ARTIFACTS FROM THE KHIRBET YAJUZ ARCHAEOLOGICAL SITE, JORDAN
detected by XRD and SEM-EDX. This is followed by
red-brown cuprite and a lead-rich white layer. The dark
red areas of internal dealloying were zinc depleted by the
selective removal of the more anodic metal in the alloy,
i.e., dezincification (Figure 7b).
SEM-EDX analysis and EDX elemental mapping of the
bracelet’s external corroded edge showed the presence of
Cu, Zn, Pb, C, O, P, and Cl (Figure 8a, area a), indicative
of the presence of mixed oxide, carbonates, and phosphate
Figure 8. SEM-EDX, EDX elemental mapping (a), and PLM (b) of the
corroded edge of the bracelet
227
minerals of copper, zinc, and lead, as detected in the XRD
analysis. Similar to the corrosion process of the necklace,
the internal corrosion area has been zinc depleted and is
rich in products, reflecting the chloride-based corrosion
of Cu (area b) or Sn (area c), both of which are susceptible
to oxidative hydrolysis. On the bracelet’s unetched PLM
image, the external blue-green and white corrosion prod-
ucts were analytically identified as cornetite, sampleite,
and spencerite intermixed with atacamite/paratacamite
and malachite, followed by a red-brown cuprite layer and
lead-rich white spots (Figure 8b).
SEM-EDX analysis and EDX elemental mapping of the
paten’s external corroded area showed the presence of
Cu, Zn, P, Pb, O, C, and Cl (Figure 9a), corresponding
to the cuprite, cornetite, sampleite, spencerite, and
pyromorphite identified by XRD. On EDX elemental
mapping, the zinc can be seen to have diffused and
subsequently formed precipitated minerals in the external
phosphate-rich corrosion layer, while the zinc-depleted
internal layer is rich in Cu and Cl, which form active
corrosion cells, as discussed above. The paten’s unetched
PLM image shows the blue-green, white, and red-brown
layers of the previously identified corrosion products
(Figure 9b).
The SEM-EDX analysis and EDX elemental mapping
of the spatula’s external corroded edge showed large
amounts of Cu, O, Cl, and C, and thus the presence
of atacamite/paratacamite and malachite (Figure 10a,
area a). The significant amounts of Pb, O, and P present in
the second corrosion layer (area b) indicate the presence
of cuprite, cornetite, and pyromorphite. In Figure 10, area
(c) is richer in Sn, which suggests that tin(IV) oxide forms
a primary thin corrosion layer underneath the secondary
copper corrosion products. Consistent with the EDX
elemental mapping, the internal intergranular corrosion
is Cu depleted and rich in Pb and Cl (area d), which
suggests a decuprification of the copper-rich α-phase
in an oxygenated burial microenvironment as well as
the presence of lead chloride minerals such as cotun-
nite (PbCl2), as detected by XRD analysis. The spatula’s
unetched PLM image shows stratified blue-green, white,
red-brown, and gray zones of the identified corrosion
products. These are followed by a strong intergranular
corrosion zone that extends to the internal alloy, due to
the decuprification that accompanied the chloride-based
corrosion of copper (Figure 10b).
228  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND ANALYTICAL INVESTIGATIONS

The metastable conditions of the artifacts indicated the caused the formation of copper phosphate minerals
beneficial effects of the copper phosphate corrosion that are stable and insoluble over a broad pH range, in
products, despite the presence of chloride ions in the contrast to the copper chloride minerals responsible for
burial soil and the poor environmental conditions in the bronze disease and thus active corrosion. In the storage
storage area. Phosphate ions can displace the less elec-
tronegative chloride ions critical to the active propagation
of corrosion pits (Lytle and White 2014). Therefore, in
the burial environment, the influx of negatively charged
phosphate anions near the corroding copper anode

Figure 9. SEM-EDX, EDX elemental mapping (a), and PLM (b) of the Figure 10. SEM-EDX, EDX elemental mapping (a), and PLM (b) of the
corroded edge of the paten corroded edge of the spatula
AN ANALYTICAL STUDY OF THE CORROSION BEHAVIOR AND MICROSTRUCTURAL PROPERTIES OF A GROUP OF COPPER ALLOY ARTIFACTS FROM THE KHIRBET YAJUZ ARCHAEOLOGICAL SITE, JORDAN
area, the insoluble copper phosphate corrosion products
likely prevented the diffusion of oxygen, water, and
corrosive anions into the corrosion pits or the nearby
cathodic region of the corrosion cell, which reduced the
risk of activating the cuprous chlorides present under
the external corrosion layers. Similarly, the formation
of the zinc phosphate spencerite seems to have reduced
corrosion resulting from dezincification in the zinc-rich
artifacts.
Conclusion
The multi-analytical investigation of copper alloy arti-
facts from the Khirbet Yajuz allowed their compositional
and microstructural properties to be determined. The
results of the chemical and microscopic investigations
showed the effects of the alloy’s composition and burial
environment on the types of corrosion products. The
formation of the insoluble phosphate corrosion products
on the surface of the artifacts increased their stability
and reduced the risk of activating the cuprous chlorides
present under the external corrosion layers and the
dezincification of these artifacts in the environmentally
uncontrolled storage area. Possible conservation options
for the artifacts to ensure their long-term stability include
direct intervention using corrosion inhibitors or preven-
tive conservation measures such as by controlling the
relative humidity to a stable value of < 40%.
Acknowledgments
This research was supported by a grant from the Gerda
Henkel Foundation.
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Authors
Ahmad N. Abu-Baker is the vice-dean of the Faculty of
Archaeology and Anthropology at Yarmouk University
in Irbid, Jordan. He is an associate professor of metals
conservation at the Department of Conservation and
Management of Cultural Resources.
Corrosion Analysis and Assessment of a Collection of
Archaeological Copper Alloy Objects from Sagzabad,
Northern Iran
Omid Oudbashi* Sepehr Bahadori
Department of Conservation of Department of Conservation of
Cultural and Historical Properties, Cultural and Historical Properties,
Art University of Isfahan Art University of Isfahan
Isfahan, Iran Isfahan, Iran
Department of Scientific Research, s.bahadori@aui.ac.ir
The Metropolitan Museum of Art
New York NY, USA
o.oudbashi@aui.ac.ir
Abstract
Among the most important objects excavated from the
archaeological site of Sagzabad in northern Iran is a collection
of metal objects that includes a significant number of copper
alloy objects. The objects were excavated during archaeological
activities at the site that spanned approximately 50 years. They
are now stored at the Institute of Archaeology, University of
Tehran. The condition of the copper alloy objects is not ideal,
and evidence of active corrosion is visible on some of them.
The environmental conditions appropriate for the storage
and long-term preservation of these objects have not been
established. The aim of this study was to determine the
conservation state of the copper alloy objects using analytical
tools. In addition to an assessment of the storage/display
environment, microscopic observations were used to determine
the condition of the objects. Eight samples were selected for
microanalytical study by metallography and scanning electron
Introduction
The archaeological site of Sagzabad, also known as Tappeh
Sagzabad, is located in the Qazvin Plain in northern
Iran (Figure 1a). This plain is a very important region
of prehistoric archaeological research in Iran, as it thus
far includes 30 archaeological sites containing archae-
ologically significant remains (Fazeli et al. 2005). The
Sagzabad site, together with Zagheh (Tappeh Zagheh)
and Qabristan (Tappeh Qabristan), was one of the most
important settlements in this region. At all three, the
stratigraphic layers form a sequence ranging from the
Neolithic to the Iron Age (6th to 1st millennium BC).
The sites are located close to each other, less than 3 km
along a straight line between Qabristan and Zagheh, with
Sagzabad located in between (Figure 1b, 1c). Based on the
findings of archaeological excavations that began in the
1970s by the Institute of Archaeology at the University
Ahmad Aliyari
Department of Archaeology,
University of Tehran
Tehran, Iran
aliyaria@ut.ac.ir
*Author for correspondence
microscopy with energy-dispersive X-ray spectroscopy. The
results revealed active corrosion or bronze disease due to the
burial of the objects in Cl−containing soil, which caused the
formation of copper oxide and copper chloride compounds.
A lack of environmentally controlled storage has exacerbated
the corrosion processes over several decades, leading to a
transformation of the remnant metallic structure into copper
corrosion products, and in some cases, the formation of new
copper chloride powdery compounds on the surface. Based on
the condition of the objects, a preservation strategy consisting
of preventive conservation measures for the collection is
proposed.
Keywords
archaeological copper alloys, corrosion, bronze disease,
preventive conservation
of Tehran, Zagheh was identified as a Neolithic village
dating to the 6th and 5th millennia BC, while Qabristan
was a settlement from the Chalcolithic period (5th and
4th millennia BC) that was abandoned in the early
3rd millennium BC. Sagzabad is a large settlement that
includes graveyards and dates from the Late Bronze Age
and Iron Age (Negahban 1973 and 1977).
During the excavation of Sagzabad a collection of metal
objects consisting of more than 200 copper alloy and a
few iron objects was recovered. The collection includes
weapons, tools and decorative objects made from copper,
tin bronze and arsenical copper (Mortazavi et al. 2011,
Oudbashi et al. 2021). All objects were recovered in
the 1970s during archaeological excavations at the site
directed by E.O. Negahban.
232  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
However, the objects have been stored under less-than-
ideal conditions, in storage enclosures such as boxes
and plastic bags (Figure 2a). A few objects are displayed
in showcases in the small museum of the Institute. No
climate control system is installed in the storage and
display spaces and no monitoring process was ever estab-
lished to evaluate the objects. Evidence of active corrosion
is visible on most of the objects and in some cases the
Figure 2. (a) Copper alloy objects excavated from Sagzabad. The objects
are stored in plastic bags, untreated and lacking preventive conservation
treatments. (b–e) Different groups of objects have been placed in a
single bag and show active corrosion, pale-green corrosion products
and spots on the surfaces of the objects. Some parts of objects are
completely corroded
ANALYTICAL INVESTIGATIONS
Figure 1. (a) Map of Iran
and the location of Qazvin
Plain in north-central Iran.
(b) Schematic view of the
location of three important sites
in the Qazvin Plain: Zagheh,
Qabristan and Sagzabad
(Negahban 1977). (c) Aerial
view of the region showing the
location of the archaeological
sites in the Qazvin Plain (image
 credit: map.google.com)
metallic substrate has been completely converted into
corrosion products (Figure 2b–e). This shows that the
burial environment was corrosive and that the storage/
display environment at the Institute was not appropriate
for the long-term curation of the collection. Thus, the
authors initiated a multi-analytical study to characterise
the corrosion morphology and processes and to assess
the conservation conditions.
Materials and methods
To study the corrosion morphology and assess the
condition of the objects, eight representative objects were
selected from the collection: two arrowheads, a ring, a
rod, a pin, a vessel, a fragment of an unknown object and
a broken pipe (Figure 3, Table 1).
Microscopic and microanalytical investigations were
conducted using a small sample (~2 mm thick) cut
from each object using a jeweller’s saw. The sample
was mounted in a two-part epoxy resin, and ground
Figure 3. The eight copper alloy objects analysed in this study. The
objects are from the Sagzabad collection, belonging to the Institute of
Archaeology, University of Tehran
CORROSION ANALYSIS AND ASSESSMENT OF A COLLECTION OF ARCHAEOLOGICAL COPPER ALLOY OBJECTS FROM SAGZABAD, NORTHERN IRAN 233

Table 1. Results of SEM-EDS of all phases marked in Figures 6 and 7 (SEM-BSE micrographs), reported in wt%

Object type Analysis Cu O Cl S Sn As Fe Pb Mg Al Si P K Ca

SAG-02 Arrowhead A 100 – – – – – – – – – – – – –
B 79 7.9 13 – – – – – – – – – – –
C 97 2.8 – – – – – – – – – – – –
D 36 25 1.5 – – – 3.8 – 1.3 4.7 25 – 1.3 1.5
E 83 1.0 16 – – – – – – – – – – –
SAG-04 Ring A 67 13 3.1 3.1 – – 0.4 – – 1.7 9.8 – 0.91 0.64
B 69 8.2 – 8.8 5.0 7.3 1.8 – – – – – – –
C 73 15 2.0 0.87 2.1 5.9 0.97 – – – – – – –
D 58 12 6.7 1.9 8.7 9.7 3.4 – – – – – – –
E 74 9.1 12 0.46 0.48 3.6 0.48 – – – – – – –
F 35 5.5 4.5 – 8.1 18 3.21 26 – – – – – –
G 18 10 – 1.9 46 15 7.78 – – – 0.9 – – –
SAG-05 Arrowhead A 100 – – – – – – – – – – – – –
B 97 3.2 – – – – – – – – – – – –
C 76 – 24 – – – – – – – – – – –
D 97 2.9 0.35 – – – – – – – – – – –
E 81 7.6 11 – – – – – – – – – – –
SAG-06 Fragmented rod A 8.3 41 0.19 2.3 – – 2.0 – 0.58 3.1 19 – 1.2 22
B 79 9.4 12 – – – – – – – – – – –
C 95 3.3 1.7 – – – – – – – – – – –
D 78 8.9 13 – – – – – – – – – – –
E 41 9.0 – – 1.0 33 – 16 – – – – – –
F 58 9.4 9.3 – 19 2.4 0.98 0.7 – – 0.29 – 0.02 0.66
SAG-07 Fragment A 81 6.9 12 – – – – – – – – – – –
B 84 3.6 1.7 – 9.7 – 1.5 – – – – – – –
C 16 9.4 0.05 – 71 – 3.9 – – – – – – –
SAG-08 Fragment of vessel A 90 – – – 9.7 – – – – – – – – –
B 88 1.2 – – 11 – – – – – – – – –
C 89 – – – 11 – – – – – – – – –
D 91 – – – 8.5 – – – – – – – – –
E 86 – – – 14 – – – – – – – – –
F 74 2.7 – – 23 – – – – – – – – –
G 92 – – – 8.5 – – – – – – – – –
SAG-09 Pipe A 96 – – – 3.7 – – – – – – – – –
B 76 – 24 – – – – – – – – – – –
C 69 1.6 17 – 12 – – – – – – – – –
D 97 3.2 – – – – – – – – – – – –
SAG-10 Pin A 100 – – – – – – – – – – – – –
B 97 3.1 0.2 – – – – – – – – – – –
C 66 14 3.4 – – – – – – – 5.9 5.9 0.87 3.5

and polished with abrasive paper and diamond paste,
respectively, to obtain a smooth and suitable surface. The
mounted cross-sections were initially observed without
etching and studied with low magnification optical
microscopy (OM), using a Zeiss reflected and trans-
mitted light microscope (model Primotech) with plane
polarised light (PPL) and crossed polarised light (XPL),
at the Central Laboratory of Art University of Isfahan.
The cross-sections were gold-coated for scanning elec-
tron microscopy coupled with energy dispersive X-ray
spectroscopy (SEM-EDS). The microstructure of each
sample was observed at different magnifications under
backscattered (BSE) mode. The chemical composition
of the layers and small phases was determined by EDS.
All available phases were analysed using an area analysis
to obtain accurate chemical data from the metallic and
234  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
corroded phases. The analysis was conducted using a
Philips XL30 scanning electron microscope, equipped
with a BSE detector and EDAX silicon drift detector
(HV: 20 kv and spot: 5) in the SEM laboratory of the
Faculty of Materials Engineering, Isfahan University
of Technology.
Results and discussion
Optical microscopy
Figures 4 and 5 show PPL and XPL micrographs of a
cross-section of each object. Complex corrosion crusts
can be clearly seen on the surfaces, and some objects
are completely corroded, consisting solely of corrosion
products. The objects were accordingly classified in two
main groups based on their corrosion stratigraphy:
• Completely corroded objects, in which the metallic
substrate has been completely converted into corrosion
products with different layers in various shades and
colours. Some evidence of the limit of the original
Figure 4. Optical microscopy images of cross-sections from samples
SAG-02, SAG-04, SAG-05 and SAG-06, showing the limit of the original
surface, under plane polarised light (PPL) and crossed polarised light (XPL)
ANALYTICAL INVESTIGATIONS
surface, referred to as the ‘limitos’ (Bertholon 2000), is
visible between the corrosion layers [samples SAG-04
(ring), SAG-06 (rod fragment) and SAG-07 (uniden-
tified fragment)].
• Partially corroded objects in which some parts of the
metallic structure are preserved underneath layers
of corrosion. The corrosion layers vary in thickness
and no uniform corrosion is visible on the surface of
the respective objects [samples SAG-02 (arrowhead),
SAG-05 (arrowhead), SAG-08 (vessel fragment),
SAG-09 (pipe), SAG-10 (pin)].
The corrosion crust is made up of corrosion layers with
a wide range of colours, from greyish-white to red,
green and sometimes blue, thus revealing the different
corrosion products that formed during burial and after
excavation.
The microstructure and corrosion morphology of sample
SAG-08 are of particular interest (Figure 5). The object
is partially corroded and a very thin layer of corrosion
Figure 5. Optical microscopy images of cross-sections of samples SAG-07,
SAG-08, SAG-09 and SAG-10, showing the limit of the original surface,
under PPL and XPL
CORROSION ANALYSIS AND ASSESSMENT OF A COLLECTION OF ARCHAEOLOGICAL COPPER ALLOY OBJECTS FROM SAGZABAD, NORTHERN IRAN
covers the surface, whilst the metallic structure is well
preserved. A partial needle-like grain microstructure is
visible, with numerous spread metallic islands (phases).
The corrosion rate is significantly lower than that of
the other objects in this study, although the needle-like
matrix is corroded in some areas and is visible due to
internal corrosion of the metallic structure, thus revealing
the grain shapes.
SEM-EDS
SEM-EDS revealed several aspects of the morphology and
mechanisms of corrosion. An analysis of the alloy compo-
sition of five samples (SAG-02, SAG-05, SAG-08, SAG-09,
SAG-10) by semi-quantitative EDS (Table 1) showed
impure copper in three samples (SAG-02, SAG-05,
SAG-10) and tin bronze in the other two samples (SAG-08
and SAG-09). The concentration of tin is 3.7 wt% in
sample SAG-09 but > 10 wt% in sample SAG-08.
Figure 6. Scanning electron microscopy in backscattered mode (SEM-
BSE) of cross-sections from all eight samples, including the marked
analysed phases reported in Table 1
235
The SEM-BSE micrographs showed differences in the
corrosion layers between the two groups (Figure 6),
consistent with the differences in the chemical composi-
tion of the layers. Table 1 presents the EDS results of the
areas analysed, as shown in the SEM-BSE micrographs
in Figure 6. Copper, oxygen and chlorine are the most
frequent major constituents. Tin, arsenic and lead were
detected in the internal corrosion layers and phases of
samples SAG-04, SAG-09, SAG-06, SAG-08 and SAG-07.
Soil elements, such as Si, Al and Mg, were detected based
on the composition of the external corrosion layers.
The microstructure of the completely corroded samples
includes a tin-rich phase in the centre of the cross-sec-
tions of samples SAG-04/G and SAG-06/F. This observa-
tion implies that both objects are made of tin bronze and
contain a central tin-rich phase, as previously observed
in other archaeological tin bronze objects (Oudbashi and
Emami 2010, Oudbashi 2015). The use of tin bronze in
Iran dates to the 3rd millennium BC (Late and Middle
Bronze Age) but it became widespread during the 2nd
and 1st millennia BC (Late Bronze Age and Iron Age)
(Pigott 2004, Oudbashi et al. 2021).
The results of the chemical analysis allowed two types of
corrosion layers to be distinguished: (i) corrosion layers
composed of copper and oxygen and (ii) corrosion layers
composed of copper and chlorine; with the additional pres-
ence of small amounts of oxygen and chlorine in all layers.
Accordingly, copper oxides and copper chlorides are the
main corrosion products, with their formation occurring
either during burial or during storage after excavation.
Figure 7. SEM-BSE micrograph of sample SAG-08 under higher
magnification shows the matrix and islands scattered in the
microstructure. The chemical composition of the marked phases is
reported in Table 1
236  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
SAG-08 was subjected to further analysis as its micro-
structure differs in several respects from the other
samples, as described above. The SEM-BSE micrograph
obtained at high magnification (200 ×) (Figure 7) shows
a microstructure similar to a typical so-called beta bronze
or white bronze (Scott 1991), which are high-tin bronze
alloys with a tin content of ~20 wt%. The alloy is heat-
treated and then quenched to retain the less brittle beta
phase, which can be more easily worked and avoids the
risk of embrittlement (Scott 1991). This technology was
already well known ~1000 years ago in Iran, India and
the Far East (Korea) (Park and Gordon 2007, Oudbashi
et al. 2017, Chattopadhyay et al. 2020). The earliest
examples of beta bronzes are from the Sassanid empire
in Iran (3rd to 7th centuries AD) (Oudbashi et al. 2017)
but the technique was widespread in the Iranian Plateau
during the Islamic period (10th to 14th centuries AD)
(Melikian-Chirvani 1974). Nevertheless, the chemical
analysis of the phases scattered in the microstructure of
SAG-08 showed that the tin concentration is lower than
in beta bronzes. Specifically, while high-tin bronze objects
have a tin concentration of ~20 wt%, the tin content of
sample SAG-08 is ~10 wt% (Table 1). Thus, the discovery
of object SAG-08 in the Sagzabad prehistoric site raises
many questions that remain to be explored.
Corrosion mechanisms and assessment
The analyses of the corrosion mechanisms, corrosion
morphology and stratigraphy of the eight copper alloy
objects provided several insights into the corrosion of
archaeological copper alloy objects. According to the
EDS results, two objects are made of tin bronze albeit
with differences in their tin concentrations (SAG-08 and
SAG-09), and three objects are made of impure copper
(SAG-02, SAG-05, SAG-10). For the three completely
corroded objects, analyses of their corrosion layers
showed the presence of tin-rich layers, suggesting
that they were originally made of tin bronze (SAG-04,
SAG-06, SAG-07). The corrosion rate of some objects
led to the complete conversion of the metallic structure
into corrosion products. In addition, in nearly all of the
samples the high concentrations of chlorine were detected
in some of the corrosion layers. Together, these obser-
vations indicate that the main corrosion mechanism in
the eight objects is bronze disease, an active corrosion
process driven by the presence of soluble chloride salts
and humidity in the burial environment (Scott 2002,
Selwyn 2006). Based on the chemical composition of the
ANALYTICAL INVESTIGATIONS
corrosion layers, the main corrosion products are copper
oxides (probably cuprite) and copper trihydroxychlorides
(probably atacamite and paratacamite), visible as the
red and green tonalities, respectively, seen in the OM
micrographs (Figures 4, 5).
The presence of a tin-rich corroded core in samples
SAG-04 and SAG-06 (and probably in sample SAG-07,
as observed in its OM micrograph) may be due to the
selective dissolution of copper, thereby increasing the
concentration of tin in the interior of the corroded
structure. This phenomenon, known as copper leaching
in tin bronzes, has been observed in many archaeological
objects buried in highly corrosive environments (Scott
2002, Oudbashi et al. 2010, Oudbashi 2015). The leaching
of copper during burial followed by the internal oxidation
of tin in the centre of the object corresponds to the type
II corrosion of tin bronzes, as described in the classifi-
cation system proposed by Robbiola et al. (1998). Those
authors together with Piccardo et al. (2007) proposed a
corrosion morphology classification system based on the
shape and sequence of the corrosion layers, the presence
or absence of the original surface and the thickness and
chemical composition of the corrosion layers. According
to this classification system, two types of corrosion are
visible in the tin bronze objects studied:
• Type I: This superficial, two-layered corrosion
morphology is characteristic of alkaline and moder-
ately corrosive soil burial environments. The original
shape (or original surface) of the artefact is retained,
and macroscopic traces of polishing or use may be
present.
• Type II: The corrosion morphology involves three
layers and is characteristic of corrosive chloride-con-
taining soil burial environments. The corrosion crust
is coarse (rough) and much thicker than in type I,
possibly transforming the artefact into a multi-layered
bulk material without any remaining metal.
In the Sagzabad copper alloy there is a predominance of
type II, although, in some cases, there is evidence of the
original surface in the corrosion products.
While the corrosion process may be partially influenced
by the original composition of the alloy, the analytical
results and literature reports (for example, Robbiola et al.
1998, Scott 2002, Piccardo et al. 2007) indicated that the
corrosion morphology and mechanisms of the sampled
objects were strongly influenced by the presence of chlo-
ride ions in the soil, leading to the formation of bronze
CORROSION ANALYSIS AND ASSESSMENT OF A COLLECTION OF ARCHAEOLOGICAL COPPER ALLOY OBJECTS FROM SAGZABAD, NORTHERN IRAN
disease, completely corroded objects and considerable
copper leaching during burial. Nevertheless, some objects
are not heavily corroded, and a significant amount of their
metallic structure has been preserved under the corrosion
crust. The corrosion layers in these objects (SAG-02,
SAG-09, SAG-10) are composed of copper oxides and
copper chlorides, likely reflecting the variable chloride
concentrations in different levels or areas of the soil and
thus the different corrosion rates, as observed at another
Iranian site (Haft Tappeh, southwestern Iran) with high
chloride concentrations in the soil (Oudbashi 2015).
Consequently, both known corrosion morphologies,
type I and type II, were observed in the Sagzabad copper
alloy objects (Robbiola et al. 1998, Piccardo et al. 2007).
Conservation strategy for the collection
The presence of bronze disease places the objects at high
risk of further corrosion, a situation made worse by the
fact that, currently, no suitable storage conditions are
available at the Institute of Archaeology. Furthermore,
since their excavation, the majority of the copper alloy
objects have not been treated by conservators. Only a few
objects are in display cases, and the majority of the copper
alloy objects are in storage (Figure 2). The archaeological
metal collection must be preserved in an environment
with low relative humidity (RH) to control active corro-
sion. The corrosion processes affecting some of the
objects have continued since their excavation or have even
been exacerbated during their storage or display at the
Institute over the last 50 years. Unfortunately, there are
no recorded data from the storage/display environment
of the collection and a monitoring strategy has yet to be
established. The institute is located in the north of Tehran,
which is humid during winter (average RH between 50
and 80%) but much dryer in summer (RH between 15
and 40%). The pale-green powdery corrosion products
visible on the surface of some objects may be copper
trihydroxychlorides, formed after exposure to the high
RH in the storage or display environment.
A preventive conservation plan that includes controlling
the RH to < 45% (Scott 1990) is necessary together with
a storage method in which the objects (currently stored
together in old plastic enclosures) are stored separately
in appropriate boxes and cabinets made of neutral (such
as polyethylene) or buffered materials. The RH can be
controlled by installing a dehumidification system or by
using silica gel or Art-Sorb boxes in the storage cabinets
237
or even inside the storage boxes. However, due to budget
limitations, mechanical methods of controlling the RH
may not be possible in the short term.
A plan to initiate ongoing monitoring of the collection is
needed. Conservators should also assess the condition of
all materials in storage (including the metal collection) as
a prerequisite to deciding the best method for the long-
term preventive conservation of the collection. Finally, an
interventional conservation approach by conservators is
needed, including stabilisation treatments of the objects
such as by desalination and inhibition methods. Indeed,
this study of the copper alloy objects from a collection in
Iran demonstrates the importance of having conservators
at the field excavation sites and at museums, to evaluate
the corrosion/deterioration processes after excavations
and during long-term storage.
Conclusion
In this study, the corrosion mechanisms and morpholo-
gies of eight copper alloy objects excavated from the site
of Sagzabad in northern Iran were investigated using
microscopy and microanalytical methods. The interac-
tion between the aggressive burial environment and the
copper alloy objects led to the formation of a variable
range of corrosion morphologies, mainly the selective
dissolution of copper in the tin bronze objects. Partially
thin corrosion crusts are observed in three objects. Most
of the objects have undergone type II corrosion (i.e.
complete corrosion of the object) and bronze disease,
but there are also a few cases of type I corrosion. As the
main corrosion products are copper oxides and chlorides,
the soil environment of the site was likely to have been
corrosive. This is supported by the high concentration
of chlorine in the corrosion layers of all objects and the
significant amounts of soluble chlorides, inducers of
bronze disease. To address the active corrosion process
and the unsuitable storage/display conditions at the Insti-
tute of Archaeology, University of Tehran, a preventive
conservation plan, including proper storage cabinets
and boxes, as well as a method to control the RH in the
storage and display areas, were proposed.
Acknowledgements
The authors are grateful to the reviewers for their
comments and edits. This study was undertaken with
the financial support of the Deputy of Research and
Technology, Art University of Isfahan, Iran.
238  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
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Authors
Omid Oudbashi has a BSc, MA and PhD in conserva-
tion of cultural and historical properties from the Art
University of Isfahan, Iran, and is currently associate
professor in the Department of Conservation of Cultural
and Historical Properties at the same university and
senior scientist in the Department of Scientific Research
at the Metropolitan Museum of Art, USA. His research
interests are the deterioration of archaeological objects,
especially the corrosion mechanism of ancient metals in
terrestrial, marine and outdoor environments; preventive
and archaeological conservation; archaeometallurgy and
CORROSION ANALYSIS AND ASSESSMENT OF A COLLECTION OF ARCHAEOLOGICAL COPPER ALLOY OBJECTS FROM SAGZABAD, NORTHERN IRAN 239

ancient metalworking; metallography of ancient and

historic metals; and ancient techniques and methods of
production and decoration in other inorganic materials.

Sepehr Bahadori has completed a BSc in conserva-

tion of cultural and historical properties and a MSc in
archaeometry of inorganic materials at the Art University
of Isfahan, Iran. His research interests include the study
of archaeometallurgical remains, such as prehistoric
metals, ores and slags, using multi-analytical methods,
such as chemical analysis and metallography, to obtain
knowledge related to the technology and production
methods used by ancient craftsmen.

Ahmad Aliyari received a MA in archaeology from the

University of Tehran and a PhD in prehistoric archae-
ology from the Art University of Isfahan. He is currently
a chief researcher in the Institute of Archaeology at the
University of Tehran. He previously held the positions
of vice director, head of the Research Department and
head of the Research Archaeological Museum at the
Institute and was a key collaborator on several Institute
projects. He has participated as a researcher and member
of several archaeological teams excavating in the Qazvin
Plain and the Tehran Plain in Iran, and the Tepe Sanjar-
Shah in Tajikistan.
The Effect of Synthesis Routes on the Ability of
Akaganeite to Corrode Iron
Nicola J. Emmerson* Kimberly Roche
Cardiff University Warren Lasch Conservation Center
Cardiff, UK Charleston SC, USA
emmersonnj@cf.ac.uk roche4@clemson.edu
David E. Watkinson Jerrod H. Seifert
Cardiff University Cardiff University
Cardiff, UK Cardiff, UK
watkinson@cf.ac.uk seifertjh@cf.ac.uk
Abstract
Akaganeite (βFeOOH) occludes chloride within its crystal structure
and adsorbs it onto its surface during its formation. βFeOOH was
synthesised by solid-state and aqueous precipitation routes. The
amount of adsorbed chloride removed by a single aqueous wash
was measured. The impact of the synthesised βFeOOH on the
oxidation rate of iron was determined using a remote oxygen
sensing technique to record oxygen concentrations within a
sealed vessel, internally controlled to 80% relative humidity and
Introduction
Conservation practitioners devise and apply treatments
to fulfil perceived goals and require quantitative and
qualitative research to evidence whether these are
attained. The research design dictates the value of its
outcomes to conservation practice and, if this design
is flawed, it can foster misinterpretation and increase
risk in conservation practice. Within any experimental
design, the sample introduces variables that impact on
data quality, range, reproducibility and relevance to the
question being addressed. While analogue samples can
provide reproducibility, they are often problematic as
they seek to replicate outcomes that may have taken years
or centuries to achieve, such as patinas and corrosion
product layers. In order to study corrosion or decay
processes, research may require synthesis of compounds
that are produced naturally on objects. While this often
seems straightforward to achieve, questions remain
regarding whether the synthesis routes produce similar
chemistry and morphology to the compounds formed on
objects, whether formation routes for analogues produce
the same end product, how well an analogue represents
contextual reality and, consequently, whether research
Johanna C. Thunberg
Cardiff University
Cardiff, UK
thunbergjc@cf.ac.uk
*Author for correspondence
containing a mixture of βFeOOH and iron powder. The oxidation
rate of iron was directly related to the mass% of adsorbed
chloride removed by the aqueous wash. This contributes to an
understanding of both iron corrosion and the development of
conservation treatments.
Keywords
iron, corrosion, archaeological, akaganeite, chloride
results are transferable to conservation practice. This
research considers these questions for the experimental
use of synthesised akaganeite (βFeOOH) to parallel the
role of naturally formed βFeOOH in the corrosion and
treatment of archaeological iron.
Archaeological iron: The corrosion problem
Chloride plays a major role in the post-excavation corro-
sion of archaeological iron. Turgoose’s (1982a) corrosion
model for buried archaeological iron reports Cl− ions
accumulating at the metal surface to provide charge
balance for anodically generated Fe2+. Above this, there
is a dense corrosion product layer (DPL) that normally
comprises a goethite, magnetite and maghemite matrix,
overlaid by an altered porous layer of iron corrosion
products and soil particles (Reguer et al. 2006, Neff et al.
2007). Localisation of chloride occurs at anodes on the
metal, due to strips of magnetite that conduct electrons
into the DPL where ingress of moisture and oxygen
support the cathode reaction (Neff et al. 2007). Highly
mobile Cl− ions from the soil pass through the corrosion
matrix and associate with Fe2+ ions at the anode. They
THE EFFECT OF SYNTHESIS ROUTES ON THE ABILITY OF AKAGANEITE TO CORRODE IRON
can exist in solution and Reguer et al. (2006) identified
the β-Fe2(OH)3Cl iron hydroxy-chloride ferrous phase
occurring next to the metal surface, postulating that it is
a precursor for the formation of the oxidised ferric phase
β-FeOOH, which is detected above it. Turgoose (1982b)
identified β-FeOOH on archaeological iron post-exca-
vation, attributing it to oxidation of a Fe2+/Cl− solution
at the metal surface by atmospheric oxygen and fresh
oxidation of iron with chloride as an electrolyte. Iron
oxidation generates more Fe2+ ions and their hydrol-
ysis lowers pH in the thin moisture film which makes
βFeOOH formation thermodynamically favourable in the
prevailing high Cl− ion concentration (Turgoose 1982b,
Rémazeilles and Refait 2007).
βFeOOH occludes chloride in its crystal structure and
adsorbs it onto its surface (Mackay 1962). The overall
chloride content can vary, but substantial amounts are
often surface adsorbed. Reguer et al. (2009) produced
βFeOOH with 12%mass chloride, attributing 6.7%mass
of this to being within the crystal structure as determined
by X-ray diffraction (XRD) structural analysis. They
reduced chloride content to 4.5%mass after 10 washes in
deionised water, which removed the adsorbed chloride
and reduced the chloride in the crystal structure by 20%.
The mobility of the adsorbed chloride in water and water
vapour makes it readily available for corrosion of adja-
cent iron (Turgoose 1982b, Watkinson and Lewis 2005,
Thickett and Odlyha 2013, Watkinson and Emmerson
2016). Lowering the amount of adsorbed chloride present
on βFeOOH by aqueous washing treatments reduces
the extent and rate of corrosion it produces on iron
(Watkinson and Emmerson 2016). While the residual
chloride in the crystal structure of βFeOOH is unavailable
to support corrosion, it remains a risk if transformations
occur and it is released.
βFeOOH has been identified on archaeological objects
(Thickett and Odlyha 2013) many times post-excavation
and poses a major corrosion threat as it and any ferrous
chloride present are hygroscopic, hence their corrosion
threat is a function of prevailing relative humidity (RH)
(Watkinson and Lewis 2005, Watkinson et al. 2019).
For βFeOOH mixed with iron powder, corrosion ceases
below 15% RH (Watkinson and Lewis 2005, Thickett
and Odlyha 2013) and for ferrous chloride below 20%
RH (Turgoose 1982b, Watkinson and Lewis 2005). For
both compounds, it is very slow below 30% RH then
rises, finally escalating exponentially from 60% RH
241
upwards (Watkinson and Lewis 2005, Watkinson et al.
2019). The prevalence and form of chloride in βFeOOH
will impact on its role in corrosion processes, as will the
access of moisture and oxygen to its location. Preventing
its formation post-excavation is essential, since its growth
at the metal surface cracks overlying corrosion product
layers, which then spall off and destroy the heritage value
of an object.
Controlling corrosion of chloride-infested iron
An obvious and proven option for non-interventive
action to control corrosion is desiccation (Turgoose
1982b, Watkinson et al. 2019, Thunberg et al. 2021).
Desalination to remove electrolytes has been the main-
stay of interventive conservation treatments for over a
century, yet its effectiveness has long been questioned.
Determining an end point for desalination treatments
involves monitoring chloride release; when outward
diffusion of chloride ceases, measured as concentra-
tion of chloride in the wash bath, this is considered a
proxy measurement that all chloride is removed. To be
successful, desalination will need to remove all soluble
chlorides, adsorbed chloride from βFeOOH and access
deep-seated chloride beneath corrosion layers and in pits.
This has not been shown to be successful, as chloride
is detected within archaeological iron post-treatment
(Rimmer et al. 2012). While this may be occluded in the
βFeOOH where it does not support iron corrosion, anec-
dotal reporting of post-treatment instability of washed
iron and detection of large quantities of fresh βFeOOH
on fragmenting objects indicates not all chloride remains
in this inaccessible form. Following desalination, it
is realistic to expect iron to remain unstable but have
enhanced stability compared to its untreated state and
to corrode at a significantly slower rate.
Impact of βFeOOH on the corrosion rate of iron
Initial research used βFeOOH, produced by solid-state
synthesis involving mixing iron powder with FeCl24H2O
at 92% RH, to investigate its impact on the corrosion
rate of iron at low humidity (12%–35%) (Watkinson and
Lewis 2005). Since oxidation of iron was recorded by
mass gain, which records both oxidation and hydration,
this prevented production of an oxidation rate graph. A
remote sensing technique for quantitative measurement
of oxygen concentration in a body of air (Matthiesen
2007, Matthiesen and Wonsyld 2010) has been adopted to
242  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND ANALYTICAL INVESTIGATIONS

provide a standardised reproducible experimental design Objectives:

for determining oxygen within an enclosed volume of air
(Emmerson et al. 2021). This has been used to study the
impact of washing on synthesised βFeOOH (Watkinson
and Emmerson 2016) and corrosion rates of archaeolog-
ical iron as a function of ambient RH (Watkinson et al.
2016, Watkinson et al. 2019) and is utilised in this study.
• To synthesise βFeOOH by solid-state and precipitation
techniques, and then wash these in cold water.
• To record the oxidation rate of iron mixed with
synthesised βFeOOH using oxygen consumption and
relate this to mass% of chloride removed during the
wash process.

The data generated when using synthesised βFeOOH

to study corrosion rates is likely to be influenced by
the synthesis process. Solid-state (Turgoose 1982b) and
precipitation (Mackay 1962, Reguer et al. 2009) methods
are reported synthesis routes, but each can be expected to
produce varied chloride content, crystal shape and crystal
size in the end product. Crystal morphology influences the
amount of surface-adsorbed chloride, as does washing to
refine the synthesis product, although this may not always
be carried out. Amounts of occluded chloride can also
vary. Post-synthesis purification washing may be either
aqueous or anhydrous and it aims to remove excess reac-
tants, specifically chloride compounds. Both the solvent
used and the number of washes will influence the amount
of adsorbed chloride on βFeOOH, which is normally
reported as a mass percentage (mass%) of the βFeOOH.
Aim:
• To compare how differing synthesis methods for
βFeOOH influence its impact on the corrosion rate
of iron and consider how this informs understanding
of post-excavation corrosion and treatment of archae-
ological iron.
Method
βFeOOH was prepared either by precipitation or solid-
state synthesis (see Table 1). These were either past
or newly synthesised samples with the synthesis year
recorded in the sample labelling.
For all βFeOOH samples, synthesis products were iden-
tified immediately prior to this experimental study using
a PANalytical X’Pert Pro (CuΚα) X-ray powder diffrac-
tometer and the data was interpreted using PANalytical
X’Pert HighScore software. Imaging of βFeOOH crystals
was carried out using a CamScan Maxim 2040 scanning
electron microscope (SEM) equipped with Oxford
Instruments energy-dispersive X-ray spectrometer using
secondary electron imaging. All βFeOOH sample mass
was recorded using a Sartorius Secura 225D-1S balance
(readability 0.01 mg). Washing involved placing 0.05 g
of each sample individually in beakers, adding 10 mL of
deionised water and then stirring continuously for 2 h
at room temperature. This will not remove all adsorbed
chloride but offers a guide to the amount of chloride
available for corrosion processes on each βFeOOH

Table 1. Synthesis methods for βFeOOH samples used in experimental work

Sample-synthesis Post-synthesis
Synthesis method
year washing
(P1-2021) Precipitation from solution Acetone
3 L of 0.1 M FeCl36H2O solution in deionised water heated to 70°C for 48 h. Filtered in a Buchner funnel
(P2-2021) under vacuum. Rinsed with acetone x3. Ground with pestle and mortar for 10 minutes.
(S1-1983) Solid-state transformation Acetone
Iron powder (99.0% pure) mixed with equal mass FeCl24H2O spread in petri dish enclosed in desiccator
with beaker containing saturated solution of Na2CO3 to produce 92% ± 5 RH.
(S2-2000) Solid-state transformation None
25 g iron powder (Aldrich GPR™ 99.0% pure) mixed with 25 g FeCl24H2O (BDH Chemicals 99.0% pure)
spread in petri dish enclosed in desiccator with beaker containing saturated solution of Na2CO3 to produce
92% ± 5 RH. No post-synthesis washing.
(S3-2014) Solid-state transformation Acetone
100 g iron powder (Aldrich GPR™ 99.0% pure) mixed with 100 g FeCl24H2O (Sigma > 99% pure) spread
in petri dish enclosed in desiccator with beaker containing saturated solution of Na2CO3 to produce
92% ± 5 RH. Humidity cabinet aerated regularly to ingress oxygen for 4 months. Residual FeCl24H2O
washed off with acetone using a Buchner funnel. Wash volumes unknown.
NB: for solid-state, desiccator opened for short period of time daily to ingress oxygen over unspecified
period of months. This avoids danger of depleting oxygen to the point where magnetite (Fe3O4) is the
thermodynamically favoured product.
THE EFFECT OF SYNTHESIS ROUTES ON THE ABILITY OF AKAGANEITE TO CORRODE IRON 243

sample. Using a Microman CP M1000E pipette, 500 µL Results and discussion

(5 µL max systematic error and 3 µL max random error)
of sample solution was removed from each wash sample Composition
solution and chloride concentration was measured XRD confirmed the samples as comprising only
using a Sherwood Model 926 MKIII industrial chloride βFeOOH except for S2-2000, which contained a small
analyser (accuracy: ± 3 mg/L at 200 mg/L). This was amount of iron oxide hydroxide (αFeOOH, reference
scaled up to determine the βFeOOH mass% chloride pattern 01-076-7158 5) (Figure 1; Table 2). Where there
for each synthesis method. The reproducibility of the are mixtures of compounds and fluorescence, detection
analyser was measured using 177 ppm NaCl solution, limits are high, at potentially 15%. The βFeOOH match
before and after measuring a sample. Each solution was in all cases was reference pattern 00-042-1315.
sampled three times for reproducibility.
The βFeOOH samples were synthesised at differing times
To measure the impact of βFeOOH on the oxidation rate over a 38-year period (Table 1) and were later stored
of iron, 0.05 g of synthesised βFeOOH was mixed with either in sealed screw-top glass jars or, in the case of
0.05 g of Aldrich GPR 99.0% pure iron powder, ground for S1-1982, a clip-top plastic container. XRD performed
1 min in an agate mortar and then transferred to a plastic
weigh boat that was placed in a Mason Ball reaction vessel
Table 2. X-ray diffraction data and mass percentage chloride removed
with an airtight screw-top lid containing a Ruthenium
by washing in cold deionised water
oxygen sensor spot and 160 g of silica gel preconditioned
to 80% RH (Emmerson et al. 2021). Since this was to be Sample XRD Washing extraction
(mass%)
a comparative rate test, choosing a single, fixed high RH P1-2021 Reference pattern: 00-042-1315 1.5%
allowed comparison of the corrosion rate between the Iron oxide chloride
various βFeOOH powders and produced results quickly. Empirical formula: Cl1.3Fe8H9.7O16
Reaction vessels were placed in a Binder KBF720 climatic P2-2021 Reference pattern: 00-042-1315 2.0%
Iron oxide chloride
chamber controlled to 50% RH and 20°C. A fibre-optic
S1-1983 Reference pattern: 00-042-1315 2.6%
cable attached to a PreSens Oxy-1 SMA oxygen meter Iron oxide chloride
was fixed to a support, placed against the sensor spot and S2-2000 Reference pattern: 00-042-1315 5.9%
the fluorescence of the spot was recorded every 5 min in Iron oxide chloride
Reference pattern: 01-076-7158 5
the dark interior of the climatic chamber (Emmerson Iron oxide hydroxide FeO(OH)
et al. 2021). Quenching of fluorescence is proportional S3-2014 Reference pattern: 00-042-1315 3.7%
to oxygen pressure in the reaction vessel. Iron oxide chloride

Figure 1. βFeOOH samples: X-ray diffraction data; left to right – (top) P1-2021, P2-2021; (centre) S1-1983, S2-2000; (bottom) S3-2014
244  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
in 2021 confirmed all samples contained βFeOOH and
S2-2000 included an undetermined amount of αFeOOH,
which is a change from the original XRD data collected in
2000 which identified only βFeOOH (Table 2; Figure 1).
Gilberg and Seeley (1981) reported on the thermody-
namic instability of βFeOOH relative to αFeOOH but
cited no examples. Thickett and Odlyha (2013) reported
atmospheric transformation of synthesised βFeOOH to
αFeOOH occurring over a 6-month period, with higher
RH producing more transformation and the presence of
ethanoic acid vapour also promoting transformation.
They detected similar transformations on βFeOOH
samples formed on archaeological iron on display in
showcases. The cause of the XRD assay discrepancy
for S2-2000 between the year 2000 and 2021 cannot be
readily evidenced. Time cannot account for it, as the
older S1-1983 sample comprised only βFeOOH at its
time of synthesis and this has remained unchanged,
although S2-2000 differs in that it was not washed to
purify it post-synthesis (Watkinson and Lewis 2005).
Potentially, the post-synthesis environment and proce-
dures for washing post-synthesis may have influenced
the transformation.
Unwashed βFeOOH has already been shown to corrode
iron (Turgoose 1982b, Watkinson and Lewis 2005,
Thickett and Odlyha 2013) and its transformation
increases its ability to corrode iron by releasing chloride
from within its crystal structure. Similarly, if βFeOOH on
archaeological iron has had its adsorbed chloride mostly
or entirely removed by desalination treatments, transfor-
mation will reactivate its corrosion threat by releasing
residual occluded chloride. At present, the transformation
of corrosion products on washed archaeological iron does
not seem to have been studied.
Crystal structure and adsorbed chloride
Precipitated βFeOOH (P1-2021) produced smaller
and more rounded crystal clusters compared with the
larger and more elongated crystals in the solid-state
synthesis samples (S1-1982, S-2000, S3-2014) (Figure 2).
This outcome tends to align with reported shapes
and comparative sizes of crystals for precipitated and
archaeological samples. Somatoidal crystals have been
reported for the exact same precipitation synthesis
(García et al. 2004) and Bayle et al. (2016) identified 0.5
µm rice-shaped crystals in their precipitated βFeOOH.
While no crystal shape data is reported for solid-state
ANALYTICAL INVESTIGATIONS
synthesis used in the study reported here, Mackay
(1962) identified elongated crystals in naturally formed
βFeOOH and showed overall that crystal shapes for
βFeOOH differ according to synthesis method and
time. Rod-shaped 1 µm-length crystals were identified
in archaeological βFeOOH, which formed post-excava-
tion by transformation of β-Fe2(OH)3Cl on an iron bar
from a marine context (Bayle et al. 2016). The shape of
the βFeOOH crystals is important, since surface area
influences adsorption of chloride.
Figure 2. SEM images of the crystal structures of the βFeOOH samples
synthesised by precipitation and the solid-state reaction (4000×
magnification)
Adsorbed chloride on the βFeOOH, measured as the
%mass chloride removed by single cold water washing,
ranged from 5.9% to 1.5%mass (Table 2). βFeOOH
samples formed by precipitation had low mass% of surface
adsorbed chloride, which differed (2 and 1.5 mass%)
despite their similar synthesis (Table 1). As might be
expected, due to it being unwashed following synthesis,
S2-2000 had the most adsorbed chloride (5.9 mass%),
while the acetone-washed S1-1983 and S3-2014 had
2.6 and 3.7 mass% chloride, respectively. Differences
in crystal shape and/or acetone wash procedures could
explain why the solid-state synthesised βFeOOH had
more adsorbed chloride or, for S2-2000, transformation
to αFeOOH released occluded chloride.
The short wash time employed here has been shown
to remove a significant amount of adsorbed chloride
(Watkinson and Emmerson 2016). This identifies the
high mobility of the adsorbed chloride and leads to the
expectation that damp conditions will readily mobilise
it, which was confirmed by the oxygen consumption
corrosion rate tests carried out here (Figure 3). Once
THE EFFECT OF SYNTHESIS ROUTES ON THE ABILITY OF AKAGANEITE TO CORRODE IRON
βFeOOH receives a single cold water wash, its impact on
the corrosion rate of iron falls significantly (Watkinson
and Emmerson 2016).
Corrosion of iron by βFeOOH
Reaction of all the βFeOOH samples with iron, recorded
as oxygen consumption, was initially fast (Figure 3),
aided by the large surface area of the iron powder and
mobility of the adsorbed chloride at 80% RH. This
created an electrolyte at the interface between the
iron powder and the βFeOOH, producing Fe2+ ions
which hydrolysed, lowering the pH. According to the
ratios of Fe2+ and Cl− and the prevailing pH, different
forms of FeOOH are produced: high concentrations
of Fe2+ and Cl− favour production of only βFeOOH;
intermediate concentrations of Fe2+ favour production
of αFeOOH; and low Fe 2+ concentrations produce
γFeOOH (Rémazeilles and Refait 2007). Mixtures of
these compounds might be expected to occur in the
corrosion formed here, since pH is expected to vary as
Fe2+ is converted to corrosion products and hydrolysis is
limited. Iron is also depleted, and the crusts of corrosion
formed influence oxygen access to the remaining iron,
influencing oxygen access and hence its consumption
and the corrosion rate (Figure 3). Plotting the amount
of adsorbed chloride removed from the βFeOOH by
the cold water wash against the total amount of oxygen
consumed by unwashed βFeOOH/iron powder mixtures
over a 16-hour period, at which point reactions either
cease or are significantly slowed, revealed a linear rela-
tionship (Figure 4). As might be expected, the greater
the amount of adsorbed chloride, the faster and more
extensive the corrosion of the iron.
Figure 3. Oxygen consumption data for βFeOOH samples. Since the
volume of all components of the reaction system in each case are
identical, the mbar oxygen consumed can be used to compare rates
within this sample set
245
Figure 4. Oxygen consumed by βFeOOH/iron powder mixtures over the
16-hour logging time as a function of chloride removed by aqueous
washing tests (mbar converted to mg, see Emmerson et al. 2021)
Context for conservation practice
When carrying out experimental studies using synthe-
sised βFeOOH, extrapolating data quantitatively to
archaeological iron contexts is challenging. Quantifying
the risk of corrosion of archaeological iron as a rate factor
of synthetic βFeOOH is not possible, as the amount of
βFeOOH on objects, its adsorbed chloride mass and its
accessibility to oxygen and moisture are all unknown.
For investigating treatments aimed at removing adsorbed
chloride from βFeOOH, using synthesised βFeOOH can
offer insights into the impact of treatment parameters like
solution composition, concentration, temperature and
time on chloride removal and βFeOOH transformation.
Conclusion
The corrosion risk to iron due to the presence of βFeOOH
is a function of the mass of chloride adsorbed on the
βFeOOH surface. This can differ appreciably according
to the conditions in which βFeOOH forms and may
change with time if transformations occur that release
occluded chloride. Since solid-state formation routes are
expected to occur on iron corroding in high humidity, the
mass% of surface adsorbed chloride is likely to be high,
as compared to βFeOOH formed from ionic solutions.
In designing experimental studies using synthesised
βFeOOH, its synthesis route should be taken into account
when extrapolating results to practical contexts within
conservation.
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ICOM-CC Metals Working Group, New Delhi, 26–30
September 2016, eds. R. Menon, C. Chemello, and A.
Pandya, 195–202. New Delhi: International Council of
Museums-Committee for Conservation (ICOM-CC) and
Indira Gandhi National Centre for the Arts (IGNCA).
Watkinson, D.E., M.B. Rimmer, and N.J. Emmerson.
2019. The influence of relative humidity and intrinsic
chloride on post-excavation corrosion rates of archae-
ological wrought iron. Studies in Conservation 64(8):
456–71.
THE EFFECT OF SYNTHESIS ROUTES ON THE ABILITY OF AKAGANEITE TO CORRODE IRON 247

Authors
Nicola J. Emmerson is a reader in conservation at
Cardiff University with research interests in the corro-
sion and conservation of ferrous metals within heritage
contexts.

David E. Watkinson is professor of conservation at

Cardiff University where he teaches conservation of
metallic and inorganic objects and researches the corro-
sion and treatment of metals.

Kimberly Roche graduated from Cardiff University

with an MSc in conservation practice and now works at
the Warren Lasch Conservation Center in Charleston,
South Carolina, USA.

Jerrod H. Seifert gained his PhD on the corrosion and

treatment of marine cast iron at Cardiff University where
he is now an Analytical Laboratory Teaching Associate.

Johanna C. Thunberg is studying for a PhD on copper

alloy corrosion at Cardiff University where she is also
employed full-time to teach conservation.
 Young Conservation Professional

Analysis of Heterogeneous Tarnish on Silver-based Alloys

Using the Pleco for Local, Controlled Electrolytic Cleaning

Nicola Ricotta* Andrea Cagnini Christian Degrigny

Department of History,
Archaeology, Geography, Fine and
Performing Arts (SAGAS), University
of Florence
Florence, Italy
nicola.ricotta@unifi.it
www.sagas.unifi.it
Opificio delle Pietre Dure (OPD)
Florence, Italy
andrea.cagnini@beniculturali.it
www.opificiodellepietredure.it
Haute Ecole Arc Conservation-
restauration (HE-Arc CR), HES-SO
University of Applied Sciences and
Arts Western Switzerland
Neuchâtel, Switzerland
christian.degrigny@he-arc.ch
www.he-arc.ch
*Author for correspondence

Abstract
Artworks made of silver-based alloys tarnish unevenly,
which considerably compromises their surface appearance
as well as their historical and artistic value. Mechanical and
chemical cleaning methods remove silver tarnish but in
some cases are difficult to control. Electrolytic processes,
which are often preferred because they retain some of the
constituent materials, require an appropriate protocol to
avoid side effects such as overcleaning and black spots. Using
the representative example of a heterogeneously tarnished
silver-based artwork, we demonstrate the potential of the
Pleco electrolytic pencil to identify the nature of the tarnish.
Artificial coupons mimicking the artwork were employed to
optimise the use of the Pleco in the local, controlled cleaning
of metal surfaces.
Keywords
silver-alloy, heterogeneous tarnish, Pleco®, artificial coupon,
linear sweep voltammetry, analysis

Introduction
The tarnishing of silver-based objects is a common
problem faced by conservation professionals. The metal
surface tarnishes unevenly, with the colour varying from
yellow to black depending on the thickness of the tarnish.
In addition, the composition of the alloy, the environ-
ment and previous conservation interventions influence
the nature and appearance of the alteration. The main
components of silver tarnish are silver sulfide (Ag2S) and
silver chloride (AgCl), but the presence of other elements
in the alloy, such as copper, leads to the formation of other
compounds (Cu2O, Cu2S, etc.) (Costa 2001).
Local identification of the silver tarnish is crucial to
appreciate its heterogeneity and the likely composition
of the underlying metal but also to define appropriate
cleaning protocols. The Pleco electronic pencil was
developed in 2016 by the Haute Ecole Arc Conserva-
tion-restauration in Neuchâtel and has proved to be a
versatile tool for the analysis and local cleaning of silver
tarnish. Unlike conventional cleaning methods, it also
allows the reduction of silver tarnish. Linear scanning
voltammetry (LSV) is used to identify tarnish compounds
based on their reduction peaks and then to define treat-
ment parameters (Degrigny et al. 2016).
The Pleco pencil is expected to solve the problem
of overcleaning of heterogeneously tarnished silver
surfaces during electrolytic immersion cleaning. Over-
cleaning occurs because: (i) the same treatment param-
eters are applied to the whole metal surface and (ii) the
polarisation of less tarnished areas is similar to that of
heavily tarnished ones, causing hydrogen to be released
from the former and resulting in excessive cleaning.
Furthermore, black spots due to the reduction of copper
compounds may appear (Ricotta et al. 2019). The Pleco,
however, works selectively and can clean differently
tarnished metal surfaces as appropriate (Degrigny et al.
2015). Nonetheless, it poses a few technical problems
for end users. For example, the identification of small
reduction peaks on LSV plots is difficult due to their
masking by current fluctuations. These fluctuations
are caused by the pumping system, which heteroge-
neously supplies and extracts the electrolyte on the
metal surface.
ANALYSIS OF HETEROGENEOUS TARNISH ON SILVER-BASED ALLOYS USING THE PLECO FOR LOCAL, CONTROLLED ELECTROLYTIC CLEANING 249

Our approach Table 1. XRF analysis of the different elements of the Valadier cooler

Measuring points Ag% Cu% Trace elements

The objective in this research was to further optimise
1 93.6 ± 0.1 6.4 ± 0.2 Zn
the use of the Pleco as an analytical tool allowing correct Inner upper plate
2 94.1 ± 0.1 5.9 ± 0.2 Zn
tarnish reduction for local, controlled cleaning.
3 94.1 ± 0.1 5.9 ± 0.2 Zn and Fe
Body 4 95.0 ± 0.1 5.0 ± 0.2 Zn and Fe
Valadier case study
5 96.3 ± 0.1 3.7 ± 0.2 Zn and Fe
The Valadier cooler, made by the Roman silversmith 6 90.7 ± 0.1 9.3 ± 0.1 Zn, Fe and Pb
Handle
Giuseppe Valadier in 1810, is part of the collection of 7 90.4 ± 0.1 9.6 ± 0.1 None
Gallerie degli Uffizi, Tesoro dei Granduchi in Flor- 8 92.4 ± 0.1 7.6 ± 0.2 Zn and Pb
Base
ence (Inv. Pitti Art Objects (1911) n. 1838). It depicts 9 90.0 ± 0.1 10.0 ± 0.1 None

mythological scenes (Figure 1a) and consists of a 10 93.3 ± 0.1 6.7 ± 0.2 Zn
Inner bottom plate
11 92.4 ± 0.1 7.6 ± 0.1 Zn
body, handles and a base, all made by casting from a
silver alloy. The object has decorations in relief that
have been chased and both polished and matt surface Preliminary LSV plots performed with the Pleco on
finishes have been applied. Silver-alloy foils have been two discrete, randomly chosen areas (1 and 2), located
embossed to fit inside the cooler and its base. All opposite each other on the surface of the cooler body
elements are secured by a central bolt and nut. Non-in- (Figure 2), showed the presence of different corro-
vasive X-ray fluorescence (XRF) analyses, performed sion products. On one side, only silver compounds
with the portable XRF spectrometer ELIO (XGLab) were detected, and on the other side additional copper
and without any preliminary surface cleaning, revealed compounds were found. This result suggested that the
that the elements of the cooler consist of different composition of the cooler body surface is not uniform. To
silver-copper alloys. Quantitative analysis results were confirm this hypothesis, smoother plots were required.
obtained using bAxil BrightSpec software and a certified Indeed, the high current fluctuations between −1 and
Ag% 92.44 ± 0.12 Cu% 7.59 ± 0.14 standard and were −2V/GC (glassy carbon) prevented a correct visualis-
normalised to 100% (Table 1). ation of any small reduction peaks. However, one such
peak may have been present on the plot of side 1, around
Like many objects in the museum’s storage, the Vala-
−1.6V/GC (Figure 3).
dier cooler is heterogeneously tarnished. As shown in
Figure 1a, some parts of the body, handles and base
are more tarnished (either the hollow parts or chased
backgrounds, Figure 1b), while the polished figures
and other reliefs seem to be only slightly tarnished
(Figure 1c). The differences could be due to intentional
depth effects or to regular maintenance of the object, as
shown by the thick tarnish layers in some grooves that
are more difficult to reach than the embossed surfaces.
This condition demonstrated the importance of a more
selective cleaning, such as is possible using the Pleco.

Figure 2. Electrolytic setup to obtain LSV plots of the body of the Valadier
cooler using the Pleco

Electrochemical study of coupons simulating the

Figure 1. Valadier cooler: general view (a) and details of the scenes
depicted on the body (b) with different levels of tarnish (c)
Valadier cooler
To optimise the LSV plots, metal coupons made from
sterling silver (Ag7.5%Cu) plates were used. Some were
flat, matt and chased (4 × 2 cm, Figure 4a), and others
were polished and curved (6 × 4 cm, Figure 4b).
250  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Figure 3. LSV plots of two sides of the Valadier cooler body. The different
compounds are identified by the potentials located at the intersection
between the tangents of the slopes of the reduction peaks and the
potential axis. The reductions of AgCl, Cu2O and Cu2S are hypothetical.
Note the possible presence of a peak on the blue plot around −1.6V/GC
Figure 4. Metal coupons used to mimic the behaviour of the Valadier
cooler: matt and chased (a) and polished and curved (b)
The metal coupons were artificially aged in a 24 h expo-
sure to warm hard-boiled eggs, peeled and cut into four
sections. The coupons, handled without gloves so as to
induce the formation of fingerprints, quickly tarnished,
acquiring a heterogeneous appearance ranging from
yellow to blue (Figure 5).
Figure 5. Artificial tarnishing of the metal coupons in a desiccator using
warm hard-boiled eggs, peeled and cut into four sections (a), and the
surface of the coupons after a 24 h exposure (b)
LSV plots on the tarnished sterling silver plates (bluer
areas) showed an electrochemical behaviour similar to
that of body side 2 of the Valadier cooler (Figure 6). The
same compounds appeared, although the maxima of the
peaks of the Valadier cooler shifted to more negative
potentials in areas of presumably thicker corrosion
products.
ANALYTICAL INVESTIGATIONS
Figure 6. Comparison of the LSV plots on side 2 of the Valadier cooler
body and the artificial coupon
As the artificial silver-based coupons correctly simulated
the electrochemical behaviour of the Valadier cooler, they
were employed to optimise the use of the Pleco.
Optimisation of the Pleco
Several parameters were studied to minimise the current
fluctuations seen in the LSV plots:
• The circulation rates of the diaphragm pumps. If the
extraction flow rate is too high, the Pleco’s micropo-
rous polyvinyl formal (PVFM) pad dries out, reducing
fluctuations, whereas if it is too low, the electrolyte
leaks out of the pad and induces more fluctuations.
• A large pad (pad 1 in Figure 7) compressed when
inserted into the Pleco nozzle causes smaller current
fluctuations but also prevents electrolyte renewal on
the metal surface. Conversely, a small pad promotes
electrolyte renewal but also causes electrolyte leakage
(pad 3 in Figure 7).
• By changing the shape of the pad (from flat, round,
slightly sharp to conical; Figure 7), the contact surface
with the metal surface is reduced, causing larger fluc-
tuations of current that can be reduced by increasing
the extraction flow rate.
Figure 7. Different sizes and shapes of the tested pads, inserted in the
nozzle of the Pleco
ANALYSIS OF HETEROGENEOUS TARNISH ON SILVER-BASED ALLOYS USING THE PLECO FOR LOCAL, CONTROLLED ELECTROLYTIC CLEANING
LSV plots on the Valadier case study
The best LSV plots were obtained with conically shaped
pad 2 (medium size), which resulted in supply and
extraction flow rates of 10 and 90, respectively. A total
of nine LSV measurements were performed under these
conditions on the Valadier cooler body. The studied areas,
preliminarily degreased with alcohol and acetone, were
randomly selected on sides 1 and 2, considering only the
most tarnished surfaces and different surface finishes.
Three measurements were made on polished areas and
six on chased areas.
On side 1, the tarnish was shown to consist mainly of
Ag2S and AgCl (?) (Figure 8). On side 2, reduction peaks
of Cu2O (?) and Cu2S (?) were also present (Figure 9).
Figure 8. LSV plots on different areas of side 1 of the Valadier cooler body
Figure 9. LSV plots on different areas of side 2 of the Valadier cooler body
These results suggested that the Valadier cooler body
had been superficially treated during its production, to
enrich its silver content. As a result of repeated tarnishing
and cleaning interventions, part of the enrichment layer
abraded, exposing the underlying metal. Why one side
of the body was apparently differently preserved from
the other is unknown.
To validate these results, further LSV measurements will
be made, with the measurement areas chosen according
to the different chromatic types of surface tarnish
observed under binocular microscopy. This will allow
mapping of the surface and the assignment of a specific
composition to each aspect of the surface tarnish.
251
Conclusion
The Pleco device and the accompanying LSV plots are a
valuable diagnostic tool, providing critical information
on the tarnishing of silver-based objects. However, the
accuracy of the analysis requires an understanding of
the effects of the parameters that influence the presence
of current fluctuations in the LSV plots. The Pleco
pencil is perfectly adapted to the study of heterogeneous
tarnish, but it is invasive, as the measurement point on
the surface of the object where the reduction reactions
occurred is visible. However, this disadvantage becomes
secondary if cleaning the object after the diagnostic
steps is planned.
Acknowledgements
The authors wish to thank Regione Toscana POR FSE
2014–2020 for funding this PhD research project, COST
Action PortASAP – CA16215 for funding the short-term
scientific mission at HE-Arc CR, OPD and HE-Arc CR
for their technical support, and Gallerie degli Uffizi,
Tesoro dei Granduchi for allowing access to their collec-
tion.
References
Costa, V. 2001. The deterioration of silver alloy and some
aspects of their conservation. Studies in Conservation
46(suppl. 1): 18–34.
Degrigny, C., R. Jeanneret, and D. Witschard. 2015.
Local cleaning with the Pleco electrolytic pencil of
tarnished Saint Candide reliquary head at the Treasury
of Saint-Maurice Abbey, Valais (Switzerland). e-Preser-
vation Science 12: 20–27.
Degrigny, C., R. Jeanneret, D. Witschard, C. Baudin, G.
Bussy, and H. Carrel. 2016. A new electrolytic pencil for
the local cleaning of silver tarnish. Studies in Conservation
61(3): 162–73.
Ricotta, N., C. Degrigny, A. Cagnini, and C. Ortolani.
2019. Design of a suitable cleaning procedure for the
tarnished silver elements of the reliquary bust of Santa
Vittoria, Diocesan Museum of Agrigento, Sicily. In Metal
2019: Proceedings of the Interim Meeting of the ICOM-CC
Metals Working Group, Neuchâtel, 2–6 September 2019,
eds. C. Chemello, L. Brambilla, and E. Joseph, 261–64.
Paris: International Council of Museums–Committee
for Conservation (ICOM-CC) and Haute Ecole Arc
Conservation-restauration (HE-Arc CR).
252  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND ANALYTICAL INVESTIGATIONS

Authors
Nicola Ricotta is a conservator and PhD student at the
University of Florence, Italy.

Andrea Cagnini is a chemist and professor at the Scuola

di Alta Formazione e di Studio, Opificio delle Pietre
Dure, Florence, Italy.

Christian Degrigny is an electrochemist and professor

at the Haute Ecole Arc Conservation-restauration,
Neuchâtel, Switzerland.
Using Epidemiology to Validate Scientific Results for
Complex Situations
David Thickett
English Heritage
London, UK
david.thickett@english-heritage.org.uk
Abstract
Science can help in some aspects of improving conservation
practice. Laboratory experiments have elucidated many factors
for preventive conservation of archaeological iron and copper
alloy objects. However, these rely on simple model systems
(powder mixtures) and objects are much more complex in
nature. Epidemiological methods can be readily adapted to
conservation problems. Analysing the results of two large
criteria-anchored surveys has shown that the experimental
results do represent a good portion of archaeological iron and
Introduction
Burial profoundly changes metal artefacts and can
significantly alter their response to the environment.
It introduces reactive species, alters the structure and
dramatically increases porosity and often the fine-scale
porosity responsible for uptake of water vapour and pollu-
tion. As well as significant differences between objects
from the same archaeological site, burial can cause great
differences throughout an object.
Scientific methods can help understand the impor-
tant factors in preventive conservation and treatment.
However, this requires near-identical replicates for expo-
sure or treatment. Three broad options exist:
• the use of low-value objects, such as nails;
• the use of replicates, which are particularly difficult
to produce for archaeological metals;
• exposure of objects only to the same conditions they
will be exposed to in display or storage, which, given
changes are slow, mainly requires very sensitive analyt-
ical techniques.
Two pieces of work on the required relative humidity
(RH) and carbonyl pollutant conditions for archaeolog-
ical iron and copper alloy have been published (Thickett
and Odlyha 2013, Thickett 2016). These used iron/iron
chloride and copper/copper chloride powder mixtures
copper alloy responses. The graphs generated can be used for
other collections and to carry out similar surveys and analyse
the results. The approach requires very large numbers if based on
visual observation, but these can be reduced with more sensitive
analytical methods. Oxygen depletion has been demonstrated
to provide useful conclusions using a much smaller sample set.
Keywords
iron, copper alloy, surveys, epidemiology, oxygen depletion
and measured the amount of akaganeite formed or
oxygen depleted to quantify deterioration. Significant
analytical evidence exists that archaeological copper does
indeed contain copper chloride (Scott 1990) and iron
chloride was analysed in archaeological iron (Thickett
2012). Whilst this research provides powerful evidence
to inform preventive conservation strategies, there is
a concern that simple model mixtures may not fully
represent very complex objects. This has been addressed
in two ways:
• Two surveys were undertaken of almost all of the
archaeological iron and copper alloy objects on display
at English Heritage sites and objects in store from
excavations at those sites.
• Measurements were taken of oxygen depletion rates
from a large number of real objects and compared with
the RH measured in other studies on powder mixtures.
Several important criteria for object response studies
have already been considered within the field of epide-
miology, such as sample size, appropriate statistics,
experimental design, quality of evidence and potential
bias (Kelsey et al. 1996, Fleis et al. 2003, Dean et al. 2021).
One useful concept in epidemiology is the hierarchy of
methods, which indicates the reliability of different types
254  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
of evidence, as summarized in Table 1. Randomised
controlled studies (comparing two cohorts – groups) are
considered the strongest of the unfiltered (experimental)
methods. So-called filtered information is considered to
be higher quality evidence in epidemiology. However,
this does not exist at the moment in this field. There are
certainly critical knowledge gaps in preventive conser-
vation for a number of materials (Thickett and Lankester
2012). The sample size for such unfiltered studies is
essentially determined by the smallest change detectable.
Figure 1 shows the required sample size in each cohort
for differing percentages of the exposed object cohort
with observed deterioration (Kelsey et al. 1996, Fleis
et al. 2003). An alpha value of 0.05 (95% certainty that
the two cohorts represent the population from which
they are drawn) and a beta value of 0.2 (80% chance of
avoiding a false positive result) were used to construct
Figure 1. This followed the methodology described in
detail in the OpenEpi website (Dean et al. 2021: OpenEpi,
Version 3, open.source.calculator, SSCohort). Figure 1
was generated by feeding several hundred values into
the calculator to produce a smooth line. The OpenEpi
site not only provides extensive background information
but also leads a user through all the necessary steps and
decisions to undertake these kinds of studies.
Table 1. Hierarchy of epidemiological methods
Information Quality of
Study type
type evidence
Systematic reviews Filtered
Critically appraised topics Filtered
Critically appraised individual articles Filtered
Randomized controlled trials Unfiltered
Cohort studies Unfiltered
Case-controlled studies Unfiltered
Background information/expert opinion Unfiltered
Figure 1. Number of objects required for cohort sizes for different
observed reaction rates
ANALYTICAL INVESTIGATIONS
The x scale is essentially the increased number of
objects responding to the environment. The Fleis
method produces a higher number of objects and,
therefore, should be more robust. It uses continuity
correction, a process to allow a continuous distribu-
tion (normal) to approximate a discrete distribution
(binomial). Less sensitive detection, such as visual
observation, will produce a smaller number of objects
with observed changes. For example, for cracking
wood, observation by eye may detect increases in crack
length of perhaps 1 mm. More sensitive instrumental
techniques, for example acoustic emission, has been
shown to detect crack increases in wood in the order
of microns, which means changes in more objects
will be detected. This moves the experiment into the
right-hand portion of the graph, requiring less objects
in each cohort. Advances in instrumentation promise
significant improvements over visual observation,
hence higher percentages of objects with observable
deterioration. The curves in Figure 1 can be used in
other studies, provided the researchers are prepared
to accept the alpha and beta value used.
The feasibility of cohort studies with visually assessed
survey data of archaeological metals, supplemented
by analysis, was investigated. In the first study, objects
from the same archaeological site were grouped together.
Different burial environments are known to affect reac-
tivity significantly. Conservation treatments can have
a significant effect. Although complete conservation
records from excavation to the present day were not
available, objects from the same site are more likely to
have had similar treatments than those from different
sites. The first study investigated archaeological iron.
Cohorts were formed from objects kept at different RH
levels (5 or 10% bands of maximum RH) and under low
(< 1000) and high (> 1001 µgm−3) concentrations of acetic
acid in a series of showcases.
The complex nature of archaeological iron and copper
artefacts makes measuring deterioration rate difficult
via normal analytical techniques, with several complex
layers of corrosion needing to be identified and quanti-
fied. In many instances oxygen reduction is considered
to be the main cathodic reaction. If it is also the rate
limiting reaction, then measuring oxygen consumption
would indicate the corrosion rate of iron or copper.
Enclosing an object in an impermeable container of
fixed volume or measured volume, controlling the RH
USING EPIDEMIOLOGY TO VALIDATE SCIENTIFIC RESULTS FOR COMPLEX SITUATIONS
and measuring the oxygen content of the air periodically
allows measurement of the oxygen consumption rate
(Thickett 2021).
Whilst the oxygen depletion technique can provide very
valuable results, there are limits to the atmospheres that
can be generated and maintained in a very well-sealed
container. The author is unaware of any method to
produce mixtures of room-type pollutants, nitrogen
dioxide, ozone and sulfur dioxide that is suitable for the
closed environments of this testing. Whilst enclosing
room air provides an initial concentration, this will
tend towards zero as the gas is consumed in reaction.
Any pre-mixed atmospheres would rapidly lose pollu-
tion gases as they react with the objects, altering the
concentrations. Additionally, heritage environments
can be quite complex and fluctuate over wide ranges
with time.
Methods
Surveys
Archaeological iron
For each of 31 sites, archaeological iron objects on
display and in low RH storage were surveyed. Just over
1,600 objects from 121 showcases and 1,200 objects
in store were investigated. The objects were assessed
visually, using a criteria-anchored methodology (Sully
and Suenson-Taylor 1996). Cracking, flaking and
percentage powdering visible on the surface were
assessed, according to four defined categories, as shown
in Table 2. All objects were surveyed by the primary
author and photographs of representative objects used
to improve long-term consistency (Thickett and Odlyha
2013). Many of the displays had condition photographs
taken at the time of installation. These were consulted
to determine if the present damage had occurred during
the display period.
Table 2. Criteria used for surveys
Iron
Degree, score Corrosion visible on surface Cracking
None, 0
Some, 1 1 or 2 spots, < 1% coverage 1 or 2 cracks, < 1 mm total length
Medium, 2 3 to 10 spots, < 5% coverage 1 or 2 cracks, < 5 mm total length
Heavy, 3 > 10 spots, > 5% coverage Multiple cracks, > 5 mm total length > 10 flakes, > 5% coverage
255
The results were assessed to determine if enough
objects had been surveyed to produce a statistically
valid randomised controlled study (Kelsey et al. 1996,
Fleis et al. 2003). The sample size for such studies is
determined by the increase in proportion of the exposed
sample cohort with the outcome over the unexposed
sample cohort or, in this instance, the sample cohort
exposed to different conditions. Samples of corrosion
were taken from all objects and analysed by Fourier
transform infrared (FTIR) spectroscopy (PerkinElmer
2000 FTIR with Amplif-IR diamond ATR using 32 scans
and 4 cm−1 resolution) and some by X-ray diffraction
(XRD) (Phillips 1830/1840).
As the room environments and showcases for the iron
were highly variable, the display material had been
exposed to a wide range of environmental conditions
(RH and acetic acid concentrations). RH was measured
with SmartReader SR002 loggers or Meaco radiotelem-
etry sensors with Rotronic HygroClip 2 probes. For
each showcase, changing silica gel or the seasonal RH
pattern leads to one or two maximum RH values per
year. These values were recorded over several years.
Acetic acid concentrations were determined using
diffusion tubes analysed with a Dionex DX600 ion
chromatograph and AS14 column (Gibson et al. 1997).
One measurement (two replicate analyses if within 10%
of each other and repeated if otherwise) was undertaken
in each showcase during August or September. Expe-
rience has shown that these months give the highest
acetic acid concentrations in most showcases in rooms
in the UK without air conditioning. The RH results
were initially considered in 5% bins (e.g. 35%–40%)
of maximum RH measured for two sets of showcases,
those above 1001 µg/m3 acetic acid and those below
1000. If a maximum reading was not reached for
half of the instances (each showcase had between 9
and 70 maximums), a lower maximum RH was used
which met that criterion. The OpenEpi website was
used to undertake t-tests (two-sided, 95% confidence
Copper alloy
Flaking Corrosion visible on surface
1 or 2 flakes, < 1% coverage 1 or 2 spots, < 1% coverage
3 to 10 flakes, < 5% coverage 3 to 10 spots, < 5% coverage
> 10 spots, > 5% coverage
256  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND ANALYTICAL INVESTIGATIONS

interval) comparing adjacent RH bins. If significant, measured in 10% of the containers with calibrated
these were accepted; if not statistically significant, they iButton (± 2%) temperature and RH data loggers. No
were repeated with the next two bins combined (10%) excursions from the expected conditions were deter-
and then with the next three (15%) until statistically mined. Oxygen concentration was measured with a
significant results were obtained (Dean et al. 2021). PreSens 4 oxygen meter with PreSens Sp-PSt3-NAU-
Objects from the lowest display RH were compared D7-YOP self-adhesive oxygen spots through the glass
to those in store. Stored iron is kept below 16% RH in container walls.
pollution-free (certainly in terms of carboxylic acids)
Tests were undertaken at 30, 35, 40, 45, 50 and 55% RH to
polypropylene boxes.
investigate where the curve appears to be most complex
Archaeological copper alloys in shape. A group of 60 archaeological iron objects were
analysed at each RH value sequentially. A similar-sized
A series of previously reported results for observed
group of archaeological copper artefacts were also
bronze disease on circa 3,800 Egyptian copper alloy
analysed. Higher RH values of 60 and 65% were also used
artefacts were also re-evaluated in these terms (Thickett
for the 54 objects that had previously been exposed to
et al. 2008). The data was reprocessed with the statis-
those RH values on display.
tical methods described. That survey, undertaken two
decades previously, did not use a criteria-anchored
method, which was under development at the time.
Results
Photographs of so-called ‘index objects’ were used to Surveys
define the assigned category boundaries. For some dete-
rioration phenomena, there are issues with visual iden- Archaeological iron
tification under low magnification. Different corrosion Data from a selection of the 121 showcases assessed are
products or materials can look similar and be mistaken shown in Figure 2.
for each other (Argyropoulos, pers. comm., 2007;
Thickett and Pretzel 2010). Samples of all observed
corrosion products were collected and analysed with
FTIR spectroscopy (Nicolet 510PC) using a diamond
cell and beam condenser.

A further similar survey to that for iron was undertaken

on 1,200 objects on display in 84 showcases at 41 sites
and 1,000 objects in store. A number of objects were
assessed with oxygen depletion.

Oxygen depletion
The oxygen depletion rates of objects identified in the
surveys as being representative of the types and degree
of deterioration were measured. Most sites showed
two groups of objects from previous tests (Thickett
2021): those that did not react, even at very high RH,
and those that did. Only reactive objects were selected.
Objects were selected that had been exposed to at least
55% RH. The objects were placed in variously sized
sealed glass containers (Quickfit laboratory glassware,
Bernardin or Bocal mason jars, corrosion jars and
borosilicate glass jars with polypropylene screw tops
blocked with aluminium foil) with glycerol solutions
to control RH (Milner and Dalton 1953). The RH was
Figure 2. Maximum RH values and acetic acid concentrations in
showcases (numbered 1–17)
This includes the maximum RH and acetic acid values
and a spread of the values observed.
English Heritage has approximately 85% of its collection
in store. For this approach, the maximum sample size
was determined by the number of objects on display in
similar conditions. The number of objects in dry storage
is almost always significantly larger. Table 3 shows the
object numbers on display and the calculated required
cohort sizes for 11 selected sites.
USING EPIDEMIOLOGY TO VALIDATE SCIENTIFIC RESULTS FOR COMPLEX SITUATIONS 257

Table 3. Selected cohort sizes mined and afterwards the statistical significance between
Percentage Number required Number of archaeological different RH bands.
Site
reacting in cohort iron objects on display
The grey and red lines are experimental data on powder
1 11.18 139 286
2 12.31 122 276
mixtures from Thickett (2012). It was not possible to
3 25.00 46 104 determine errors for the survey results. It would be
4 26.67 41 39 possible to have multiple surveyors assessing the same
5 26.88 41 92 objects, but as this would involve visits to 72 sites over a
6 27.08 41 73 very wide geographic area, this was considered prohib-
7 28.88 37 90 itively expensive. Published research on surveys of
8 29.44 37 38 archaeological iron objects indicated errors in the order
9 28.57 37 72 of 10% (Leese and Bradley 1995). As can be seen, there is
10 29.74 34 64 a very good correlation between the two data sets. Figure
11 66.67 11 14 3 also includes similar data for higher concentrations of
acetic acid (red line and red diamonds).
The FTIR and XRD analyses showed three sites that
Again, a good correlation is shown. There are no survey
contained a high proportion of corrosion products other
points below 40% RH, as these were all older wooden
than akaganeite (goethite and rozenite, iron sulfate).
showcases with relatively high air exchange rates and
As the corrosion products are different, caution had
even large amounts of silica gel, very low RHs cannot
to be exercised when considering these sites, and they
be maintained. Many of these cases have been replaced
were excluded from the analyses. The survey scores in
in the last decade, hence the smaller number of points.
a particular RH and acetic acid band were added to
give the survey value. If a showcase had eight objects Archaeological copper alloys
surveyed as 1, 1, 2, 2, 2, 3, 4, 4, the survey value was the
For the copper alloy artefacts, a much smaller percentage
sum (19 in this case). The survey score was normalised
difference was observed, meaning larger sample sizes
based on the number of objects and multiplied by 100 to
would be required. The number required for a signifi-
give manageable numbers, i.e. 19/8, 237.5. All the show- cant response at the visually observed difference levels
cases in the same acetic acid and maximum RH band is shown in Figure 4.
were added together. The experimentally determined
risk was then set to the survey score at the highest RH
point (80%). Figure 3 shows the statistically significant
points from the survey overlaid with the response line
generated from powder experiments (partial results in
Thickett and Odlyha 2013, full results in Thickett 2012).
The points were first assessed for the number of objects
in the cohort, then the corrosion products were deter-

Figure 4. Number of objects required for cohorts for observed copper

alloy degradation rates

This was generated by entering the percentage of non-cat-

Figure 3. Experimentally derived reaction risk compared to cumulative
scores from object assessments for low and high acetic acid environments
egory 0 objects from each site into the OpenEpi website.
Taking the raw, visually assessed data, the 17 sites
required cohort sizes of between 130 and 911. This is
an example of the sample sizes required and no further
statistical analyses were undertaken with this data. For
258  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
many collections, these numbers would rarely be on
display. The effect of acetic acid (and formic acid and
formaldehyde) is much smaller than for iron, so more
showcases can be grouped together to provide larger
numbers. The types of corrosion analysed for these
objects are shown in Figure 5.
Figure 5. Copper alloy corrosion products determined by site
Many of the objects recorded as having bronze disease
from visual examination (mainly spots of bright green
corrosion) were found by FTIR analysis to have minerals
other than atacamite or paratacamite (labelled as bronze
disease in Figure 5) on their surfaces. Hence, the propor-
tion reacting with actual bronze disease is lower and the
required cohort size greater.
The significant results from the second copper alloy
criteria-anchored survey are shown in Figure 6.
Figure 6. Experimentally derived reaction risk compared to cumulative
scores from object assessments for copper alloys
The blue line is from experimental data on powder
mixtures from Thickett (2012). Only five points were
determined to be statistically significant. They follow
the basic shape of the experimentally derived response
ANALYTICAL INVESTIGATIONS
curve, but because there is so little available data, it can
only be considered an indication.
Oxygen depletion
Archaeological iron
Figure 7 shows the results of oxygen depletion meas-
urements on 60 archaeological iron objects. Minimum,
maximum and interquartile ranges are shown. The red
bars are experimental powder results (same of the raw
data can be seen in the grey line in Figure 3, but the graph
is scaled to fit the survey results).
Figure 7. Oxygen depletion rates measured for 60 archaeological iron
objects
There was a sizeable spread of data similar to the results
reported by Watkinson et al. (2019). The ranking of each
individual object compared to all those tested across
the RH values tended to remain similar. It is reasonably
clear that the bulk of the data follows the experimentally
derived data.
Archaeological copper alloys
Figure 8 shows the results for the archaeological copper
alloy objects.
Figure 8. Oxygen depletion rates measured for 56 archaeological copper
alloy objects
USING EPIDEMIOLOGY TO VALIDATE SCIENTIFIC RESULTS FOR COMPLEX SITUATIONS
Again, within the range of responses, it appears the
experimentally derived bars provide a reasonable fit for
actual object response.
Discussion and conclusion
The surveys produced results in agreement with exper-
imental powder studies, validating the adoption of
their results and enhancing confidence in their use to
improve preventive conservation. The iron powder
research elucidated the impact on the reactions of RH,
acetic and formic acid and formaldehyde concentration,
temperature to a degree, the presence of copper (from
associated burial), humic acid, goethite and akaganeites
formed under different RH conditions, and the metal to
chloride ratio. The impact of short periods of higher RH,
such as when showcases or storage boxes are opened, and
the influence of still and flowing air were also investi-
gated. Many factors remain to be elucidated: the effect
of the metallurgy of the object, the different forms of
chloride present, differences in the reactivity and stability
of the akaganeites present, the reactions generating
goethite, and iron carbonate and iron sulfate. Whilst
the selection of objects for display in each showcase is
clearly not random, tests were undertaken that took into
consideration object typology and burial depth using
the diehard test suite (Florida State University 1995) for
four sites. Over 98% of the p-values were between 0.025
and 0.975, indicating the randomness tests were passed
at a 0.05 level.
The number of objects on display was found to be a
limiting factor in several instances and especially with
the less responsive copper alloy objects. The oxygen
depletion measurements produced more finely graded
results and could determine much smaller differences in
response with smaller numbers of objects. Techniques
from epidemiology proved extremely useful to the devel-
opment of the study. Together, the methods provided
confidence that the experimental corpus of results repre-
sents a good portion of archaeological iron and copper
alloy responses. The methods described can readily be
used by other researchers. The OpenEpi website guides
users through the decisions needed. The cohort number
requirements shown in Figure 1 give a general indication
for required sample sizes for such studies. Previous work
has shown that surveys of small subsets can give fairly
robust estimates for percentage reaction rates for archae-
ological metal collections. The distribution of the results
259
determines whether statistically significant differences
can be detected between cohorts, and these numbers are
always higher than those from the Fleis equation. Epide-
miology also has potential as a primary research method
and the advantage of considering the full complexity of
real objects in real environments provided methods to
accurately determine small changes are developed.
References
Argyropoulos, V. Technological Educational Institute of
Athens, Greece, personal communication, 25 February
2007.
Dean, A.G., K.M. Sullivan, and M.M. Soe. OpenEpi:
Open source epidemiologic statistics for public health,
version 3.01, updated 2013/04/06. www.openepi.com/
(accessed 25 October 2021).
Fleis, J.L., B. Levin, and M.C. Paik. 2003. Statistical
methods for rates and proportions, 3rd ed. New Jersey:
John Wiley & Sons.
Florida State University. 1995. The Marsaglia random
number CDROM including the diehard battery of tests of
randomness. Tallahassee: Florida State University.
Gibson, L.T., B.G. Cooksey, D. Littlejohn, and N.H.
Tennent. 1997. A diffusion tube sampler for the determi-
nation of acetic acid and formic acid vapours in museum
cabinets. Analytica Chimica Acta 341: 11–19.
Kelsey, J.L., A.S. Whittemore, A.S. Evans, and W.D.
Thompson. 1996. Methods in observational epidemiology.
Oxford: Oxford Academic Press.
Leese, M.N. and S.M. Bradley. 1995. Conservation condi-
tion surveys at the British Museum. In CAA94. Computer
applications and quantitative methods in archaeology
(BAR International Series 600), eds. J. Huggett and N.
Ryan, 81–86. Oxford: Tempus Reparatum.
Milner, C.S. and N.N. Dalton. 1953. Glycerol, 269. New
York: Reinhold Publishing Corporation.
Scott, D.A. 1990. Bronze disease: A review of some chem-
ical problems and the role of relative humidity. Journal of
the American Institute for Conservation 29(2):193–206.
Sully, D. and K. Suenson-Taylor. 1996. A condition survey
of glycerol treated freeze-dried leather in long-term
storage. In Archaeological Conservation and its Conse-
quences: Preprints of the Contributions to the Copenhagen
Congress, 26–30 August 1996, eds A. Roy and P. Smith,
177–81. London: International Institute for Conservation.
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Thickett, D. 2012. Post excavation changes and preventive chloride on post-excavation corrosion rates of archae-
conservation of archaeological iron. PhD dissertation, ological wrought iron. Studies in Conservation 64(8):
University of London, UK. Available online at www. 456–71.
english-heritage.org.uk/siteassets/home/learn/conser-
vation/collections-advice--guidance/thickettthesisfinal- Author
version.pdf (accessed 25 October 2021).
David Thickett has a degree in natural sciences, a PhD
Thickett, D. 2016. Critical relative humidity levels in archaeological conservation and chemistry and worked
and carbonyl pollution concentrations for archaeo- for two years in industrial ceramics research. He joined
logical copper alloys. In Metal 2016: Proceedings of the the British Museum in 1990, specialising in preventive
Interim Meeting of the ICOM-CC Metals Working Group, conservation and inorganic materials conservation
New Delhi, 26–30 September 2016, eds. R. Menon, C. research. He joined English Heritage in 2003 as a senior
Chemello, and A. Pandya, 0401_24. New Delhi: Interna- conservation scientist, mainly researching preventive
tional Council of Museums-Committee for Conservation conservation. Recent projects have focussed on historic
(ICOM-CC) and Indira Gandhi National Centre for the house environments, acoustic emission, collections
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Thickett, D. 2021. Oxygen depletion testing of metals. microclimate frames and optical coherence tomography.
Heritage 4(3): 2377–89. He sits as a UK expert to the European Standards CEN/
TC 346 (conservation standards) and is a directory board
Thickett, D. and B. Pretzel. 2010. Micro-spectroscopy: A
member of the Infrared and Raman Users Group (IRUG).
powerful tool to understand deterioration. E-Preservation
Science 7: 158–64.
Thickett, D. and P. Lankester. 2012. Critical knowledge
gaps in environmental risk assessment and prioritizing
research. Collections 8(4): 281–96.
Thickett, D. and M. Odlyha. 2013. The formation and
transformation of akaganeite. In Metal 2013: Proceedings
of the Interim Meeting of the ICOM-CC Metals Working
Group, Edinburgh, 16–19 September 2013, eds. E. Hyslop,
V. Gonzalez, L. Troalen, and L. Wilson, 103–109. Edin-
burgh: International Council of Museums-Committee
for Conservation (ICOM-CC) and Historic Scotland.
Thickett, D., S. Lambarth, and P. Wyeth. 2008. Deter-
mining the stability and durability of archaeological
materials. In Art08: 9th International Conference on NDT
of Art, Jerusalem, Israel, 25–30 May 2008. www.ndt.net/
article/art2008/papers/024Thickett.pdf (accessed 25
October 2021).
Thickett, D., V. Vilde, P. Lankester, and E. Richardson.
2017. Using science to assess and predict object response
in historic house environments. In Preventive Conserva-
tion in Historic Houses and Palace Museums: Assessment
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Silvana Editoriale SpA.
Watkinson, D.E., M.B. Rimmer, and N.J. Emmerson.
2019. The influence of relative humidity and intrinsic
Long-Term Provision of Stable Environments for Metals
Conservation
Paul Lankester*
English Heritage
London, UK
paul.lankester@english-heritage.org.uk
David Thickett
English Heritage
London, UK
david.thickett@english-heritage.org.uk
Abstract
Preservation of metals often requires dry environments.
Several aspects of generating such environments over many
years have been investigated, building on previous research.
The measurement of low relative humidity values, even
with electronic probes, requires well-adapted calibration
procedures for accurate results. Long-term changes in silica
gel performance were measured. The provision of suitable
low air exchange rate showcases and the changes in their
performance over 13 years were investigated. Pollutant gas
build-up in showcases over decades were assessed as well as
dehumidifier performance. The performance and ageing of
Lock & Lock boxes for storing archaeological metals with silica
Introduction
Providing suitable environments for long-term metals
preservation requires dehumidification and control of
pollutants. Sometimes concentrations must be very low
and careful testing of materials in enclosures is required to
avoid internally generated pollution. Archaeological iron
and copper can deteriorate at ambient relative humidity
(RH) values. Research has improved understanding of
the processes involved and curatorial debate at English
Heritage has settled on values of 30% for iron and 35% for
copper while on display, and 16% for both archaeological
metals in storage, to manage losses of value (Thickett
2012, Thickett and Odlyha 2013, Thickett 2016). For
preventive conservation to work as a strategy, these condi-
tions need to be achieved over very long time periods.
Additionally, increasing awareness of anthropological
climate change means it will be important to predict
the carbon footprint of such approaches. Organisation
is always critical to success for such endeavours, but
Sally Johnson
English Heritage
Silsoe, UK
sally.johnson@english-heritage.org.uk
*Author for correspondence
gel were also investigated. Relevant issues and observations
are discussed. The work clearly concludes the necessity for
suitable calibration to achieve accurate low RH readings
and the superiority of certain showcase designs in terms of
both initial and long-term air exchange rate. The importance
of accelerated ageing to predict long-term performance
in materials was demonstrated and improvements to dry
environment lifetime in real storage situations using a certain
type of lockable box were shown.
Keywords
showcases, storage, dehumidifier, pollution
there are also several technical aspects that can affect
long-term performance. The actual impact of these has
been investigated.
Development of low-cost methods for measuring air
exchange rates (AERs) and protocols for repeatable
measurements were critical in providing a pathway to
predict, specify and guarantee showcase performance in
the wide range of environments across English Heritage’s
estate (Calver et al. 2005; Thickett, forthcoming). Lower
air exchange rates help to control RH but increase the
concentration of damaging internal pollutants, if present.
A series of simple spreadsheet-based models have been
tested and shown to accurately predict internal RH
performance based on room values (Thickett 2020b;
Thickett, forthcoming). These can be used with data
from any space to predict the likely performance (internal
RH) of showcases and of using dehumidifiers. Thomson
262  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
(1977) developed an approximation for hygrometric
half-life:
tH1/2 = 4MHB/n(1)
Where tH1/2 is the hygrometric half-life, the time it takes
for the RH of the case/box to move halfway towards
the room RH (days); MH is the moisture-specific buffer
reservoir corrected for hysteresis (g/kg/%); B is the buffer
loading (kg/m3); and n is the AER (day−1). See Weintraub
(2002) for an explanation of the practical use of silica
gels, hysteresis and M and MH.
The models were shown to give sufficiently accurate
results when iterated at 15, 30 or 60-minute intervals
provided that the air is well mixed in the display volume
and between any silica gel compartment and the display
volume. The half-life concept can be used to estimate the
demand for dry air to keep a showcase below a certain
RH in a given room. Coupled with capacity information
on dehumidifiers, this can accurately predict the energy
use (Thickett 2020b).
Both sorbents and dehumidifiers have been used in
different showcase situations to reduce RH. Carbon
footprints have been assessed for silica gel-controlled
showcases (Thickett 2020a). Long-term performance
has been assessed with carefully calibrated RH meas-
urements.
RH measurement
Previous work has shown issues with the ageing of
RH001 indicator strips and the fact that they give low
reading after 6 years of use (Thickett 2012). Strips are
now replaced every 5 years. Electronic probes have better
precision than indicator cards and better accuracy when
carefully calibrated. Their calibration for low RH has
been investigated.
Changes to showcase AER and silica gel
performance
The two factors likely to degrade dry showcase perfor-
mance have been investigated. The increases in AER
in varying designs of showcases as they age have been
measured. Changes to silica gel isotherms after prolonged
use have also been measured with water vapour uptake
and dynamic vapour sorption. Cases can be controlled
with dehumidifiers, and some results have already been
published (Thickett et al. 2007). As many dehumidifiers
ANALYTICAL INVESTIGATIONS
have far greater capacity than is required for a single
showcase, multiple cases can be controlled from a single
dehumidifier. Performance has been assessed with cali-
brated monitoring.
Oxygen depletion testing has also been developed
and tested against long-term changes and can identify
those iron and copper alloy objects that are stable at
high RH and do not need controlled RH environments
(Thickett 2021).
Non-archaeological metals are much less RH sensitive,
but control is still important. The strategies listed above
have been used in many display and storage situations
successfully. At suitable RH values for non-archaeolog-
ical metals, silica gel calculations become more complex
because of hysteresis (above 40% RH). They are sufficient
to model showcase performance in particular envi-
ronments (Thickett, forthcoming). In some instances,
an additional amount of silica gel has been added to
compensate for uncertainty in the value.
Materials testing
Pollutant gases from showcase materials are probably the
most significant risk that showcases pose to metals. Lead,
copper alloys, steels and archaeological iron are corroded
by acetic and formic acid. A full review of the reported
damage is given in Thickett (2020b). Many methodolo-
gies exist for testing and several are being actively devel-
oped. The Oddy test, an accelerated corrosion test with
metal pieces acting as corrosion sensors, is widely used.
Reduction of the test time from the established Oddy
test is a common theme, with more sensitive analytical
methods postulated to bring improvements. The param-
eters of such tests have been investigated. Experiments
have identified materials that only emit late on in the
Oddy test, and the presence of acetic, formic and nitric
acid in these tests has been assessed. Ambient temper-
ature tests have been undertaken to examine emission
profiles of both acetic and formic acid for these materials
(Thickett et al. 2007).
Performance of polymer boxes for dry storage
Polyethylene boxes (frequently the Stewart brand or ‘old
Stewart’) with dry silica gel have been used for storage of
archaeological iron for decades. The boxes changed to
polypropylene in the mid-1990s (‘new Stewart’). Storage
of archaeological metals in Stewart boxes with silica gel
LONG-TERM PROVISION OF STABLE ENVIRONMENTS FOR METALS CONSERVATION
to keep RH values below 16% for several years in 50%
dehumidified rooms has been investigated. Newer box
designs (with locking lids) potentially offer longer silica
gel replacement lifetimes (Thickett and Odlyha 2010).
Lock & Lock boxes have been used for a decade. Recent
research has identified variability in the performance of
some brands (Thunberg et al. 2021). Similar tests have
been carried out in actual stores and ageing of the boxes
undertaken to indicate future performance. Previous
work showed the iterated Thomson equation worked
well for old-style (polyethylene) Stewart boxes as most
of the leakage occurred through the seals and not via
permeability through the box body (Thickett 2010). The
much tighter seals of the newer boxes could change this
and experiments were undertaken to estimate the ratio
of water vapour transfer between the two mechanisms.
Some aspects of ageing of the newer boxes have been
analysed, investigating the change in crystallinity, which
is related to permeability (Thickett 2012).
This study aims to address several important questions
related to safely maintaining environments for metals:
• measurement of RH
• design of showcases for low AER and how this degrades
with age
• changes in performance of silica gel and whether it
needs periodic replacement
• long-term performance of dehumidifiers
• the requirement for accelerated ageing in materials
testing for damaging pollutant emissions
• long-term performance of polymer boxes for dry
storage.
Methods
Measuring RH
The performance of electronic probes for RH often
changes with time. The RH response of a series of six
Vaisala HUMICAP probes was measured by exposing
them above glycerol solutions at 5% RH intervals at
between 0 and 80% in polycarbonate chambers in
an oven at 15°C. The RH was checked with two new
Rotronic HygroClip II probes manufacturer calibrated
at five points with a reported accuracy of 0.8%. Two
Hanwell HumBug loggers were new, two had been used
for 3 years in environments between 30 and 70% RH
and two were 6 years old and had been used in similar
environments. The effect of two-point calibrations at
33 and 75% and at 20 and 80% RH was assessed by
263
mathematically manipulating the curves measured to
fit the pair of RH points.
Silica gel
A series of 35 samples of silica gel (variously sized bags,
but mainly 500 g) were collected at random from those
held by English Heritage to map the range of gels pres-
ently used. The samples were selected according to a
range of yellowness (a rough indication of number of
reconditioning cycles) as determined by eye. Five new
samples were also tested. The mass increase of new and
old silica gel was measured by drying the gel at 110°C for
48 hours, followed by exposing it in a chamber at 30%
RH (generated by a Munters MG50 dehumidifier) and
measuring the mass gain until no further increase was
recorded. Each bag was measured with a Minolta 2600D
colorimeter and the b* value was used as an indication of
yellowing. There is a general link between the yellowing
of the cotton bags and the number of times they have
been reconditioned (heated to 110°C), but as the bags
may contain different bleaching agents, this cannot be
considered a definitive measure (Farzana and Akter
Smriti 2015). The water uptake measurement gave an
indication of the important M value (Weintraub 2002).
Changes in hysteresis may affect performance, with a
modified hysteresis corrected for MH value. For low
RH situations, this would only occur in heated rooms
in winter, when lower RHs (< 30 or 35%) can be gener-
ated. Ten representative silica gels were further tested
with dynamic vapour sorption (DVS) using a Surface
Measurement Systems Adventure. Initially isotherms at
20°C were generated between 5 and 80% RH and then
MH values were calculated by cycling 5 times between 25
and 30% and then 30 and 35%.
Dehumidifiers
The maintenance and failure rates of Munters MG50
dehumidifiers were assessed from records of 34 units
used at 13 English Heritage and British Museum sites.
For 12 dehumidifiers, the dehumidification capacity was
assessed by the manufacturers between 6 and 12 years
after installation.
Showcases
The air exchange rates of over 300 newly procured show-
cases from six manufacturers were measured using the
carbon dioxide tracer gas decay method (International
 Table 1

Type Dimension range Materials Tabela formatada

(m)
Table 1 le width height
264  ICOM-CC  |  METAL Type
2022  | HELSINKI, FINLAND n
Dimension range Materials Tabela formatada
ANALYTICAL INVESTIGATIONS
gt
(m)
h
le width height
Bottom-hinged n 0. 0.3 0.3 to 9.4, 11.2 mm
Table 1. Showcase details
desktop gt 4 to 0.6 laminated
h to 2.0 glass, steel,
Bottom-hinged 0. 2.0.3 aluminium,
0.3 to 9.4, 11.2 mm
desktop 4 0to 0.6 Dimension
laminated
gas lift assist
range (m)
Type to 2.0 glass, steel, Materials
2. length
aluminium, width height
0 gas lift assist
Bottom-hinged desktop 0.4 to 2.0 0.3 to 2.0 0.3 to 0.6 9.4, 11.2 mm laminated glass, steel,
aluminium, gas lift assist
Top-hinged 0. 0.3 0.3 to 9.4, 11.2 mm
desktop 6 to 0.4 laminated
Top-hinged 0. to
0.3 0.8 0.3 to 9.4, 11.2 mmsteel,
glass,
desktop 6 1.to 0.4 laminated
aluminium,
to 20.8 glass, steel,
some gas lift
Top-hinged desktop 1. 0.6 to 1.2 aluminium, 0.3 to 0.8
assist
0.3 to 0.4 9.4, 11.2 mm laminated glass, steel,
2 some gas lift
assist aluminium, some gas lift assist

Hinged upright 9.4, 11.2 mm

Hinged upright 9.4, 11.2 mm
laminated
Hinged upright laminated
glass, steel, 9.4, 11.2 mm laminated glass, steel,
glass, steel,
aluminium
aluminium aluminium

Pull-and-slide
Pull-and-slide 9.4, 11.2 mm
9.4, 11.2 mm
Pull-and-slide upright upright
upright laminated
laminated 9.4, 11.2 mm laminated glass, steel,
glass, steel,
glass, steel,
aluminium, aluminium, slide mechanisms top and
aluminium,
slide
slide
mechanisms
bottom
top andmechanisms
bottomtop and
bottom

Organization for Standardization (ISO) 2017). The designs
fell into four main categories, described in Table 1.
To assess air exchange between silica gel trays and the
display volume, initial trials used perforated powder-
coated steel baseboards with Baumann Ultra II cotton
fabrics adhered to them. The perforations were 5 mm and
8 mm diameter holes, each covering 25% of the baseboard
area. RH probes were placed in the display volume and
silica gel tray of eight showcases. The number of days it
took for the RH in the two compartments to achieve a
3% difference was recorded.
Having settled on the 8 mm holes, similar measurements
were taken on 40 showcases of three different designs.
The air exchange rates were re-measured in 46 showcases
after periods of use of between 2 and 13 years, sometimes
at multiple time periods.
Pollutants
A previously unpublished protocol for the Oddy test
examined coupons in a test tube after 7, 14 and 21 days
in the oven as well as at the normal end of the test after
28 days. Four materials that were assessed as showing no
corrosion after 14 or 21 days but observed to cause signif-
icant lead corrosion and, in two instances, copper corro-
sion after 28 days were subjected to further testing. As
the materials are no longer available, they have not been
named. Samples (20 g) of each material were enclosed
in 1 L corrosion jars with diffusion tubes (Gibson et al.
1997) and 0.5 mL of water for 7, 14, 21 and 28 days at
60°C. The diffusion tubes were extracted with 5 mL of
18.2 MOhm cm−1 water, filtered to 50 μm and analysed
for acetate, formate and nitrate ions with a Dionex DX600
with an AS14A column, 8 mM of sodium carbonate and
18 mM of sodium bicarbonate eluent.
Two of the materials were available as large samples.
These were tested periodically (1, 3, 5, 8, 10 and 15 years)
with emission tests designed to replicate those under-
taken industrially to methods that became ISO 16000
part 6 and 11. The samples were kept in ambient room
conditions of 10°C–24°C and 30%–75% RH. A 70 × 70 cm
sheet of each sample was placed in a stainless steel box
(80 × 80 × 40 cm) and kept at 23°C and 50% RH in a
Sanyo environmental chamber. Air was fed into the box
using a pump (Cassella) at a rate designed to give an
air exchange rate of 0.18/hour. The air in the box was
sampled (120 L at 2 L/min) using the same type of pump
into a potassium carbonate solution and analysed with
ion chromatography as previously.
Storage boxes
Two types of polypropylene boxes were investigated:
Stewart Sealfresh (1 L) and Lock & Lock Classic (1 L
polypropylene with a silicone strip seal and locking tabs).
LONG-TERM PROVISION OF STABLE ENVIRONMENTS FOR METALS CONSERVATION
Tests were conducted similar to those described by
Thunberg et al. (2021), with 44 g/L of dry silica gel in the
box and a calibrated RH probe. The boxes were placed
in dehumidified storerooms used for archaeological
metal and kept at between 48 and 53% RH. Twenty-eight
boxes of each type were tested in three different stores
for between 6 and 18 months.
To investigate the amount of water vapour permeation
through the box body, the sides and tops of the boxes
were covered in 3M 425 aluminium tape, leaving the seal
exposed. The RH increase tests were then repeated and
compared with the same box in its original state.
The potential ageing of the Lock & Lock boxes was inves-
tigated, both by accelerated ageing and by comparing the
performance of boxes used in stores for the past decade
with newly purchased ones.
New 1 L Lock & Lock boxes (that had previously had
their performance measured) were aged at 40, 50, 60 and
70°C for 14 days in quadruplicate. The environmental
chamber was run at 50% RH and 500 g of dry silica gel
was placed in the boxes to replicate their use. Before
and after ageing, attenuated total reflectance (ATR) with
Fourier transform infrared (FTIR) spectroscopy were
used on a sample cut to expose the full cross-section
(Bruker Alpha FTIR with a diamond ATR). The degree
of crystallinity was calculated using the peak ratios at
997, 972 and 917 cm−1 following the method used by
Yakimets et al. (2004). The reaction rate was calculated
as the percentage change in crystallinity per year.
Results and discussion
Measuring RH
The measured versus actual RH for the six loggers is
shown in Figure 1.
Figure 1. Calibration data for HUMICAP probes showing measured RH
versus actual RH
265
As can be seen, the response of the probes decreases
at higher RH values as they age. The new probes are
perfectly linear. It is important to undertake three-point
calibrations to detect loss of linearity as the probes age.
The black line shows the effect of recalibrating the 6-year
probe B at two points: 30 and 75%. This introduces
very large errors (up to 8%) in the low RH region. This
is a combination of the non-linearity of the response
of the aged logger and the two-point calibration used.
Unfortunately, a two-point calibration will not detect
non-linearity in the probe response. Several other RH
probes commonly used in cultural heritage show similar
behaviour. Three-point calibration should be undertaken
over the region of interest (5%–30% or 40% for this
application), with the calibration points just bracketing
the RH region. All previous calibrations (over 3600)
have shown good linear performance in even very aged
probes in the 5%–40% RH region, which indicates that
with careful calibration, accurate measurements are
certainly possible.
Silica gel
Figure 2 shows the mass uptake of the silica gels at 30%
RH, plotted against the yellowing of their cotton bags.
Figure 2. Silica gel mass uptakes at 30% RH
The mass uptakes cover less than a 1% range, indicating
that M values do not change significantly with ageing
(provided the isotherms have no significant hysteresis up
to 30% RH). There does not appear to be a correlation
between the water mass uptake and yellowing which is
indicative of ageing. This indicates the response of the
gel is not affected by the number of times it has been
reconditioned (likely related to its age).
Isotherms for three representative silica gels of the ten
measured are shown in Figure 3.
266  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND ANALYTICAL INVESTIGATIONS

Figure 3. Silica gel isotherms showing moisture content versus RH

The isotherms are very similar. There is slight hysteresis
starting around 27% RH. The hysteresis-corrected MH
values were all within 3% of the M value (Figure 4), indi-
cating this would only introduce very slight differences
in performance.
Figure 5. Measured maintenance and failure rates for Munters MG50
dehumidifiers
cation capacity had not fallen below 90% of performance
when new in any of the 12 instances measured.
Showcases
The AERs as measured just after installation of the
showcases are summarised in Table 2.

As can be seen, the type of design has a significant

Figure 4. Difference between M and MH for naturally aged silica gels
The silica gel does not appear to be ageing in a way that
affects its performance.
impact on performance. There is a large spread of values.
Bottom-hinged desktop showcases have produced
consistently lower AERs. Top-hinged desktop showcases
have the highest measured AERs, probably due to leakage
in the hinge mechanism. Leak detection with Inficon
D-Tek and the UE Systems Ultraprobe 100 equipment
indicated most of the leakage was from the hinge in the
26 instances tested (Calver et al. 2005). The pull-and-slide
doors produced lower AER in upright showcases than
in those with hinged doors.

Dehumidifiers The number of days to equilibrate the tested showcases

The vast majority of the units maintain the showcase (for the RH in the showcase to drop within 3% of that in
environment below the desired RH level. Some instances the silica gel compartment) is shown in Table 3.
(5) were observed of the humidistat calibration moving,
Table 2. Measured AER of as-installed showcases
generating higher RHs. All units have on-line monitoring
to allow swift diagnosis of failure, and this is now moni- AER (/day)
Number
tored for increases due to humidistat calibration drift. Type
tested Minimum Lower Upper
Maximum
quartile quartile
The collated failure and maintenance rates for the 34 Top-hinged 61 0.08 1.2 4.5 35
units are shown in Figure 5. desktop
Bottom-hinged 126 0.03 0.12 0.75 2.5
Five of the 34 units failed and were uneconomic to repair. desktop
Sixteen visits were required by the manufacturer, leading Hinged upright 48 0.23 0.81 1.84 12.4
to on-site maintenance or repair and in three instances Pull-and-slide 92 0.02 0.62 1.24 3.6
repair at the manufacturer’s premises. The dehumidifi- upright
LONG-TERM PROVISION OF STABLE ENVIRONMENTS FOR METALS CONSERVATION 267

Table 3. Effect of hole diameter in metal baseboards on RH equilibration time

T (°C), RH (%) Hole diameter(mm) AER (day-1) Days to equilibrate

Porchester 10–16, 63–91 Case 1 5 0.65 60
Case 2 5 0.45 65
Case 3 8 0.30 <1
Case 4 8 0.13 <1
Pevensey 15–22, 61–89 Case 4 5 0.48 54
Case 5 8 0.57 <1
Dover 11–18, 62–73 Case 6 5 1.45 52
13 – 17, 63-67 Case 6 8 1.45 <1
Rangers 14–19, 45–53 Case 7* 8 0.03 <1
16–23, 41–61 Case 7* 5 0.03 55
20–29, 41–56 Case 7* 8 0.03 <1
21–27, 43–61 Case 7* 5 0.03 54
21–33, 35–61 Case 7* 8 0.18 <1
20–34, 35–61 Case 7* 5 0.18 49
20–22, 40–51 Case 7* 8 0.18 <1
20–22, 38–52 Case 7 5 0.18 61

The 8 mm holes clearly work with very rapid equilibra-
tion between the silica gel and display volumes for the
bottom-hinged desktop showcases and environments
shown in Table 3. The 5 mm holes obviously limit air
exchange between the two volumes very significantly
under a variety of temperature conditions. How much
of a risk this poses depends on what RH the silica gel is
changed at.
Figure 6 shows the percentage increase in AER versus
the number of years since installation. A log scale was
used to accommodate the very wide range in values. The
markers are hollow for those showcases that were still
within AER specification after ageing and solid for those
that were above specification after ageing.
values measured just after 10 years after installation were
due to the cases being moved without consultation of the
technical staff and without being levelled. The pull-and-
slide upright cases came next. It is difficult to separate
the drop in long-term performance of the top-hinged
desktop cases and the hinged upright cases. The hinged
upright cases are more closely grouped together, whilst
the top-hinged desktops show some higher but also lower
increases. It should be noted that the highest increases
came from showcases with lower as-installed AERs. It is
clear that the type of showcase has a significant impact
on the AER and particularly its performance after ageing.
Showcase performance can be affected by a number of
factors. On many types of wooden floor, showcases will
move from level over time. Repeated knocks from the
public can also cause this. The mass of glass can deform
door supports and repeated opening can damage seals.
Silicone seals shrink with age and can embrittle and creep,
reducing their efficiency. Dust particles trapped in seals
also reduce their performance.

Pollutants
The amounts of acetic, formic and nitric acid emitted
from the four materials in the tests are shown in Figure 7.

All of the materials show no detectable emissions

Figure 6. AER increases versus showcase age (0.001 mg for acetate and formate, 0.005 mg for nitrate)
in the first 14 days of ageing at 60°C. Amounts are
It is clear the bottom-hinged desktop cases retain their expressed as weights as the diffusion coefficients are not
performance better in the long term. The four higher known for these species at 60°C. Two materials emitted
268  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Figure 7. Pollution concentrations emitted from materials at 60°C and
near 100% RH after 1, 2, 3 and 4 weeks
damaging acetic and formic acid after 21 days, while all
four emitted acetic, formic or nitric acid after 28 days.
This clearly shows the materials are emitting the gases late
in the test, as no or very low levels of gases were present
after 14 days. Increasing the sensitivity of the detection
system will not detect gases that are not present.
Two of the materials had large enough samples for
chamber emission tests and were tested periodically.
At 1 and 3 years, sample B did not emit any detectable
formic acid (12 µg/m3). After 5 years, 1,567 µg/m3 was
detected. This concentration is quite high and poten-
tially damaging to a range of materials (Norwegian
Institute for Air Research 2012). No acetic acid was
detected from sample A after 1, 3, 5, 8 and 10 years of
natural ageing (22 µg/m3). After 15 years, 1,023 µg/m3
of acetic acid was detected. Under natural ageing, both
samples showed very delayed emissions of formic and
acetic acid, with extremely low amounts present in the
early years. This indicates a risk when these materials
are used in showcases at ambient RHs. The newly
developed ambient/low temperature tests – BEMMA
(Bundesanstalt für Materialforschung und -prüfung
n.d.), ISO 16000-9:2006 (ISO 2006) and SMART testing
(National Conservation Service n.d.) – do not assess
ageing and will certify these materials, which will go
on to pose a risk in several years.
Storage boxes
The hygrometric half-lives of the boxes are shown in
Figure 8.
The values and spread of data for the Stewart Gastronorm
boxes are similar to those reported by Thunberg et al.
(2021). Blocking most of the permeation through the
ANALYTICAL INVESTIGATIONS
Figure 8. Hygrometric half-lives of storage boxes
Figure 9. Arrhenius plot of accelerated ageing of polypropylene boxes
at various temperatures and 50% chamber RH with the rate of decrease
in degree of crystallinity
polypropylene has some effect but changes the values by
less than 20%. The measured Lock & Lock box values
in the actual storerooms are both somewhat higher and
much less varied than those reported for an environ-
mental chamber (Thunberg et al. 2021) and higher than
the Gastronorm boxes. The 10-year-old boxes do appear
to have lower hygrometric half-lives, although there is
significant overlap in the data. The values with most of the
permeation blocked with 3M 425 tape are significantly
higher still for unaged boxes and the 10-year-old boxes
appear to perform to a similar level.
The Arrhenius plot from the accelerated ageing data is
shown in Figure 9.
As can be seen, the data follows a solid straight line and
the data from natural ageing also fits reasonably well. The
decrease in crystallinity observed would be expected to
increase permeability and may account for some of the
decreased hygrometric half-life for the naturally aged
Lock & Lock boxes in Figure 8. The overall performance
of the box is also influenced by the seal. Experiments are
ongoing to assess its long-term ageing properties.
LONG-TERM PROVISION OF STABLE ENVIRONMENTS FOR METALS CONSERVATION
Conclusion
The necessity for three-point calibration at lower RH
values has been shown to generate accurate RH data in
dry environments. The design of showcases is impor-
tant for the initial AER but much more so to ensure a
showcase retains a low AER over time. Bottom-hinged
desktop showcases have been assessed to perform best,
followed by upright showcases with pull-and-slide doors.
The performance of regular silica gel does not appear
to degrade over time (although bags will embrittle and
eventually burst, requiring replacement). Examples of
emissions from enclosed materials have been measured
after 3 or 4 weeks at 60°C but only after several years
under ambient conditions. This confirms the need for
accelerated ageing to assess materials for long-term use
with metal collections. One brand of lockable polypro-
pylene box has been found to perform somewhat better
than the commonly used Stewart boxes under actual
day-to-day conditions. Its long-term ageing behaviour
has begun to be investigated. Arrhenius-type ageing
showed increased permeability of the polypropylene.
The seal performance has yet to be studied but is another
important contributor to the box’s utility.
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Gibson, L.T., B.G. Cooksey, D. Littlejohn, and N.H.
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tion of the emission of volatile organic compounds
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materials – Determination of specific airflow rate in build-
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Author
Paul Lankester is a conservation scientist at English
Heritage responsible for caring for our historic collec-
CONSERVATION PRACTICES
The Reanimation of a Renaissance Automaton: Diana and
Stag at the Museum of Fine Arts, Boston

Susanne Gänsicke* Rolf Lang

J. Paul Getty Museum
Los Angeles CA, USA
sgaensicke@getty.edu
Independent watchmaker and
conservator
Dresden, Germany
lang-in-dresden@gmx.de
*Author for correspondence

Abstract
The preservation of museum artifacts with a functionality,
whether musical instruments, industrial heritage, or other
works of art, presents numerous challenges. Mechanical devices
date back to antiquity, were explored in the 12th century by
the Turkish engineer Al-Jazari, and during the Renaissance in
Europe generated considerable interest. Among the many types
of devices were self-propelled automata that featured opulent,
three-dimensional precious metalwork of mythological scenes
and other figural compositions. During drinking games, these
apparatuses likely moved across banquette tables, powered
by wind-up mechanisms incorporated into their bases. This
paper traces the multifaceted history of one such elaborate
Trinkspiel, Diana and Stag, housed at the Museum of Fine
Arts, Boston. Over time, both its appearance and function
deteriorated. The treatments applied to address the alterations
of the automaton and the decision to restore its mobility are
reviewed in the context of other “moving objects” and their
mechanisms.
Keywords
automaton, Joachim Fries, gilded silver, Renaissance, reverse
engineering, Trinkspiel, watchmaker, wind-up mechanism

Introduction
The preservation of museum artifacts with a function-
ality, whether musical instruments, industrial heritage,
or other works of art, presents numerous challenges.
In the following we present a case study, based on the
Diana and Stag automaton by Joachim Fries (Figure 1),
to discuss the strategies and resources needed for the
conservation of this and related objects. The article
traces the multifaceted history of this Trinkspiel, or
dinking game, which is housed at the Museum of Fine
Arts, Boston (MFA). Over time, both its appearance and
function deteriorated. The treatments applied to address
the alterations and the decision to restore the automaton’s
mobility are discussed in the context of other “moving
things” and their mechanisms.
Mechanical devices date back to antiquity, although they
are primarily known from the literature, which is the
source of the term automaton (Greek: “acting of one’s own
will”). The most famous surviving ancient apparatus, the
Antikythera Mechanism, from the 2nd century BC, has
been compared to an early computer (Marchant 2009,
Freeth et al. 2021). In the 12th century, Turkish scholar
and engineer Al-Jazari explored and developed moving
machines, such as water clocks, on a large scale, and
though none survived, his book and drawings provide
a glimpse of his ingenious inventions (Al-Jazari 1974).
After the development of clockworks in Europe in the
14th century, craftsmen across disciplines used state-
of-the-art technologies to create animated displays and
automata. These objects were intended as luxury goods,
entertainment, and for political messaging (Maurice and
Mayr 1980, Keating 2018, Koeppe 2019).
Renaissance automata feature opulent, three-dimen-
sional, precious metalwork depicting mythological
scenes and other figural compositions. Self-propelled
apparatuses are said to have navigated banquette tables
by wind-up mechanisms incorporated into their bases.
During ritualized festivities and ceremonies, special
drinking vessels and automata, referred to as Trinkspiel,
featured prominently. These extravagant gold and silver
machines were highly treasured possessions, along with
exotic materials and imports, in German princely collec-
tions and would have been displayed in the Kunstkammer
THE REANIMATION OF A RENAISSANCE AUTOMATON: DIANA AND STAG AT THE MUSEUM OF FINE ARTS, BOSTON
Figure 1. Diana and Stag automaton, Trinkspiel, MFA 2004.586a-d,
Joachim Fries (1579–1620), German (Augsburg), about 1610–20. Cast
and chased silver, partially gilded and painted with translucent lacquers,
iron, wood. Height: 33 cm; width: 24.3 cm; diam. 25.4 cm. Other (base
dimensions): 24.3 × 10.2 cm. Museum purchase with funds donated
anonymously and the William Francis Warden Fund, Frank B. Bemis Fund,
Mary S. and Edward Jackson Holmes Fund, John Lowell Gardner Fund,
and by exchange from the Bequest of William A. Coolidge. Photograph
© Museum of Fine Arts, Boston
or Wunderkammer, the forerunner of modern museums.
The southern German city of Augsburg was a center
of goldsmithing and production and held a monopoly
on these courtly drinking amusements during the
early 17th century, when a large inventory took shape
(Seling 1994, 22). Today, the Grünes Gewölbe, Staatliche
Kunstsammlungen, Dresden, holds the richest collection
of these objects (Syndram and Schermer 2004).
Diana and Stag was a popular theme, as the goddess of
the hunt was well-suited for festivities that often revolved
around hunting (Michie 2018). The story of Diana and
the stag is told in Ovid’s Metamorphoses, whose alle-
gories also influenced other Kunstkammer creations.
Three master goldsmiths, Jacob I. Miller (1550–1618),
Joachim Fries (1579–1620), and Matthias Walbaum
273
(1544–1631/32), manufactured a group of about 30
Diana and Stag automata (Seelig 1994, 154–9). Those by
Fries were found in eight collections in 1967 (Dietschy
1967), but since then more have appeared, or perhaps
reappeared or circulated.1 At least five of the automata
(in addition to the MFA’s Diana) contain a wind-up
mechanism; but if these are original and functional is not
known to the author.2 Even more spectacular self-pro-
pelled apparatuses and Tischspiele with more complex
moving superstructures are known from the same period
as Fries’ Diana and Stag (Seelig 1994, 137–8).
The desire for European luxury goods from as far as
India was documented by Francisco Pelsaert in the
17th century, in lists of items that were shipped from
England to Asia, which included “art ware inlaid with
gold and gems … new inventions and curiosities such
as have never seen before” (Moreland and Geyl 1925,
25–26).3 A 1620 watercolor from the St. Petersburg album
depicts a fictitious meeting between Jahangir and Shah
Abbas, displaying a table of luxury goods from the East
and West, and a courtier cradling a Diana automaton
(Figures 2, 3) (Ettinghausen 1961, pl. 13). The dates of
the watercolor and the creation of the Diana automata
correspond well and support the notion of the contem-
porary import of this new invention to the Mughal court.
The fascination with moving things, and animation in
general, was and remains universal. The repair and treat-
ment of moving clockworks and automata lie at the inter-
section of horology and conservation. Multidisciplinary
approaches are required that combine craftsmanship and
skills in the fabrication of mechanical gears and springs
with historical connoisseurship, scientific examination,
as well as conservation and ethical concerns. However,
the conservation literature on automata, and especially
on Renaissance mechanisms, is limited (Lang 1987;
Lorenz 2008; Vincent 2016, 75).4 The conservation of a
mechanical bird formed the central element of a novel,
perhaps loosely based on the Bowes Museum’s Silver
Swan automaton.5
The Diana and Stag automaton at the MFA
The superstructure of the MFA’s Diana and Stag autom-
aton, created by Joachim Fries likely between 1610 and
1620, is an example of Augsburg’s finest goldsmithing
tradition. A large hollow stag, wearing eardrops and
elaborate trappings, leaps upwards from an octagonal
base. A silver figure of Diana, with her quiver, sits side-
274  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Figure 2. Jahangir entertains Shah Abbas with a display of international
luxury items, circa 1618–22. Opaque watercolor, gold and ink on paper.
Height: 25 cm; width: 18.3 cm. Album leaf with painting. Attributed to
Bishandas / Freer Gallery of Art, Smithsonian Institution, Washington,
D.C.: Purchase – Charles Lang Freer Endowment, F1942.16a
Figure 3. Detail with Diana automaton. Jahangir entertains Shah Abbas
with a display of international luxury items, circa 1618–22. Opaque
watercolor, gold and ink on paper. Height: 25 cm; width: 18.3 cm.
Album leaf with painting. Attributed to Bishandas / Freer Gallery of Art,
Smithsonian Institution, Washington, D.C.: Purchase – Charles Lang Freer
Endowment, F1942.16a (detail)
CONSERVATION PRACTICES
saddle. Under the stag, there is a group of smaller figures,
including two sizable dogs, both leashed to the goddess,
and several much smaller figures, including a small horse
(its rider has been lost), a tiny hunter, a rabbit, an array
of small lizards and insects, and a flower arrangement.
Their respective sizes bear no relation to reality. Some of
the hollow shapes were likely worked by repoussé, with
sections joined by soldering, and some parts, such as the
openwork, were cut from sheet metal. Other elements
were cast and some of the small animals may have been
life casts (Koeppe 2019, 45–47, 68). Most connections
between the elements are mechanical. The stag, base,
one dog, and selected decorative elements retain what
appears to be the original amalgam gilding. The small
animals are covered with what has been described as
Kaltemail or cold enamel, likely a type of paint (Weinhold
et al. 2018).6 The overall impression is one of rich shapes,
textures, and contrasting materials.
The hollow base contained a spring-based steel mech-
anism, to be wound up using a key; the released spring
would propel the work across a banquet table. The stag
and dogs are hollow and removable, as are their heads,
and would have contained wine during celebrations.
During the Trinkspiel, once the automaton came to a
standstill, the diner closest to it removed an animal head,
sipped or drank the wine from its body, or perhaps fully
emptied the animal; the large stag was to serve a man,
the smaller dog a woman (Menzhausen 1987).
The Diana and Stag automaton traced a far longer
journey prior to joining the collection of the MFA in
2004. After its creation by Fries, the object entered the
possession of Prince Heinrich the Younger of Reuss,
known as Posthumus (1572–1635), between 1610 and
1620, and was kept in the possession of the family at
Osterstein Castle, Gera, Germany. During World War II,
the castle was completely destroyed in an air raid on
April 6, 1945, and its ruins were leveled by deliberate
detonation in 1962. Diana was presumed lost, along
with other precious collections. While the princely
family was rumored to have hid their treasures in the
garden for fear of looting, it is also possible that the
automaton was among the objects taken from a shelter
at the castle when the House of Reuss was dispossessed
by the Soviet Army. Nonetheless, some artworks were
discovered during construction work at the beginning of
the 1980s and reappeared in 1985 in a private collection,
allegedly as an inheritance.
THE REANIMATION OF A RENAISSANCE AUTOMATON: DIANA AND STAG AT THE MUSEUM OF FINE ARTS, BOSTON
Thus, Diana and Stag and the other artworks assumed to
have been lost came into possession of the city of Gera,
which secured the objects in the Museum für Geschichte,
where they were partially conserved and displayed in
1987 (Menzhausen 1987, Mues 1987).7 After Germany’s
reunification in 1990, Diana was restituted to the princely
House of Reuss but then offered in the art market more
than a decade later, when it was acquired by the MFA.8
Conservation history
The gap in Diana’s history created by World War II
leads to speculations derived from careful examina-
tion of the automaton’s condition. Safekeeping during
the war, and afterwards, may have included burial or
an unsuitably moist environment. After the object’s
arrival at the Museum in Gera in the 1980s, it was docu-
mented and treated by conservator and watchmaker
Rolf Lang (Lang 1987). The corrosion observed on the
different metals of the automaton is an excellent illus-
tration of the behavior of precious versus non-precious
metals in corrosive environments and of the enhanced
galvanic corrosion that occurs when different metals
are in contact. When Lang first saw the automaton,
the gears had been separated from the superstructure
but whether they had been in direct contact during the
time of possible burial remains unknown. The gold
and silver survived exposure or burial for over 40 years
in a corroded yet salvageable condition, but the steel
wind-up mechanism did not and was mineralized and
damaged beyond repair (Figure 4).
Figure 4. Diana and Stag automaton, MFA 2004.586a-d. Deteriorated
steel wind-up mechanism, top and partial side views. Photograph ©
Museum of Fine Arts, Boston
275
According to Lang (1987), the surface of the silver and
gilded silver was sandy, while the steel mechanism was
not fully recognizable and its condition resembled that
of an archaeological find. There were some losses to
the small figures as well as breaks and damage to the
silver openwork. The gold surface of the stag exhibited
both blue-green copper corrosion related to its alloy
composition, and iron stains, and some of the silver was
blackened. Surface cleaning of the superstructure was
carried out with complexing agents, EDTA, and thiourea,
followed by buffing with a wool cloth and jeweler’s rouge
and surface-coating with Paraloid B-72. Thus the orig-
inal aesthetic appearance of the object was restored, but
its function was not. The steel drive was mineralized to
a degree that prevented cleaning and it was therefore
treated with tannin followed by wax impregnation. From
that point forward, the mechanism remained separated
from its superstructure. Overall, the treatment held up
well, and in 2004, upon the automaton’s arrival at the
MFA, both parts were stable and apparently unchanged,
except for minor tarnish.
Fries’ Diana and Stag had remained largely unaltered
since its manufacture, and its shapes and surfaces are
consistent with the original concept. A small rock
crystal cross was added to a chain in Diana’s hand, which
would originally have held a dog leash. When and why
this modification was carried out is unknown. This
rare, nearly original condition is important, since most
automata were altered and repaired over time, as demon-
strated by the Metropolitan Museum’s Diana, described
as having undergone alterations in the 19th century
(Seelig 1991, 112).
Re-creation of the wind-up mechanism
Lang had carefully documented the individual parts in
1986 and was able to recognize fragments of toothed
wheels or broken levers. From this information, he
worked out the motor’s construction, calculated the
gear train, and determined the axel distances. Given
his expertise in the conservation of Renaissance objects
and his familiarity with the concepts, techniques, and
design of related mechanical works, Lang was interested
in making a copy of the motor. However, at that time the
project was not pursued and a few years later, when the
political landscape in Germany changed dramatically,
the automaton left Gera.
276  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND CONSERVATION PRACTICES

The idea of creating a new mechanism was revisited at

the MFA soon after it was realized that Lang was the
first conservator to have examined Diana. This led to
discussions about the possibility of reverse engineering
the motor. The information preserved in the corroded
but relatively intact gears was of critical importance and
its potential was recognized by Lang.

The Renaissance wind-up mechanism may be perma-

nently defunct, but it retains value and information vital
for the interpretation of the entire object. X-radiographs
Figure 6. 3D reconstruction of the mechanism. Graphic © Rolf Lang
taken at the MFA provided new insights into the wind-up
gears that allowed the approximate dimensions of the side
plates for the gears, wheels, drives, spring, and a wooden
spindle to be determined (Figure 5).

Figure 7. Separate, new gear parts prior to assembly. Photograph ©

Rolf Lang

Figure 5. Diana and Stag automaton, MFA 2004.586a-d. X-radiographs

showing gears; top and side views. 120 kV, 3 mA, 2.0 min, December 14,
2013 (for both). Photograph © Museum of Fine Arts, Boston

In 2013, the original, corroded work was shipped to

Lang’s workshop, near Dresden. After detailed study of
the elements, an initial 3D model was created (Figure 6).
Little is known about the original movement of Fries’
Dianas, nor that of the other Diana automata. Rosen-
berg (1922, 92) mentioned a run of 80 cm around a
Figure 8. The wind-up mechanism assembled. Photograph © Rolf Lang
square table for the Basel Diana, also by Fries. Based on
Lang’s calculations and an evaluation of the corroded
steel elements, the gears of the MFA’s Diana only move could be manufactured and positioned similar to the
forward, over a random course of 2.64 m. original (Figure 9). One difference is a larger cut-out in
the new base plate, as the position of the original wheel
New gears of the wheels and levers were made from steel could not be accurately established.
(grade ST35) and hand formed, as was done centuries ago,
although some larger parts were roughly shaped using Diana’s mechanism, although compromised, is fully
laser technology and then processed by hand (Figure 7). preserved without recent alterations, which allowed
The wooden worm was turned on a lathe (Figure 8). a determination of its individual parts and dimen-
Since the base plate, made of fire-gilded copper alloy, sions. This was particularly important since most of the
was available with its original slots and holes, the drive drinking games are now defunct or have been modified.
THE REANIMATION OF A RENAISSANCE AUTOMATON: DIANA AND STAG AT THE MUSEUM OF FINE ARTS, BOSTON 277

The automaton, with its new mechanism temporarily

installed inside the base (Figure 10) for demonstration
to MFA staff, was recorded in motion in a video. Today,
an interactive on an iPad at the museum allows visitors
to see Diana and Stag in movement, propelled by Lang’s
new gears.10 What the small screen does not convey is
the rather unruly and wobbly gait of Diana, the rasping
sounds of the works, and the jingling of the dangling
decorations, as also observed by Keating (2018, 212)
in other automata. While Diana scoots across the table
in formidable form, other types of automata flaunt
further animated features: some roll their eyes, shoot
arrows, or flap their wings. Videos of other moving
devices can be found at other museum websites, such
as the Kunstkammer video channel of the Kunsthistor-
isches Museum in Vienna, which features a number of
astounding examples. 11

Figure 9. Diana and Stag automaton, MFA 2004.586a-d. The old

mechanism next to its reconstruction. Photograph © Rolf Lang
Figure 10. Rolf Lang inserts the new mechanism into the automaton in
April 2014. Photograph © Museum of Fine Arts, Boston
Ultimately, the information was applied to create a new
drive almost identical in its technology and design. While Diana is on display, the two mechanisms, old and
new, remain in storage and are available for further study.
The study of the Diana and Stag automaton opens ques-
Preservation also encompasses the full research potential
tions for further research and technical examination. It
of the object. Beyond mechanics, the mineralized element
would be of interest to compare the extant mechanisms
retains memories of recent German history. Its inclusion
and their movement in greater detail to determine the
in future displays, real or virtual, will contribute to reflec-
similarity of the works and their movements.9 In the
tions on the horrors of war or on a particular aspect of
process, more might be learned further about the clock-
the German narrative.12
makers who produced the Trinkspiele, as they generally
did not sign their works (Vincent 2016, Keating 2018).
Conclusion
During the project at the MFA, 3D scanning was not
The MFA’s Diana and Stag was set again into motion with
employed, but it may offer new information about the
a working replica of its original gears, while the Renais-
interior of the base. The development of digital models
sance drive remains highly compromised but preserved
and their movement may provide new possibilities
and available for future examination and interpretation.
for comparing and quantifying the movements of the
In Boston, a video of the animated Diana automaton,
remaining automata.
with its new, temporarily installed wind-up mechanism
and in motion, has become integral to its display in the
Movement and presentation at the MFA
museum’s galleries. Lang brought not only his technical
The Kunstkammer gallery at the MFA features rare watchmaking skills to the project, but also his familiarity
and wonderful objects, including Diana and the Stag. with similar objects as well as a personal connection to
278  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
the object’s wartime woes.13 The story of this particular
object, its demise and resurrection, is deeply linked to
the 20th-century history of Germany: World War II,
division of the country, and unification. As history has
shown, movement of these machines across continents
is a continuum, as will hopefully be the new knowledge
gained and its renewed presentation.
Acknowledgments
At the Museum of Fine Arts, Boston, Curator of Deco-
rative Arts Tracy Albainy (†) enthusiastically supported
initial discussions in 2004 about recreating the mecha-
nism, after the object was acquired; Richard Newman
provided radiography. Special thanks to Thomas S. Michie
for helping to realize the project, to MFA photographers
and the digital team, and to Abigail Hykin for assisting
with questions and logistics.
Notes
1
 ccording to Dietschy (1967), some 20 Diana and
A 10
Stag automata can be attributed to Joachim Fries,
Walbaum, and Miller. He lists eight Dianas by Fries:
Basel (Historisches Museum Basel), Darmstadt (Hessis-
ches Landesmuseum), Frankfurt am Main (former
collection Freiherr Karl von Rothschild), Hamburg
(Sammlung Udo and Mania Bey), Lugano (Gräfin M.
Batthyany), Mailand (Ambrosiana), Moscow (Kremlin),
and New York (The Metropolitan Museum of Art),
although the exact location could not be confirmed for
all objects. Since his publication, one more Fries Diana
and Stag automaton was added to the collection in
Liechtenstein (2010) and to the Museum of Fine Arts,
Boston (2004). He omitted the Walters Art Gallery
Diana automaton.
2
 istorisches Museum Basel (Inv. 2005.336); Liechten-
H Berlin, this collaboration would have been beyond
stein, The Princely Collections, Vienna (Inv. No. SI261);
Metropolitan Museum of Art, New York (17.190.746);
Sammlung Udo and Mania Bey; and Walters Art
Gallery, Baltimore (57.923), which is dated to either
1620–1635 or the early 19th century.
3
 n illustrious, precious object, the Gemma Constan-
A berichte: 29–39.
tiniana, combining a large ancient gem in an elaborate
bejeweled and enameled gilt silver frame (Rijksmuseum,
Leiden, GS-11096), was in Peter Paul Ruben’s collection
in 1620. It was likely destined for sale to the Mughal
Court but was shipwrecked near the coast of Australia
in 1629 (Henderson 2016, 18–31).
CONSERVATION PRACTICES
4
M emoria Technica. https://mechanicalcurios.
com/49278-2/ (accessed 28 November 2021).
5
Peter Carey, The chemistry of tears, 2012, New York,
Alfred A. Knopf. Bowes Museum, Durham, UK: www.
thebowesmuseum.org.uk/Collection/Explore-The-Col-
lection/The-Silver-Swan (accessed 29 November 2021).
6
 he polychromy on the small shapes has not been
T
analyzed to date. It is opaque with color modulations
typical of paint or lacquer, rather than enamel.
7
See Gera-Chronik: www.gera-chronik.de/www/gera-
historie/ (accessed 28 November 2021).
8
S old by the princes of Reuss to Rudigier Gallery, Munich
and London. Sold in 2004 by Rudigier Gallery to the
MFA.
9
 ang believes the complexity of the automata would
L
demand individual manufacturing rather than mass
production, although some standardized elements may
have been used.
Museum of Fine Arts, Boston: www.youtube.com/
watch?v=EbmhpNaVtts (accessed 28 November 2021).
The installation was well and generously received
by the local press: www.wbur.org/news/2014/06/05/
diana-mechanical-drinking-game-mfa (accessed 29
November 2021).
11
 unsthistorisches Museum Wien: www.khm.at/en/
K
visit/collections/kunstkammer-wien/video-channel/
(accessed 28 November 2021).
12
O bjects with recent war damage are featured in
museums, for example, in the Neues Museum, Berlin,
Germany, and the National Museum, Beirut, Lebanon.
13
 he author wishes to acknowledge a deep personal
T
connection to this project. Born and raised in West
imagination for the first half of my life.
References
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Ettinghausen, R.  1961. Paintings of the sultans and
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Henderson, G. 2016. The Dutch East India Company’s
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Al-Jazari, I.R. 1974. The book of knowledge of ingenious
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Keating, J. 2018. Animating empire: Automata, the Holy
Roman Empire, and The Early Modern World. University
Park: The Pennsylvania State University Press.
Koeppe, W. 2019. Making marvels: Science and splendor
at the courts of Europe. New York: The Metropolitan
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Lang, R. 1987. Die Restaurierung des Geraer Diana-Au-
tomaten. Neue Museumskunde 30(4): 292–4.
Lorenz, K. 2008. Les automates du XIXème siècle:
Réflexion sur la conservation préventive et la restaura-
tion. Coré: Conservation et Restauration du Patrimoine
Culturel 20(2008): 15–21.
Marchant, J. 2009. Decoding the heavens. Solving the
mystery of the world’s first computer. London: Windmill
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Maurice, K. and O. Mayr. 1980. Die Welt als Uhr: Deutsche
Uhren und Automaten, 1550–1650. München: Bayerisches
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Joachim Fries. Neue Museumskunde 30(4): 290–91.
Michie, T.S. 2018. Hunter or hunted? A drinking game of
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178–9. Cambridge, MA: Harvard Art Museums.
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Mues, S. 1987. Wertvolle Kunstschätze an die Museen
der Stadt Gera übergeben. Neue Museumskunde 4: 287–9.
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Baumstark, H. Seling, L. Seelig, U. Arnold, and Bayer-
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Authors
Susanne Gänsicke, Head of Antiquities Conservation,
J. Paul Getty Museum, Los Angeles, USA, graduated in
archaeological conservation (Römisch Germanisches
Zentralmuseum, Mainz, Germany, 1987). She was objects
conservator at the Museum of Fine Arts, Boston (1990–
2016), where she remains a project member of “The auloi
from Meroë” (funded by the European Research Council).
Her research interests include manufacturing techniques
of ancient and historic metalwork, and the intersection
of traditional craftsmanship and conservation. In 2016,
she received an individual grant for fieldwork on metal
preservation in Nepal (Asian Cultural Council, NY).
She co-authored, with Yvonne Markowitz, Looking at
Jewelry (2019).
Rolf Lang, master watchmaker in private practice (since
2012), is developing a high-quality watch line, Canaletto,
and exquisite art objects. He holds a degree from the
University of Applied Sciences for Finance, Gotha, and
a diploma in conservation (1985) from the Deutsches
Museum, Berlin, GDR. In 1981, he founded the Watch
Restorers working group in Dresden. Lang served at
the State Mathematical and Physical Salon, Dresden, as
280  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND CONSERVATION PRACTICES

clock conservator (1979–1987) and as head conservator

(1987–1989). In 1989, he founded a conservation studio
and continued to develop watches. In 2003–2007 he was
operations manager/senior developer for H. Moser &
Cie, Schaffhausen.
Building an Ironclad System: A Quarter-Century of
Innovation in the Conservation of USS Monitor
Erik Farrell Lesley Haines
The Mariners’ Museum and Park The Mariners’ Museum and Park
Newport News VA, USA Newport News VA, USA
efarrell@marinersmusuem.org lhaines@marinersmusuem.org
www.marinersmuseum.org www.marinersmuseum.org
Elsa Sangouard Laurie King
The Mariners’ Museum and Park The Mariners’ Museum and Park
Newport News VA, USA Newport News VA, USA
esangouard@marinersmusuem.org. lking@marinersmusuem.org
www.marinersmuseum.org www.marinersmuseum.org
Abstract
In 1987, The Mariners’ Museum and Park partnered with the
National Oceanic and Atmospheric Administration (NOAA) to
be the official repository of artifacts raised from the United
States’ first National Marine Sanctuary. Starting in the late 1990s,
archaeologists from NOAA, partnering with the US Navy, began
a major effort to recover artifacts from the wreck of USS Monitor
(1862), the US Navy’s first commissioned ironclad. Objects
retrieved from the vessel encompassed nearly the entire engine
room and its iconic revolving gun turret. With the arrival of
Monitor’s turret in 2002, the Museum held over 208 tonnes of
archaeological material and had to build a conservation program
from the ground up. The huge scale of the project initially
necessitated the use of materials on hand, rather than an ideal
facility and equipment. Objects were stored outside in tanks
as there was not a dedicated conservation space large enough
to contain them. Following a multi-year capital campaign, the
Batten Conservation Complex (BCC) officially opened along
with an artifact exhibition space in 2007, having been designed
utilizing available conservation knowledge. Although the BCC
Introduction
To date, the USS Monitor Project is the largest marine
archaeological metals recovery and conservation initi-
ative ever undertaken. Due to the scale and complexity
of the retrieved artifacts, personnel at The Mariners’
Museum and Park have had to chart a relatively unknown
course over the last 20 years. Not only have staff had to
build a robust conservation program from scratch, they
did so before and during the construction of a conserva-
tion facility. This paper highlights experiences gained and
lessons learned on how the Museum has dealt with space
and physical considerations, conservation documenta-
tion, research and treatment, health and safety issues, and
Molly K. McGath William Hoffman*
The Mariners’ Museum and Park The Mariners’ Museum and Park
Newport News VA, USA Newport News VA, USA
mmcgath@marinersmuseum.org.org whoffman@marinersmusuem.org
www.marinersmuseum.org www.marinersmuseum.org
*Author for correspondence
was completed in less than three years, it took time to build out
internal capabilities as the conservation staff gained experience
working with, or at times even within, the artifacts. This work
allowed conservators to fully understand the artifacts’ needs,
which created pathways to tailor the laboratory system and make
the project more efficient. While the conservation of USS Monitor
is a massive endeavor from every conceivable angle, it has been
made possible through continued adaptation by conservators and
supporting staff at the Museum. The impacts of this effort have
improved all aspects of the project, including documentation,
health and safety, space and scale needs, treatment and research,
work planning, expertise, public engagement, and funding
challenges. Looking at the project from these perspectives, this
paper focuses on sharing nearly 25 years of growth, change, and
learning undertaken to conserve artifacts from USS Monitor.
Keywords
marine archaeological conservation, long-term project,
industrial archaeology, shipwreck, conservation laboratory
the facilitation of long-term project administration, all
while remaining publicly engaged over multiple decades.
Background
On December 31, 1862, USS Monitor was caught in a
storm and sank 16 nautical miles off the coast of Cape
Hatteras, North Carolina, in over 70 meters of water.
The vessel sank stern first and turned over such that its
revolutionary 104-tonne revolving gun turret separated
and became pinned under the ship on the seafloor. The
remains of the vessel were discovered in 1973, confirmed
282  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
in 1974, and in 1975 the wreck fell under the jurisdiction
of the National Oceanic and Atmospheric Administration
(NOAA) with the establishment of the Monitor National
Marine Sanctuary.
Archaeological investigations and recovery of small
objects were conducted throughout the late 1970s and
early 1980s, and in 1987 The Mariners’ Museum and
Park in Newport News, Virginia, was designated as
the repository for the management and curation of
Monitor-related materials.
By the late 1990s, NOAA archaeologists determined
that Monitor was in an advanced state of deterioration
and planned a major recovery effort in partnership with
the US Navy to retrieve the ironclad’s most significant
artifacts (Broadwater 2012). Due to the turret resting
underneath the aft portion of the vessel, a multiphase
plan was developed to retrieve the engineering section
first, followed by the turret (Figure 1).
Figure 1. Detail of the recovery plan for USS Monitor. Courtesy of NOAA,
Monitor Collection
Between 1998 and 2001 nearly the entirety of Monitor’s
engine room was recovered and transferred to the
Museum via barge. Objects included the propeller and
nine-meter shaft, skeg assembly (supported propeller
and rudder), the 24-tonne steam propulsion engine
and its supporting bulkheads, hull fragments and other
structural members, four additional steam engines, steam
lines, plumbing, stairs, railings, the propulsion engine
throttle and reversing wheel, engine room flooring, and
the steam condenser. In 2002, structural elements over the
turret were separated and the massive object was raised
using a two-part lifting system. With the turret’s arrival,
the Museum became home to approximately 20 percent
of USS Monitor.
CONSERVATION PRACTICES
Space and physical considerations
From the onset of excavations, space and physical consid-
erations became the primary challenge. Transferring
objects to the Museum required coordination between
several institutions and the use of multiple ships, cranes,
and flatbed trucks. However, communication was not
always clear on what was arriving and when, making it
difficult to plan how to best receive materials. Storage
tanks were acquired as needed; larger assemblies like the
turret required custom tanks from the beginning, but
many smaller objects were stored in converted dump-
sters as they were large, watertight, and easily available
(Figure 2). It was clear that this ad hoc situation was not
ideal and that dedicated facilities were required.
Figure 2. Early image of the conservation facilities, with large dumpsters
in the foreground used for the wet storage of engineering components
and the large tank in the background containing the turret. Courtesy of
The Mariners’ Museum and Park
The Batten Conservation Complex
Completed in 2007 as part of a USD 31 million capital
campaign, The Batten Conservation Complex (BCC) is a
1,850-square-meter facility consisting of a large industrial
space for wet object treatment (the wet laboratory), a
clean laboratory for final treatment of small to midsized
artifacts, and a dedicated collections storage area. Perma-
nently positioned within the wet laboratory were seven
oversized tanks housing the turret, propulsion engine,
steam condenser, and the turret’s two Dahlgren guns
and their carriages (Figure 3). All tanks were installed
before the walls and roof were built. Integrated trench
and plumbing systems were constructed into the floor,
allowing the movement of storage solutions to and from
the artifact tanks and acting as an emergency water
capture and leak/overflow detection system. To move
BUILDING AN IRONCLAD SYSTEM: A QUARTER-CENTURY OF INNOVATION IN THE CONSERVATION OF USS MONITOR 283

Figure 3. View of the wet laboratory with the square engine tank in
the foreground, the octagonal turret tank in the background, and the
yellow bridge crane above. Courtesy of The Mariners’ Museum and Park

artifacts and materials around, an overhead bridge crane

was installed with the capacity to lift up to 41 tonnes.

Space limitations
Although originally intended to house many more large
tanks, once staff occupied the facility, open space was
quickly consumed for other purposes. Due to a short Figure 4. Large objects being removed from their tank via a contracted
planning and construction timeline, compounded by crane for mechanical cleaning. Courtesy of The Mariners’ Museum and
the inability to fully know how the conservation project Park

would unfold, the long-term functionality of the labo-

ratory could not be vetted. Over time, areas within the
wet laboratory were carved out for a fabrication shop,
X-radiography booth, additional equipment, and spaces
to physically work on artifacts.

As a consequence of limited space, some artifact tanks

had to remain outside. This required additional fund-
raising to build an exterior storage, treatment, and work
area. However, the exterior facility did not include an
overhead crane, so conservation staff must contract a
local lifting and rigging company to move objects in
and out of treatment tanks (Figure 4). Therefore, crane
rental fees and a detailed schedule of object treatment
have had to be built into the yearly budget.

Another major factor affecting laboratory space has been

composite object disassembly.

As described by Krop and Nordgren (2011), a key step

in the treatment of Monitor’s artifacts is disassembling
them, treating the pieces individually, and ultimately reas-
sembling them, if feasible, after conservation. While the
Figure 5. (A) propulsion engine after deconcretion; (B) rack storage of
24-tonne propulsion engine would never be described as small components removed from larger engineering assemblies in the
small, it is at least compact (Figure 5A). However, disas- steel tanks behind. Courtesy of The Mariners’ Museum and Park
284  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND CONSERVATION PRACTICES

sembling it exponentially increases its footprint. As a result, and electrolysis, with quarterly reports compiled by the
there is not enough room to simultaneously disassemble conservation department’s scientist and reviewed by the
and treat all objects. For example, Monitor’s condenser conservation team to guide future treatment decisions.
could not be disassembled until one gun carriage was
Composite artifact disassembly has been fully docu-
completed and its tank emptied, which was itself a complex,
mented using photographs, diagrams, and written notes
multiyear disassembly process requiring multiple treat-
(Figure 6). The collections manager has often assisted
ment tanks and containers for storing component parts
with disassembly, assigning newly removed component
(Figure 5B). Good space management is key, which in turn
parts with catalogue numbers and recording their exact
necessitates time management and organization.
orientation in consultation with the conservators. This
Spatial limitations have also affected long-term artifact process ensures that composite objects can be accurately
storage and display. At the time of construction, these reassembled later. Institutional knowledge alone is
areas faced the same unknowns, and the intended collec- unreliable; even without staff changes, it is unlikely that
tion storage area has since been consumed by growing people will remember exactly what they did years before.
numbers of microclimate cabinets and Marvelseal-lined
crates. Compounding the challenge, this space lost much
of its initial footprint after construction with the instal-
lation of a photography studio and walk-in refrigerator.

As the USS Monitor exhibition space was built long before

the start of major conservation work, it was impossible
to accurately plan for final artifact display. Consequently,
the Museum has been faced with the challenges of floor
loading in multilevel galleries, providing accessibility for
heavy lifting and rigging equipment to move artifacts,
and maintaining microclimates in aesthetically pleasing
display designs.

Project documentation
As with any archaeological conservation endeavor, overall
project, treatment, and artifact documentation is critical.
This can be challenging with a short-term project, but
even more so when working with a complex assemblage
over multiple decades. Accurate records for numerous
small artifacts and complex composites must be main-
tained while dealing with staff turnover and technological
advances. This has been made easier by the addition of
a dedicated collections manager who has maintained
object records and coordinated with federal personnel,
allowing conservators to focus on treatment.
Treatment documentation
Although conservators within the BCC are assigned
individual objects, overall laboratory treatment docu-
mentation has been a group effort. As of 2021, the wet
laboratory houses 29 tanks containing either a single
large artifact assembly or batches of smaller objects.
Shared responsibilities include tracking desalination
Figure 6. Diagram of fragments from a wool coat found in the turret with
each assigned an individual object number. Courtesy of The Mariners’
Museum and Park
Photodocumentation
Evolution in documentation techniques is common
during lengthy conservation projects and this cannot
be more evident than with photographic documenta-
tion. When the Monitor project began, film, slides, and
early digital techniques were utilized. This has shifted to
exclusively digital photography alongside 3D modeling.
When possible, pre- and post-treatment photography
has been conducted utilizing professional, in-studio
photographic equipment. To capture treatment steps
in progress, smartphones have often been employed,
protecting more expensive cameras from dirt and debris.
Where image quality has been paramount, especially
during larger treatment operations, a museum photogra-
pher has been employed to document the work. This has
allowed conservators to focus on the work at hand and
BUILDING AN IRONCLAD SYSTEM: A QUARTER-CENTURY OF INNOVATION IN THE CONSERVATION OF USS MONITOR
created easy pathways to provide images for marketing
and social media.
Research and treatments
Due to the scale and complexity of Monitor artifacts,
conservators have faced a variety of treatment challenges,
which were unpredictable at the onset of the project.
When a new conundrum has presented itself, often
there have been limited comparative reference examples.
Therefore, conservators have invested extensive time
and resources in modifying existing treatment methods
or developing new ones. The culmination of these
processes has improved laboratory efficiency, increased
understanding of the stabilization needs of artifacts, and
made future challenges more approachable. The nature of
this work also highlights the need for quality, adaptable
research skills to be emphasized in early conservation
training. While suitable techniques can often be found
in other conservation specialties and from industry,
creativity is required in their application.
Scale
Although mechanically removing corrosion on small iron
artifacts is relatively straightforward, cleaning a six-meter
diameter, three-meter-tall gun turret has been a much
more difficult and time-consuming task. To address
this, conservators adapted dry ice blasting technology
and established cleaning parameters for wrought iron
(Hoffman and King 2019). Not only has the technique
allowed more rapid cleaning of large surfaces, it has also
enabled easier and more effective removal of components,
such as bolts and screws. Improved cleaning on fastener
heads has allowed for a better grip with extraction tools,
minimizing damage.
A similar challenge of scale occurred when removing
concretion within the two four-meter-long, seven-tonne
Dahlgren guns (Figure 7). While the boring of marine
archaeological artillery has been undertaken in the past,
these were the largest caliber guns to be cleaned to date
(Farrell 2020). Therefore, after several years of designing
and adapting previous boring systems, and at a cost of
approximately $25,000 (USD), BCC conservators part-
nered with several companies to build a custom machine.
Importantly, the new equipment has been designed to
accommodate multiple-sized guns, allowing its use on
other artillery within the Museum’s collection and any
future archaeological projects (Farrell 2022).
285
Figure 7. Conservator Erik Farrell cleaning the barrel of USS Monitor’s
starboard Dahlgren gun utilizing a bespoke drilling system. Courtesy of
The Mariners’ Museum and Park
Artifact disassembly
Artifact disassembly has been by far the project’s greatest
challenge. Disassembly has primarily been associated
with large mechanical components, having required
method and technique development for very specific
purposes. These include custom-made machinery to
separate materials, like hardened rubber gaskets holding
degraded metal elements together. Equipment was
designed utilizing elevated water temperatures to soften
the gaskets, allowing conservators to take the components
apart without damage (Hoffman and Spohn 2021).
However, artifact disassembly has not always been
feasible, creating practical and ethical dilemmas regarding
non-separable composite objects. There is still no ideal
way to treat wooden objects with embedded iron elements
without having to “choose” one material over the other.
Therefore, multiple years of research have been devoted
to corrosion inhibitors to protect metallic parts while
treating organic constituents (Sangouard et al. 2015,
Sangouard 2019).
External expertise
Given the Monitor project’s industrial nature, some tasks,
such as re-supporting the turret, required external tech-
nical expertise. The two-part lifting/supporting apparatus
used to raise and transport the turret in 2002 was never
intended as a storage mount, and a replacement was not
funded in the initial planning. Consequently, access to the
exterior of the turret’s roof was severely limited. When it
became clear that a purposely designed support system
was needed, and that the conservation team did not have
286  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
the expertise or capability to lift the 104-tonne object,
they approached the local shipbuilding industry in 2011.
Having limited dedicated funding for large-scale projects,
conservators have often relied on in-kind or at-cost
support, which can take time to set in motion. For the
turret, the re-support endeavor took eight years of onsite
consultations, email threads, and executive meetings
to arrange. Ultimately, three independent shipyards
came together in 2019 to lift the turret using four
81-tonne-capacity bottle jacks. The old supports (Figure
8A) were removed and replaced by compact pedestal
stands, allowing conservation to progress (Figure 8B).
Figure 8. (A) Turret sitting on part of the recovery structure from 2002–
2019; (B) current pedestal support system. Courtesy of The Mariners’
Museum and Park
Health and safety
Due to the scope of the USS Monitor Project, maintaining
proper health and safety measures has been critical.
Treatment tank capacities range from 75 liters for small
artifacts to over 350,000 liters for the gun turret, meaning
that staff must work in confined spaces, wear specialized
respiration equipment, climb up ladders and scaffolding,
and handle large amounts of chemicals. For example, a
1% (w/w) solution for the turret tank requires 3.5 tonnes
of sodium hydroxide (NaOH) (Figure 9A). To mix this
CONSERVATION PRACTICES
Figure 9. (A) Pallets of NaOH required for the turret tank; (B) custom
pouring device being used to add NaOH into the propulsion engine
tank. Courtesy of The Mariners’ Museum and Park
solution, conservation staff has to restrict access to the
laboratory, wear full-body Tyvek suits and full-face
respirators, and utilize an in-house fabricated pouring
apparatus to add chemical to the tank over approximately
three hours (Figure 9B).
The disposal of old treatment solutions has been arranged
by working with the regional wastewater treatment
provider and an independent environmental testing labo-
ratory. The testing laboratory conducts certified analyses
of treatment solutions for heavy metals: cadmium, chro-
mium, copper, lead, nickel, zinc, and iron, and organic
nitrogen and phosphorus. The wastewater treatment
provider determines whether these solutions may be
added to general wastewater streams and at what rate
this can be done, if the solutions must be further diluted,
or if specialized chemical disposal must be contracted.
Public engagement
One of the few knowns at the onset of the USS Monitor
project was that it would be a long-term endeavor.
Explaining the process and length of treatment is not
always straightforward to communicate to broad audi-
ences, but engagement with the public has been critical
BUILDING AN IRONCLAD SYSTEM: A QUARTER-CENTURY OF INNOVATION IN THE CONSERVATION OF USS MONITOR
to ensuring that the project remains relevant. Therefore,
a large amount of staff time across multiple museum
departments has been dedicated to developing and
executing public outreach programs, and these outreach
efforts continue to evolve.
Viewing windows
The BCC was purposely built with large viewing windows
into the wet laboratory that enable the public to watch
conservation treatments unfold (Figure 10). The turret,
propulsion engine, guns, and carriage tanks are visible
through these windows, and the conservation process
is explained and supported by videos and regularly
updated signage with content reflecting current activities.
Additionally, conservation staff have been encouraged to
spend time in this part of the gallery answering visitor
questions (Figure 10A). Positive feedback about visual
access into the wet laboratory led the Museum to renovate
the clean laboratory and install viewing windows in 2020.
This provides the public with a more comprehensive view
of the overall conservation process.
Figure 10. (A) Visitors viewing Monitor objects in treatment through
windows; (B) behind-the-scenes tour of the wet laboratory. Courtesy
of The Mariners’ Museum and Park
Behind-the-scenes and in-gallery programming
Following the construction of the BCC, the Museum
began providing behind-the-scenes tours of the wet
laboratory (Figure 10B). This has expanded over the
287
years to include Monitor collection storage and the clean
laboratory. Although tours impact productivity, because
some work must temporarily halted due to health and
safety considerations, they provide a fuller view of the
conservation process. This helps visitors, potential
partners, and donors understand why conservation can
take months, years, or even decades, and why a large
laboratory is necessary. Over time, experiences gained
from these tours led the conservation staff to develop a
range of conservation-based tabletop activities that they
can take into the galleries. These hands-on activities
have provided the public with insight into what goes on
within the laboratory spaces when behind-the-scenes
programming has been unavailable.
Virtual content
Since not everyone can physically visit the Museum,
investments have been made supporting virtual content.
As part of the BCC’s construction, web cameras were
installed within the wet laboratory, aimed at several
large artifacts, and are accessible via the Museum’s
website. Over time, the conservation department’s web
presence has expanded to include regular blogs about
ongoing conservation projects and the status of treat-
ments. In addition, the conservation team has worked
with digital content personnel at the Museum and
NOAA to develop material for Facebook, Instagram,
YouTube, and Sketchfab, reaching audiences outside
the local area and encouraging guests to keep up with
the conservation work.
Administration
From an administrative standpoint, the primary chal-
lenge to Monitor’s conservation has been the longevity
of the project and the lack of a clearly defined end date.
This has a direct impact on developing effective work
plans and maintaining financial support and project
personnel.
Project funding
To date, the total operating cost for the USS Monitor
conservation project is over USD 15 million, with
major conservation efforts expected to last another
15–20 years. Financial support has come from local,
state, and federal institutions (including dedicated funds
from NOAA), multiple public and private grants, and
many individual donors and philanthropists. This has
288  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
only been possible through a robust development and
grant writing program, as well as institutional leadership
that continues to fundraise. Without sustained effort to
maintain long-term financial support, the conservation
project could not be completed.
Work plan structure
As noted throughout this paper, the speed at which the
overall project advances has been based on experience
gained in working with the artifacts, development and
implementation of new conservation techniques, acqui-
sition of new laboratory equipment, and identification
and remediation of safety issues. Factors outside the
conservation department’s control have also affected
the project timeline, including institutional leadership
changes, economic downturns, additional funding chal-
lenges, a world-wide pandemic, and staffing changes
resulting in the loss of project knowledge. As a result,
the utilization of a narrowly defined long-range (e.g.,
five-year) conservation plan has been found impractical.
Planning has shifted towards structured twelve-month
work plans targeted at different parts of the collection
each year with the overarching goal of advancing the
treatment of all objects within the collection at the same
relative rate. These yearly plans have defined goals around
which a budget (both monetary and personnel time) is
built and which can be more easily supported with private
donor funding and grant initiatives. In addition, utilizing
an annual planning system provides greater flexibility
to pivot and re-evaluate priorities and goals, enabling
changes to be made when necessary.
Personnel
As highlighted above, staffing changes have presented a
challenge to maintaining a consistent operation of the
conservation effort. Due to the complexity of Monitor’s
artifact assemblage, extensive archaeological and historic
background information, and limited availability of
marine archaeology-specific conservation training at
the graduate level, it can take several years for new staff
to become fully proficient. As a result, the loss of a staff
member has always had an impact on project planning
and ongoing initiatives. Hired personnel dedicated to the
project at any given time has fluctuated from a low of 2
to a high of 11, directly driving the amount and type of
work accomplished from year to year. In total, 33 indi-
viduals have worked on the USS Monitor conservation
CONSERVATION PRACTICES
effort, rotating on and off the staff for both personal and
professional reasons.
In addition to core department staff, volunteers have
played a critical role in advancing the project, with many
bringing with them valuable professional expertise in
engineering and chemistry.
Furthermore, to help facilitate training in marine archae-
ological conservation, The Mariners’ Museum has hosted
several interns and fellows, having supplemented their
classroom education with opportunities for hands-on
training, research, and publications.
Conclusion
The key to the success of the Monitor conservation effort
has been the ability to adapt over time in association with
sustained support (monetary and programmatic) from
The Mariners’ Museum, NOAA, and other partners.
From the onset, there were many unknown treatment
challenges, ethical considerations, and engineering
hurdles to overcome. Most importantly, the conservation
team has had the freedom to face these unknowns without
the pressure of arbitrary treatment deadlines. This has
empowered them to take the time required to fully vet
each situation, ultimately facilitating the advancement of
conservation knowledge within the BCC that can then
be shared with the greater conservation community.
References
Broadwater, J.D. 2012. USS Monitor: A historic ship
completes its final voyage. College Station, Texas: Texas
A&M University Press.
Farrell, E. 2020. A review of selected drilling methods
used to de-concrete cast iron, smoothbore, marine
archaeological artillery. Journal of the Institute of Conser-
vation 43(2): 142–61.
Farrell, E. 2022. At the core of the problem: A bespoke
method used to clean the bores of USS Monitor’s XI-Inch
Dahlgren Shell Guns. Journal of the American Institute
for Conservation. doi: 10.1080/01971360.2022.2031458.
Hoffman, W. and L. King. 2019. Equipment identification
and the development of dry-ice blasting parameters for
cleaning archaeological wrought iron, copper alloys,
and gray cast iron. In Metal 2019: Proceedings of the
Interim Meeting of the ICOM-CC Metals Working Group,
Neuchâtel, 2–6 September 2019, eds. C. Chemello, L.
Brambilla, and E. Joseph, 265–72. Paris: International
BUILDING AN IRONCLAD SYSTEM: A QUARTER-CENTURY OF INNOVATION IN THE CONSERVATION OF USS MONITOR 289

Council of Museums–Committee for Conservation
(ICOM-CC) and Haute Ecole Arc Conservation-restau-
ration (HE-Arc CR).
Hoffman, W. and R. Spohn. 2021. Hot tub time machine:
A heated water system for artifact disassembly and treat-
ment. In Proceedings of the Objects Specialty Group and
Objects and Archaeology Discussion Group Sessions 46th
Annual Meeting, Houston, 31 May–2 June 2018, eds. K.
Dodson and M. Wilcop, 74–93. Washington DC: Amer-
ican Institute for Conservation.
Krop, D. and E. Nordgren. 2011. Disassembly of USS
Monitor’s complex mechanical components. In Metal
2010: Proceedings of the Interim Meeting of the ICOM-CC
Metals Working Group, Charleston, 11–15 October 2010,
eds. P. Mardikian, C. Chemello, C. Watters, and P. Hull,
70–78. Charleston: Clemson University.
Sangouard, E. 2019. When wood and iron are inextricably
intertwined: The treatment of a gun carriage from the
USS Monitor. AIC News 44(3): 1–10.
Sangouard, E., E. Nordgren, R. Spohn, K. Brunke, and D.
Krop. 2015. Evaluation of sodium nitrite as a corrosion
inhibitor for USS Monitor artifacts. Studies in Conserva-
tion 60(4): 253–66.
Authors
Erik Farrell is an objects conservator at The Mari-
ners’ Museum and Park (TMMP). He worked previ-
ously as an archaeological conservator at TMMP for
USS Monitor and at North Carolina Department of
Natural and Cultural Resources (NCDNCR) for Queen
Anne’s Revenge. He received his master’s degree in conser-
vation from Durham University.
Laurie King is an archaeological conservator within the
Batten Conservation Complex at The Mariners’ Museum
and Park, where she conserves artifacts recovered from
the wreck of the Civil War ironclad USS Monitor. Laurie
received her MSc in conservation practice from Cardiff
University in Wales. Previously, she has worked in archae-
ological conservation at the Çatalhöyük Research Project
in Turkey and at the Colonial Williamsburg Foundation.
Molly K. McGath, PhD, is a research scientist at The
Mariners’ Museum and Park. She received her doctorate
in materials science and engineering with a focus in
conservation science and her master’s degree in organic
chemistry from the University of Arizona. McGath
previously conducted research at the Arizona State
Museum, The Library of Congress, the United States
National Park Service’s National Center for Preservation
Technology and Training, the Smithsonian Institution’s
Asian Art museums and Museum Conservation Institute,
the United States National Gallery of Art, and Johns
Hopkins University.
William Hoffman received his master’s degree in art
conservation from Queen’s University in Kingston,
Ontario, specializing in the conservation of objects. He
has worked at The Mariners’ Museum and Park since
2009 and presently holds the position of Director of
Conservation and Chief Conservator.

Elsa Sangouard is an archaeological object conservator

at The Mariners’ Museum and Park and was previously
employed at the Swiss National Museum. She received
a conservation degree from Haute Ecole Arc Conser-
vation-restauration in Neuchâtel, Switzerland, and a
master’s degree in archaeology from the University of
Nantes, France. She has been assistant coordinator for
the ICOM-CC WOAM working group since 2017.

Lesley Haines is an archaeological conservator at The

Mariners’ Museum and Park. She works predominantly
with waterlogged materials recovered from USS Monitor.
She holds an MSc in conservation practice from Cardiff
University and a MA in maritime archaeology from the
University of Bristol.
Conservation and Technical Study of Ten Objects in the
Thiriyaya Collection at the Department of Archaeology in
Sri Lanka
Kasthuri Arachchilage Anusha Kasthuri*
Department of Archaeology
Colombo, Sri Lanka
anusha.kasthuri@gmail.com
Diveesha Ruckmal Athukorala
Department of Archaeology
Colombo, Sri Lanka
divruk@gmail.com
Abstract
This paper presents a case study of ten copper alloy icons from
the Thiriyaya Collection of the Department of Archaeology in Sri
Lanka. These icons include images of Buddha, bodhisattvas, and
Tara. In 1983, the Thiriyaya Collection was discovered in a ruined
meditation hall at the Thiriyaya Girikanda temple, built during the
first political regime of the Anuradhapura Kingdom (5th century
BC–10th century AD) and thought to be the first Buddhist stupa
on the east coast of Sri Lanka. The technical investigation of
the icons included X-radiography combined with a detailed
visual examination of the surfaces using a binocular microscope.
This approach allowed identification of the manufacturing
methods and materials as well as the current condition of the
Historical background
The historical framework of Sri Lanka was divided by
Deraniyagala (1992) into three major periods: Early Historic
(500 BC–AD 300), Middle Historic (AD 300–AD 1200),
and Late Historic (AD 1200–AD 1815). Within this
framework, the Anuradhapura Kingdom, which began
in the 5th century BC, was the first political regime in
Sri Lanka and the longest stable kingdom in Sri Lankan
history. However, it was the official arrival of Buddhism in
Ceylon (now Sri Lanka), in the 3rd century BC, that rein-
forced the culture, education, arts, and social status of the
people and allowed the country to flourish. The spread
of Buddhism was accompanied by the construction of
many Buddhist monasteries, including stupas, shrines,
meditation halls, and image houses (pilimageya), all of
which became the principal types of Buddhist religious
architecture in Sri Lanka.
Before the official arrival of Buddhism in Sri Lanka,
Lord Buddha visited the country three times before he
Anuradha Fernando
Department of Archaeology
Colombo, Sri Lanka
anufernando721@gmail.com
*Author for correspondence
objects. Scanning electron microscopy was used to examine
one sample. The technical assessment of the collection resulted
in a better understanding of the surface morphology, past burial
environments, post-discovery damage, and the effects of a lack of
conservation treatments. Our methodology provides a protocol
for studying the specific metallurgy, casting technology, and
morphology of similar copper alloy objects from archaeological
sites throughout Sri Lanka and elsewhere.
Keywords
Sri Lanka, Thiriyaya, bronze, radiography, cast, Buddha,
bodhisattva, Tara
passed away in 483 BC at the age of 80 (Geiger 2014). In
the 6th century BC, Thapassu and Bhalluka, considered
to be the first disciples of the Buddhist faith, visited Sri
Lanka as merchants. According to legend, they worshiped
in the dwelling of Bodhisattva Avalokiteshvara, located
at the Girikanda in the village of Thiriyaya. The site was
later converted to a shrine with a hair relic of Buddha
placed inside (Lakdusingha 1990). The shrine consists
of a typical classical Sri Lankan Buddhist-style circular
relic house (vatadage), image houses, and other objects
of diverse type from various phases of the Anuradhapura
period (Lakdusingha 1990).
The many cast metal figures of bodhisattvas and Buddha
images discovered throughout Buddhist sites in Sri
Lanka, including the ones at the Thiriyaya site, located
69 miles from Anuradhapura, attest to the high-level
production and distribution of these objects. Thiriyaya is
of particular interest because of its large trove of standing
CONSERVATION AND TECHNICAL STUDY OF TEN OBJECTS IN THE THIRIYAYA COLLECTION AT THE DEPARTMENT OF ARCHAEOLOGY IN SRI LANKA
and seated bodhisattvas and seated Buddhas, found in
1983 under the paving stones of a ruined meditation hall
north of the temple.
The Thiriyaya Collection
Lakdusingha (1990, 347) recorded that the Thiriyaya
trove contains 31 images of Buddha, 11 of bodhisattvas,
and 3 of Tara (a consort of Bodhisattva Avalokiteshvara).
The collection from the Thiriyaya monastery dates
to different times during the Anuradhapura period.
Schroeder (1990) dated all of the Buddha, bodhisattva,
and Tara objects to the 7th–10th century and proposed
the simultaneous production of ascetic- and bejew-
eled-style bodhisattva figures. According to Schroeder
(1990), bodhisattva and Tara figures can be dated to the
7th–8th century, although some Buddha figures might
be older.
This research was a first step in the study of the specific
metallurgy, casting technology, and surface texture of the
Thiriyaya Collection. The results are relevant to related
archaeological examples of copper alloys from historic
sites throughout Sri Lanka. Our methodology can serve as
a guide to the conservation treatment of similar objects.
Technical study
This paper presents a case study of ten copper alloy
icons from the Thiriyaya Collection of the Department
of Archaeology (DOA) in Sri Lanka. The ten icons,
comprising 6 images of Buddha, 2 of bodhisattvas, and
2 of Tara, have been stored together with the rest of the
collection at the conservation laboratory in the DOA. The
collection was excavated in 1983 and each object has since
been stored in individual plastic bags (possibly polyvinyl
chloride) with a brown cardboard label enclosed inside
each one and an additional brown cardboard label on
the exterior. The bags are tied shut with cotton string.
Methodology
Visual and microscopic investigation and
chloride test
Technical features and corrosion products were identi-
fied without the aid of magnification. The fabrication
techniques, identity of the materials, and details of the
surface decoration were determined with the aid of a
binocular microscope.
291
The corrosion products on all of the objects were sampled
and tested for chloride ions using the silver nitrate
protocol described by Selwyn (2018).
X-radiography
X-radiography (200 kV for hollow-cast objects and
280 kV for solid-cast objects) provided insights into the
manufacturing methods and materials as well as the
current condition of the icons.
Scanning electron microscopy
Scanning electron microscopy (SEM) of Buddha figure
CCL/10/19 proved to be exceptionally informative as
it revealed much about the casting technology and the
choices of materials used in the manufacture of the statue.
Results
Visual examination and chloride test
The objects of the Thiriyaya Collection are chemically
and aesthetically distinct from those in other collec-
tions of the DOA, in terms of their surface textures and
morphology. Unfortunately, the original appearance of
the objects at the time of their discovery is unknown.
The Thiriyaya bronzes differ in their types and degrees of
corrosion as well as in their surface morphology. Most of
the surfaces are covered with light-green to olive-colored
corrosion, indicative of bronze disease on copper-tin alloy
objects. In addition, a white crystalline corrosion is present
on some of the objects. Observations from 2012–2013
included “warty” surfaces, pitting, cracked crust-like
corrosion products, and, on some of the objects, compact
patinas. A fair amount of surface details is still visible on
most of the objects, despite the presence of corrosion. The
corrosion products vary from quite loose and powdery to
crystalline. The corrosion beneath the powdery layers is
waxy looking. The latter was not observed on the three
Buddha figures (CCL/10/19, CCL/10/43, CCL/10/34),
which are more severely corroded.
The Thiriyaya Collection has not yet been subjected to
an elemental analysis to determine the metal compo-
sition of the objects using SEM and energy-disper-
sive X-ray (SEM-EDX) or X-ray fluorescence (XRF).
According to Reedy and Harlacher (2007), bronzes of
the Anuradhapura period of Sri Lanka often had a high
lead content, with a tin content ranging from 4 to 17%
292  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND CONSERVATION PRACTICES

Table 1. The investigated objects of the Thiriyaya Collection

Dimensions: lnvestigation method Condition Clues of

Casting
Object ID Date Material/1 Material/2 height, X-radiograpy previous
method CI− test SEM** Surface Structure
width (cm) kV/mAs* treatments
Seated Buddha CCL/10/19 AD 800–900 Cu alloy barely 14.0, 11.5 hollow Positive Three layers; 120/6/60 physical damage, poor cleaning and
discernable core:clay:metal light-green restoration with
central corrosion/previous modern resins
armature restoration
Seated Buddha CCL/10/21 ? Cu alloy – 16.0, 12.5 solid Positive NO 220/4/120 front thin light-green sound mechanical &
corrosion/back thick chemical cleaning
corrosion
Seated Buddha CCL/10/24 ? Cu alloy copper 9.0, 8.0 hollow Negative NO 140/6/50 mostly coherent and sound mechanical
chaplets compact cleaning
Seated Buddha CCL/10/25 AD 800–900 Cu alloy iron 12.7, 11.0 hollow Negative NO 150/6/60 mostly coherent sound mechanical
chaplets and compact, little cleaning
brownish iron
corrosion
Seated Buddha CCL/10/34 AD 650–700 Cu alloy iron 14.0, 11.0 hollow Positive NO 150/6/60 light-green warts medium mechanical &
chaplets and granular texture chemical cleaning
Seated Buddha CCL/10/43 AD 800–900 Cu alloy – 10.0, 9.5 solid Positive NO 220/4/120 bronze disease/deep medium mechanical
pitting cleaning
Standing CCL/10/20 AD 700–800 Cu alloy iron 20.5, 5.7 hollow Slightly NO 140/6/50 Patches of light-green uneven mechanical
bodhisattva complex positive powdery corrosion/ metal wall cleaning
armature green patina
Seated CCL/10/23 AD 800–900 Cu alloy – 6.0, 5.5 solid Positive NO 160/5/90 patches of light-green sound mechanical
Bodhisattva powdery corrosion/ cleaning
gray color patina
Standing Tara CCL/10/33 AD 700–800 Cu alloy – 16.0, 4.5 solid Positive NO 160/5/110 White to light-green poor mechanical &
goddess powdery/crystal/ chemical cleaning
waxy corrosion
Standing Tara CCL/10/37 AD 700–800 Cu alloy – 20.0, 5.5 solid Slightly NO 200/5/120 patches of light-green sound mechanical
positive powdery corrosion, cleaning
dark-green compact
patina
* kV (kilovoltage); mAs (milliampere-seconds)
**SEM: 15.0 kV, 14.1 × 37 mm (surface cracks); 15.0 kV, 14.9 × 30 mm (cross-section)

and a slightly lower lead content of 1%–16% (Reedy and
Harlacher 2007). Craddock and Hook (2007) determined
that 8th- to 10th-century Sri Lankan castings of Tara
(2 objects), bodhisattva (6 objects), and a number of male
and female figures were made of leaded bronze (Pb range
0.03%–33.7%), with a variable tin content (1.7%–7.6%).
Casting technology
Of the ten statues, five were solid cast and five hollow
cast. The solid-cast statues consist of two Buddha
figures (CCL/10/21 and CCL/10/43), one bodhisattva
figure (CCL/10/23), and two figures representing Tara
(CCL/10/33 and CCL/10/37). The hollow-cast objects
comprise four Buddha figures (CCL/10/19, CCL/10/24,
CCL/10/25, and CCL/10/34) and one bodhisattva figure
(CCL/10/20).
While a preliminary examination of the surface textures
together with other casting evidence suggested that all
of the figures were cast, two major types of production
can be recognized: solid cast and hollow cast by direct
or indirect casting methods. The direct hollow lost-wax
production of a figure usually begins with the modeling
of a refractory core, generally a mixture of sand, clay, and
organic material. The core is then either clad with wax
sheets or molten wax is brushed onto it. Additional wax
is applied to create solid details, such as hair, feet, hands,
fingers, and sometimes the head or other ornaments
(Schorsch et al. 2019).
A requirement of the hollow lost-wax method is that the
core within the investment (also referred to as the outer
mold) is supported, to assure that it does not move after the
wax is melted out. This is achieved by inserting metal or
wooden core pins through the wax layer into the core that
are then secured in the investment. Generally, organic core
pins (if used) are burnt out during casting, leaving holes in
the casting that are commonly closed post-casting, either
by plugging or by patching. According to Schorsch et al.
CONSERVATION AND TECHNICAL STUDY OF TEN OBJECTS IN THE THIRIYAYA COLLECTION AT THE DEPARTMENT OF ARCHAEOLOGY IN SRI LANKA
(2019), in some cases the core is built around the metal
armature, which extends into the investment to support
the core during casting. The core may also be extended
through the wax layer in one or more areas such that it
engages the investment and is thus stabilized. Filled or
unfilled undercuts, cast-in repairs, remains of sprues, and
core pins are expressive and naturalistic in direct or indirect
lost-wax casting (Strahan 2010). It is generally believed
that historic bronze statuary was in most cases verti-
cally cast, usually upside down. Kasthuri (2016a, 2016b)
suggested that horizontal casting configurations were used
to produce most deities in the Buddhist pantheon in Sri
Lanka, such as the lokapala guardian deities. However,
the Buddha and bodhisattva figures were invariably cast
in vertical positions (Kasthuri 2016a, 2016b). In vertical
position casting, sprues, undercuts, and projections are
observed under the feet or around the head, while major
casting porosity at the site of gates indicates the orientation
of the statue during horizontal casting (Kasthuri 2016a,
2016b). During the Sri Lankan Historic periods, small
Buddha and bodhisattva figures were cast predominantly
in the vertical position. In this study, details of the casting
methods were revealed by the presence of chaplets, internal
armatures, and core cavities as seen by X-radiography.
The surface appearance and casting techniques of each
statue are as follows:
Seated Buddha (CCL/10/19)
The 8th- to 9th-century hollow-cast seated Buddha has
an intact core but is not structurally sound, and active
bronze disease is present on the surface. The surface
morphology of the figure’s metal is unusual. Several crusts
of corrosion have cracked or flaked off. Figure 1a shows
both how the cracks have spread through the surface and
their depth (Figure 1).
Figure 1. Scanning electronic microscopy of the cracked crust (15.0 kV,
14.1 × 37 mm), cross-section (15.0 kV, 14.9 × 30 mm) of a broken piece
from CCL/10/19: (a) outer metal layer, (b) middle clay layer, (c) carbon-
rich inner core layer. © DOA
293
The metal substance has been reduced by use, age, and
burial, as seen towards the proper-left hand shoulder,
the proper-left leg, and underneath the statue. The intact
core is black and very compact. The clay core was built
up layer by layer; once it had hardened in the kiln, the
skin of the burned clay core was covered with a fine clay
layer before the wax was applied and modeled. Three
layers (metal, unburnt clay, and burnt clay) are visually
evident in a cross-section of the broken fragments. The
SEM image of the cross-section also indicates the pres-
ence of three layers.
Voids in the metal and the central armature are visible
in the frontal radiograph of CCL/10/19, though they
are barely discernable. The core pin and cast-in repairs
are not discernable due to modern repairs and the poor
condition of the object. The core may have been built
around the metal armature, which extended into the
investment and supported the core during casting. The
statue’s deterioration can be attributed to its inherent
weaknesses as well as its previous and post-burial
environments. The modern repairs can be seen on the
statue’s head, hand, back, and underside. It is unknown
Figure 2. The corrosion products and evidence of modern repairs.
Enhanced radiography of voids in the metal and the central armature
of the Buddha statue (CCL/10/19). © DOA
294  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND CONSERVATION PRACTICES

when these repairs were made, but they were most

likely done at the conservation workshop of the DOA
(Figure 2).

A 6th-century solid-cast Buddha (1982:21) housed at

the Metropolitan Museum of Art (MMA) similarly
demonstrates later historical repairs unrelated to the
original casting. The casting flaws of the MMA’s figure
have been repaired with iron fills, which may have been
introduced during the object’s use.

Seated Buddha (CCL/10/21)

The front surface of the seated Buddha is covered with a

Figure 3. Buddha (CCL/10/24). Digitally enhanced radiographs; side by
thin layer of loose white to light-green corrosion product. side projecting chaplets. © DOA
The corrosion layer on the back is considerably thicker
and more compact than that on the front, and chloride Seated Buddha (CCL/10/25)
ions were detected. The light-gray metallic surface of
The surface of this Buddha was less corroded, more
the statue is characteristic of a high rather than a low
coherent, and compact. No chloride ions were detected.
tin content in the copper alloy. The Buddha, which is
The smooth silvery color of the surface of the body indi-
structurally sound, appears to have been solid-cast in
cated a high-tin copper alloy. However, unlike the body,
a single piece. The form and the surface-relief details
the forearms are a light-green color. This discontinuity
were achieved with tools used to work the wax model
suggests that the forearms were cast separately from
before casting (for example, the hair is modeled onto the
the body. However, in the radiograph these features are
wax layer). Also, pre-formed wax ears and a siraspatha
indistinguishable and appear opaque and dense. Tool
(ornament on top of the head) were adhered to the wax
marks on the body, including the hair, and iron core
body. The base of the sculpture is closed; cast-in repairs
pins nonetheless indicate the use of the hollow lost-wax
and the filed-off remains of an extension appear at the
casting method (Figure 4).
bottom of the base edge.

Buddha image (CCL/10/24)

A well-adhered and cohesive silvery color patina is

present on the majority of the surface of this seated
Buddha. The figure’s color indicates a high tin content
in the alloy. No chloride ions were detected.

In the initial study of this hollow lost-wax seated

Buddha, the right-side nipple was identified as part of
a copper core support. A radiograph taken at an angle
revealed a projecting nail from the reverse side, through
the core. The same radiograph showed one other
pin, a square-shaped plug at the chest that projected
into the center from the front. The circular primary Figure 4. Buddha (CCL/10/25). The different texture of the forearms;
cast-in fills can be seen on the reverse side of the hip iron chaplet. © DOA
and the end of the belly. Core supports made of iron
Seated Buddha (CCL/10/34)
were noted, as were copper core pins. The radiographs
revealed a rectangular-shaped, core-pin hole or repair This hollow-cast seated Buddha exhibits light-green
on the left shoulder and a primary sprue on the neck, corrosion products, “warts,” and “lumps,” and a cracked
all indicating the use of the lost-wax hollow casting crust where chloride ions were detected. The crust had
technique (Figure 3). cracked along the surface, generally in a granular shape.
CONSERVATION AND TECHNICAL STUDY OF TEN OBJECTS IN THE THIRIYAYA COLLECTION AT THE DEPARTMENT OF ARCHAEOLOGY IN SRI LANKA
The deep and unfilled rectangular undercut seen on
the underside suggested the location of the main sprue.
Radiographs also revealed the locations of cast-in repairs.
Deep undercut filled and unfilled core supports indicated
the use of the lost-wax casting process (Figure 5).
Figure 5. Buddha statue (CCL/10/34). “Warts” and cracked crust on the
metal; deep undercut and cast-in repairs and core pins. © DOA
Seated Buddha (CCL/10/43)
This solid-cast seated Buddha is structurally sound.
The physical damage on the left arm was presumed to
be a casting flaw. Chloride ions were detected, and the
object has suffered pitting corrosion due to active bronze
disease, which has disturbed the original appearance of
the fine patina. The figure has a closed base with casting
repairs that suggest the main sprue at the underside,
illustrating vertical casting (Figure 6).
Figure 6. Buddha statue (CCL/10/43). Pitting corrosion. © DOA
295
Standing bodhisattva (CCL/10/20)
This standing bodhisattva is less decorated than either
the other works in this study or the MMA’s bodhisattva
(1994.509). The figure does, however, show the addition
of the upavita (sacred thread), making it an ascetic
type of bodhisattva (Schroeder 1990). Patches of light-
green corrosion products cover most of the surface of
both sides of the icon. The chloride test was slightly
positive. An interesting technical finding was the use
of a complex vertical armature consisting of at least
five irregular iron strips joining and extending from
four places. However, it seems that structurally it is not
required by the statue. The vertical armature extends
from the head down through the body and terminates
above the knees. In the head, it is only vaguely seen in
the radiograph, due to the thickness of the cast wall.
Each joint in the armature has what appears to be a
knob, inserted pin, or clamp, most probably meant
to resist any slippage of the horizontal arms. The end
of the first section of the armature is connected to an
additional piece of metal support, probably serving as
a kind of anchor. The end of the third section of the
armature is completed by a coiled strip and clamp. The
third and fourth sections were joined with an inserted
pin. An additional piece of metal supports the last
connection (Figure 7).
Figure 7. Bodhisattva (CCL/10/20). Digitally enhanced radiographs; a
complex armature; cast-in repairs. © DOA
By comparison, the armature of the MMA’s bodhisattva
has both vertical and horizontal parts, with a continuous
twisted horizontal wire running through the shoulder
and the arm (Kasthuri 2016). Bodhisattva CCL/10/20
has three main core cavities, at the head, chest, and
lower body. Two rectangular chaplets are located at the
right thigh, and two are visible below the right shoulder.
296  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND CONSERVATION PRACTICES

Seated bodhisattva (CCL/10/23)

Patches of white corrosion products are present on the

surface of the bodhisattva figure, particularly near the
base of the figure and generally on the reverse side.
Chloride ions were detected.

The object is a solid cast and has fine details. The loca-
tion of one of the sprues is revealed by an area on the
underside where metal has been removed and filed,
leaving a bump on the surface. The top of the head
(jatamakuta), the ornament on the back of the head,
and the hip offered locations for a core extension during
casting (Figure 8).

Figure 9. Tara statue (CCL/10/33). The overlying corrosion products

conceal its details; casting repairs. © DOA

to the highest point of the mold in the horizontal casting

position (most likely face-up). The repair was made by
casting new metal directly over the first casting. Cast-in
repairs are on the knees, with one on the ankle. One
calf is substantially thicker than the others.

Tara figure (CCL/10/37)

The patches of white corrosion products seen on the

surface of this Tara figure tested slightly positive for
Figure 8. Bodhisattva (CCL/10/23). Possible location of core extensions
chloride ions, particularly those on the front of the figure
and on the reverse.
Tara figure (CCL/10/33)
The radiograph of the standing Tara showed opaque areas
The original surface of this Tara figure was entirely
of the solid lost-wax cast, with engraved lines in the waist.
concealed by an overlying powdery white to pale-green
The discontinuity and sharp lines on the radiograph
corrosion product, indicating active bronze disease.
indicated that a pre-formed wax head was attached to
This was confirmed by the detection of chloride ions.
the wax body before casting (Figure 10).
The detail on the surface is partially intact, including a
precious stone on the necklace (obscured by the corro-
sion products) and engraved lines on the robe and head
(representing hair).

The solid-cast Tara partially retains details from its

presumed original form. The casting flaws below the
proper-right knee, from the groin through the prop-
er-left thigh to the right thigh, were cast-in repaired.
These repairs are visible as opaque (white) patches on
the radiographs (Figure 9).

The precious stone at the neck may have been used to

hide the sprue left in the metal after casting. The area of Figure 10. Tara statue (CCL/10/37). Digitally enhanced radiographs;
the casting damage to the leg would have corresponded engraved lines in the waist; a pre-formed applique. © DOA
CONSERVATION AND TECHNICAL STUDY OF TEN OBJECTS IN THE THIRIYAYA COLLECTION AT THE DEPARTMENT OF ARCHAEOLOGY IN SRI LANKA
The uniform texture throughout the figure as seen on
the radiographs shows that the metal was poured all at
once during casting. A square runner can be seen on the
right and left elbows. The garland and legs may also have
served as pouring gates and runners.
Conservation treatment
The conservation treatment included a stability assess-
ment, mechanical cleaning, and chemical stabilization.
Excess burial soil, old restorations, and unstable corrosion
products were removed mechanically. Accretions and
active corrosion products were chemically stabilized. The
manufacturing process used for each bronze determined
the stabilization methods. For example, the immersion
method was employed for the solid-cast figures, and the
brush application method for the hollow-cast figures.
Surface cleaning was completed to remove dirt and
unstable corrosion products. Stable accretions of corro-
sion products were left untouched, as they may hold
information about the chemical nature of the alloy, the
object’s production, and the interactions of the object
with the burial environment. Cleaning was done using a
combination of cotton swabs and ethanol, with mechan-
ical cleaning carried out using a scalpel, dental picks, and
a glass bristle brush under the binocular microscope.
Although several methods to remove chloride ions from
the bronzes were considered, the author(s) finally decided
upon benzotriazole (BTA; 3% by weight) in ethanol.
Incralac1 lacquer in toluene was then applied as a coating
to the BTA-treated objects (Figure 10).
After conservation, the objects were sent to the
Anuradhapura Archaeological Museum to be placed
in a display funded by the US Ambassador’s Fund for
Cultural Preservation.
Discussion
Visual inspection and radiography were fundamental
tools to determine the conservation treatments appro-
priate to each of the described objects. The technical
information will be shared with archaeologists to recon-
struct the history of bronze casting in Sri Lanka. The
described icons, while heavily corroded, with areas of loss
as well as later repairs, have now been stabilized. As illus-
trated in this study, the corrosion and later, inappropriate
repairs often hid the full extent of the underlying damage
and technical details. The SEM images of the hollow-cast
297
Buddha figure CCL/10/19 were very informative and
illustrated cracks in the corrosion layers.
Most sculptures discussed herein were made with the
lost-wax casting method, although the technique used
in CCL/10/19 could not be determined. Several features,
such as undercut details, tool marks in the hair, chaplets,
and the use of wax appliques, indicate the use of the
direct lost-wax process. The statues may have been cast
vertically (indicated by casting repairs on the underside
or around the head), except in the case of the two Tara
figures, in which the wax channels and cast-in repairs are
located on the lower part of their bodies. Further evidence
of horizontal casting methods on the Tara figures includes
the casting porosity through the garlands and legs. Arma-
tures were used in varying thicknesses, sizes, and shapes
in the hollow-cast sculptures. This study also revealed
that armatures ranged from solid metal rods, strips, nails,
and dowels to coiled wires. Some parts of the armatures
were only faintly visible in the radiographs since iron in
archaeological contexts can corrode quickly. A variation
in the materials used to hold the core in place was found
in this collection. The X-radiographs showed that the
chaplets remaining in situ are made of metal and are
circular or rectangular (CCL/10/24 and CCL/10/25), with
the organic core pins burnt out during casting, leaving
holes in some cases. Some of these holes were closed by
plugging with copper or a copper alloy (CCL/10/24) or
by cast-in patching.
The deterioration of the objects is a consequence of their
manufacturing techniques, materials, and casting flaws,
as well as their previous and post-burial environments.
For example, the post-excavation storage of the objects
in plastic bags could have enhanced their corrosion and
worsened their condition. As is widely known, polyvinyl
chloride releases hydrochloric acid, which can promote
the deterioration of lead-containing metal and other
alloys. Additionally, the brown cardboard labels are
likely high in lignin, which could have released acids
harmful to the object in the long term. The formic and
acetic acids released by wood products may cause severe
damage to lead-containing alloys and other metals,
usually resulting in the formation of a white crystalline
growth attributable to formaldehyde (Hatchfield and
Carpenter 1986). Traces of previous treatments and
restoration, performed many years ago, were seen on
some figures. The acidic environment of the storeroom,
the previous treatments, and the contaminants from
298  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
long-term burials could together have accelerated the
degradation of the bronzes, resulting in the observed
corrosion products. However, given the lack of conser-
vation records, questions remain regarding the effects
of the previously used chemicals and procedures as
well as those of treatment on corrosion development.
Conclusion
A comparative investigation of the hollow and solid sculp-
tures demonstrated that the works were cast using the
lost-wax technique, with vertical and horizontal casting
positions. A complex armature was found in one figure
in this study. The objects have suffered varying degrees
and types of corrosion, including pitting corrosion and
the formation of warty corrosion products, but more
compact patinas were also found. The degradation states
of the objects likely reflected not only their burial envi-
ronments but also the post-excavation storage conditions.
The unique appearance of these sculptures in terms of
their surface textures, the white to light-green corrosion
products, and the results of the chloride test all point to
the presence of active chloride corrosion products. After
chemical stabilization with BTA, the figures acquired the
dark-green color typical of copper alloy metal surfaces.
An examination of the alloy composition used to manu-
facture these objects, including the copper alloys of the
CCL/10/43, CCL/10/34, and CCL/10/19 Buddha statues,
would thus be of interest to clarify the pitting corrosion
and the unusual granular cracked crust that flaked off
their surfaces. A metallographic analysis would also be
informative regarding the statues’ thermal history and
composition.
Acknowledgments
We are grateful to conservation staff members at the
Department of Archaeology, including Reshani Dhar-
mawardhana, Mithila Diyalagoda, Saduni Koshila,
and Dinushi Sadamali. We are also grateful to Jerry
Podany (retired Senior Conservator of Antiquities,
J. Paul Getty Museum) for his generous support for the
revision. Director General of Archaeology Prof. Anura
Manathunga, Palitha Herath, Anura Jayathilaka, Sanjaya
Perera at the Atomic Energy Authority Sri Lanka, Prof.
Harsha Rajapakse, and Sam Groveman are gratefully
thanked for providing expertise and the use of the SEM
facility at the Medgar Evers College, City University of
New York.
CONSERVATION PRACTICES
Notes
1
I ncralac contains benzotriazole and therefore does not
degrade or discolor in UV light and does not flake off
(Ogburn et al. 1977, 176).
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Schorsch, D., L. Becker, and F. Carò. 2019. Enlightened

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Authors
Kasthuri Arachchilage Anusha Kasthuri joined
the Central Cultural Fund in Sri Lanka as an artifact
conservator in 1993. Since 2005, she has worked at the
Department of Archaeology of Sri Lanka as an Archaeo-
logical Research Officer and Conservator. She is currently
pursuing a PhD in Near East Archaeology at the Freie
Universität Berlin, Germany.

Diveesha Rukmal Athukorala is an archaeological

research officer and conservator at the Department of
Archaeology in Sri Lanka since 2005. She holds a Master
of Philosophy in Archaeology from the Postgraduate
Institute of Archaeology, University of Kelaniya, Sri
Lanka. She completed her postgraduate diploma in
architectural conservation and monuments and sites
at the University of Moratuwa, Sri Lanka, in 2009. She
received her conservation training from the National
Research Institute Korea.

Anuradha Fernando has worked at the Department

of Archaeology in Sri Lanka since 2010, having been
promoted to Assistant Conservator in 2019. She received
her conservation training from the National Research
Institute of Cultural Heritage, Korea.
 Young Conservation Professional
Conservation of Copper and Copper Alloy Objects: A
Training Programme Conducted at the Mehrangarh
Museum Trust, Jodhpur
Sahitya Raja Sunayana Rathore*
Mehrangarh Museum Trust Mehrangarh Museum Trust
Jodhpur, India Jodhpur, India
sahityaraja@gmail.com sunayanarathore@yahoo.co.in
*Author for correspondence
Abstract
The Mehrangarh Museum Trust (MMT) conducted a six-
day in-house training programme for the conservation of
copper and copper alloy objects held at the Mehrangarh Art
Conservation Centre. The instructor invited was Dr Vandana
Singh, Managing Director of the Centre for Art Conservation and
Research Experts (CARE) in New Delhi. Theoretical and practical
sessions were taught on different subjects, which included
the ethics and principles related to metal conservation, the
nature of cupreous objects, scientific analysis, and chemical
and mechanical conservation treatments. The training
programme also included a session on X-ray fluorescence
analysis performed on 46 selected museum objects to identify
their elemental composition and the use of the interpreted
data for the preparation of a conservation treatment proposal.
The programme’s learning outcomes are a more nuanced
understanding of the material characteristics and technology
of metals, especially copper-based objects, and their
Introduction
The Mehrangarh Museum Trust (MMT), situated inside
the Mehrangarh Fort, was established in 1972 by His
Highness Maharaja Gaj Singh II, the 36th custodian of the
region of Marwar-Jodhpur (the south-western region of
the state of Rajasthan). The Trust is a generous patron of
the arts, music and a lively centre of academic study. The
fort and the museum are a centre of excellence in the field
Figure 1. Aerial view of the Mehrangarh Fort towering over the city of
Jodhpur
conservation needs and treatment requirements. The training
programme not only benefitted the in-house conservators and
junior conservation professionals but also helped in forming
interdisciplinary interactions with the curatorial department
and creating awareness for the conservation and preservation
of heirlooms belonging to private stakeholders. The training
programme also encouraged capacity building, innovative
thinking, creation of a strong ethical base, reflective practices
and involvement with science which are needed to establish
standards of competence in the field of metal conservation in
India. This collaborative training programme was supported by
Tata Trusts, under its Art Conservation Initiative, which selected
MMT as one of its five zonal partners.
Keywords
metal conservation, training programme, capacity building,
X-ray fluorescence (XRF)
of cultural heritage. The museum collection nurtures the
artistic and historic endeavours of Marwar-Jodhpur, and
the fort encompasses a platform for learning, research
and the revitalisation of age-old traditions.
The fort and the museum
The fort, at over 500 yards in length, is also one of the
largest in India, with its walls towering over the city
of Jodhpur, named after Rao Jodha (r. 1438–89) who
built the fort and established the Rathore kingdom of
Marwar-Jodhpur. Mehrangarh means ‘fort of the sun’
and is a reference to the Rathore clan’s mythical descent
and lineage from the Hindu sun god Surya (Jasol et al.
2018). The fort is not only a centre of culture and history
but also a home to the royal family, a former military base
and, with its many temples and shrines, a place of worship
CONSERVATION OF COPPER AND COPPER ALLOY OBJECTS: A TRAINING PROGRAMME CONDUCTED AT THE MEHRANGARH MUSEUM TRUST, JODHPUR
(Jasol et al. 2018). The Trust undertakes the architectural
conservation of the Mehrangarh Fort through a conser-
vation master plan. While the fort is its top priority, the
Trust is also actively involved in the preservation and
restoration of other heritage structures such as Nagaur
Fort, Soor Sagar Palace, the Mandore Cenotaphs and the
Step Wells of Jodhpur.1 The conservation and restoration
of historical objects and museum artefacts are conducted
by the Mehrangarh Art Conservation Centre (MACC),
established in 1996. The conservation centre has expertise
in dealing with a wide spectrum of materials, such as
paper, paintings, textiles and metal artefacts. Further-
more, the centre also undertakes projects on preventive
conservation, display and ideal storage parameters in
collaboration with the museum curatorial department.
In-house training programme on the conserva-
tion of cupreous objects at MMT
In 2019, MMT was selected as one of the five zonal
partner institutes for the north-western region under the
Tata Trusts Art Conservation Initiative.2 One of the objec-
tives of this initiative is to perform a field survey which
involves conducting condition assessments of collections
at private or public museums and historic houses in India,
provide preventive conservation training and prepare
proposals for the conservation of these collections.
MMT houses a wide variety of metallic heritage, which
reflects the rich artistic traditions of the royal dynasties of
Rajasthan and Indian courtly life (Jasol et al. 2018). This
heritage is also reflected in the collections of decorative
art and household and utilitarian objects in the historic
houses of Rajasthan. The survey revealed that most of
the private collectors were unaware of the value, origin,
provenance and design characteristics of the metal objects
in their possession. These objects also lacked care and
maintenance, leading to deterioration and corrosion,
most notably in the case of copper and copper alloys.
The zonal centres also conduct training programmes for
the in-house conservators, both junior and senior, private
collectors and the curators. The training programme
facilitates capacity building, upskilling, formulation of
innovative and novel procedures for preventive conser-
vation, and remedial treatments. The MACC decided
to conduct a metal conservation training programme
in order to learn and research copper and copper alloy
objects. The programme also helped conservators and
conservation scientists to gain comprehensive knowledge
301
on the art and history of copper and copper alloys in
Rajasthan, and their interaction with the curators and
private collectors will aid in the learning and review of
preventive conservation techniques for metal objects.
About the teaching expert
The instructor invited to conduct the training was Dr
Vandana Singh, whose experience and expertise are
applicable to the requirements of the training programme.
She has been the Managing Director of the Centre for Art
Conservation and Research Experts (CARE) in New Delhi
since 2016. Her research focuses on the scientific analysis
of metallic heritage artefacts to develop a deeper under-
standing of the history, craftsmanship, provenance, dete-
rioration process and originality of objects using advanced
material characterisation techniques (Singh 2014).
The instructor developed the curriculum, theoretical
information, conservation treatments for the practical
sessions and the portable X-ray fluorescence analysis
(pXRF).
Museum objects chosen for the pXRF analysis and
practical treatments
The museum houses an impressive number of arte-
facts – firearms, arms and armour dating from the
16th–20th centuries (Elgood 2017, Elgood 2021); utility
objects dating from the 20th–21st centuries; textiles and
costumes dating from the 18th–20th centuries; and deco-
rative art dating from the 17th–20th centuries (jewellery,
furniture, palanquins and interior décor) belonging to
the Marwari culture in Jodhpur – and showcases the
opulence of the royal family, who have created, provided
and received majestic creations from all over the world
(Jasol et al. 2018).
After the assessment of the metal collection with the help
of the curatorial department, a total of 46 objects were
chosen, which consisted of utility and decorated house-
hold objects such as storage boxes, vessels, lamps, orna-
mental plates, ornamental animal jewellery and vintage
toys. These objects were also composite, made of different
metals (soldering, plating and finishing) and materials –
for example the metallic pieces on the animal jewellery
are linked together by a textile material. The objects were
selected predominantly according to visual observation,
state of deterioration (by observing the coloured patina
and corrosion layers) and previous documentation. The
302  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
metal composition of at least 40 objects was uncertain,
hence the choice of pXRF analysis for the identification
of the elemental characteristics. Three utility objects
(storage containers), a decorative plate and a toy car were
selected for the remedial conservation treatments. The
decision-making for the treatment proposals was a core
objective of the training programme.
Syllabus and training schedule
The teaching and communication methods were both
theoretical and practical. The instructor began with an
interactive session on the nature of cupreous objects
which included alloy compositions, casting techniques,
chasing and finishing techniques (Figure 2). She also
highlighted the importance of understanding the envi-
ronmental influence on the cupreous objects, and infor-
mation was provided on the factors of deterioration,
such as the effect of moisture and relative humidity on
the formation of corrosion. Case studies on scientific
examination and analytical techniques such as optical
microscopy and XRF were provided. The instructor
also explained the use of scanning electron microscopy
(SEM) and X-radiography to understand corrosion
chemistry. Format samples of a condition assessment
report and a conservation treatment record specific to
metal objects were also provided. The rest of the subject
matter included:
• mechanical and chemical cleaning techniques;
• aesthetic and ethical considerations while performing
cleaning treatments;
• safety protocols while using chemical reagents and
solvents;
• conservation methods for treating bronze disease;
• protective coatings.
Figure 2. The instructor, Dr Vandana Singh, presenting a theoretical
session
CONSERVATION PRACTICES
Group discussions were held throughout the programme
at the end of every practical session. The instructor raised
questions on the treatments performed, choice of tools
and materials, and the outcome of the conservation
treatments.
Classroom exercises
Under the guidance of the instructor, the participants
performed photo-documentation and a condition assess-
ment for five objects: UT/32 (storage vessel), UT/15
(storage vessel), UT/254 A-B (storage container), UT/463
(toy car) and UT/468 (decorative plate) (Figure 3).
Figure 3. The five objects selected for the practical conservation
treatments: UT/32 (storage vessel), UT/15 (storage vessel), UT/254 A-B
(storage container), UT/463 (toy car) and UT/468 (decorative plate)
For the first time in Mehrangarh, XRF analysis was
performed on the 46 objects. The participants learned
about the working principles, importance of non-destruc-
tive analysis and the parameters required for selecting the
spots for analysis. The handheld XRF analyser3 identified
the elements present and their concentrations. Using
fundamental parameter (FP) algorithms, concentrations
were calculated as mass fractions normalised to 100%
to avoid systematic errors in the geometric factors used
when forward calculating X-ray intensities (Elam et al.
2002, Elam et al. 2004). These FP methods are commonly
referred to as ‘standardless’, because day-to-day measure-
ment of standards is not required to measure concentra-
tions in a sample (Table 1; Figure 4). The pXRF analysis
of the five objects revealed the major and trace elements.
Analysis of object UT/463 revealed that the toy car was
made of a binary alloy of copper (Cu-Zn) or brass.
Conservation treatment proposals were drafted incor-
porating the pXRF results, and a USB microscope was
used to investigate the deterioration process.
These portable and easily accessible microscopes were
used to view (at 50× and 100× magnification) the
CONSERVATION OF COPPER AND COPPER ALLOY OBJECTS: A TRAINING PROGRAMME CONDUCTED AT THE MEHRANGARH MUSEUM TRUST, JODHPUR 303

Table 1. Results of X-ray fluorescence (XRF) measurements (in weight %) on object UT/463

ID
Sample
Acc. No. location Fe Ni Cu Zn Ag Pb Co Cd
position
file #
Roof 122 0.07 - 64.03 35.71 - 0.19 - -
UT/463 Wheel 123 0.28 0.02 65.64 33.8 0.03 0.25 0.01 0.07
Bonnet 124 0.07 0.04 62.23 37.2 - 0.33 0.01 0.12

Figure 4. Image showing the sampling spots for pXRF analysis from Figure 6. Microscopic examination of object UT/468 to view the blue-
object UT/463 coloured corrosion product

Figure 7. Microscopic examination of object UT/254 A-B to view the

green-coloured corrosion product

which they suggested could be chlorides, carbonates,

Figure 5. Microscopic examination of object UT/463 to document the
corrosion and patina layers
different layers present on the surface, such as dust
and dirt depositions, and the oxide patina. The storage
vessels and boxes also had organic depositions, since
they were used for storing food. Grease accumulation
and oily surfaces could be seen on object UT/15, a
storage vessel locally known as thumbi/lota (in the
Marwari language), which was used to store ghee
(clarified butter) and buttermilk (Pena-Serna and
Restrepo-Betancur 2020). Object UT/468 showed bright
blue crystals in the microscopic images (Figure 6), and
object UT/254 A-B revealed a thick layer of sea-green
coloured crystals (Figure 7) which made the surface
look uneven and irregular, and different from the
smooth, brown-coloured layer which did not disfigure
the objects. Participants provided their observations
and deductions about the copper corrosion products,
acetates, sulfates, oleates or sulfides.
The causes and the factors of deterioration were discussed,
such as the influence of relative humidity, atmospheric
acidic gases, the organic constituents, mainly fatty acids
and proteins (Gebreselassie et al. 2016, Chaudhari et al.
2018), and the reaction of moisture, which leads to
the formation of corrosion products. The instructor
explained that further analysis was required to identify
the corrosion products, for which techniques such as
Raman spectroscopy and SEM-EDS could be performed.
Other damages identified included abrasions, white
accretions and adhesive labels.
After identification of the conservation problems, the
instructor explained that the objectives of cleaning were
to contribute to the long-term stabilisation of the object,
not destroy the naturally occurring protective patina
and remove the corrosive particles affecting the original
layers of the object. For example, tinning (locally called
304  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND CONSERVATION PRACTICES

kalai) was done on the insides of object UT/254 A-B,

including the lid, since the vessel was a roti daan, i.e. it
was used to store Indian bread. According to tradition,
kalai work was performed to prevent food poisoning from
the reaction of copper with organic acids. The bottom
rim and the spout were soldered with tin in the case of
object UT/32, showcasing the traditional metallic surface
coating and soldering techniques. Most of the animal
jewellery was coated with a layer of silver or gold, which
was confirmed by pXRF.

The conservation treatments started with dry brushing

of the object to remove the dust and dirt deposition. For
the removal of accumulated grease, oil and wax resi-
dues, cotton swabs dipped in chemical solvents, such as
acetone, white spirit or ethanol, were used in the presence
of a fume hood. Mechanical cleaning using a micromotor
equipped with brass bristle brushes and abrasives, such as
fine calcium carbonate and pumice powder, was tested.
A slurry of the abrasives was prepared using deionised
water (Ases Chemical Works, Jodhpur; Figure 8). The
slurry of pumice powder was applied using a cotton swab
on objects UT/254 A-B, UT/463, UT/32 and UT/15 and
was effective in the removal of the blue-green corrosion
products. However, caution was advised while using the
Figure 9. After the application of microcrystalline wax as a protective
abrasives. Gentle movements are required, since they can coating, the instructor buffs the wax using a muslin cloth to achieve a
act as stripping agents. uniform coating

and UT/32, after which a coating of Renaissance wax

was buffed using muslin cloth (Figure 9).

The training programme ended with the evaluation of

the conservation treatments applied on the five selected
objects. Group and individual discussions were held
on the topics of gel-based cleaning treatments, such as
agar and gellan gums (Giraud et al. 2021), and the use
of Incralac and its durability for the conservation of
outdoor brass objects.

Figure 8. The conservator performing mechanical cleaning of object
UT/463 with a bristle brass brush attached to a micromotor tool
For the protective coating, microcrystalline wax (Renais-
sance wax) and Paraloid B-72 (CTS Europe) were the
preferred choices, as these create a barrier between the
object and any environmental impacts and slow down
the ongoing deterioration of the metal substrate. Paraloid
B-72 was prepared by dissolving 2% w/v in acetone and a
single layer was applied on objects UT/468, UT/254 A-B
Learning outcomes of the programme
The intensive six-day training course provided an excel-
lent opportunity for the young and senior conservators,
curators, stakeholders from private sectors and volunteers
to gain comprehensive knowledge and hands-on expe-
rience in the conservation and scientific examination of
copper-based artefacts. The conservation team created
condition assessment reports and specific conservation
treatment proposals for cupreous objects. The reports
CONSERVATION OF COPPER AND COPPER ALLOY OBJECTS: A TRAINING PROGRAMME CONDUCTED AT THE MEHRANGARH MUSEUM TRUST, JODHPUR
included the curatorial aspects, such as the artistic and
historical details, and the scientific details focusing on
possible chemical testing and analysis required to identify
the corrosion products.
The use of XRF led to a eureka moment. The gold-
en-hued elephant bell, which was listed as a brass
ornament, was actually made of silver gilt (Figure
10). Similarly, the animal ornamentation (neckpieces;
Figure 11) and a decorated bedstand were incorrectly
listed as brass objects, whereas, vice versa, objects which
were thought to be made of silver, for example the deco-
rated Paan daan or betel nut box, were actually made of
tin-coated copper and zinc. The museum has prepared
documentation reports for the 46 objects under the
instructor’s guidance and their material characteristics
are now fully known.
Figure 10.
The in-house
conservator
performing a
pXRF analysis
on the
elephant bell

305
The in-house conservators performed the conservation
treatments on the remaining cupreous objects in accord-
ance with the techniques learned on the programme. A
joint proposal was presented with the curatorial depart-
ment to incorporate passive air samplers for pollutant
monitoring and for understanding the most significant
pollutants responsible for copper corrosion in order to
improve storage and environmental control for cupreous
objects. The success of the training programme opened
a pathway to plan and execute a series of object-specific
and metal-specific conservation training programmes
for artefacts, such as swords and firearms, silver objects,
armour, and the processes of sword-making and hilt
designing.
Conclusion
Strong ethics, reflection, science, preventive measures and
advocacy are all part of the modern conservation remit.
The power of collaboration is astounding and can create
partnerships that establish standards of competence in
the field of art conservation.
Acknowledgements
The authors would like to express their appreciation to
His Highness Maharaja Gaj Singh II, managing trustee
of the Mehrangarh Museum Trust, and Baijilal Sahiba
Shivranjani Rajye, CEO of the Mehrangarh Museum
Trust, for their full support throughout the project.
We are forever grateful to our previous director, Karni
Singh Jasol, for his encouragement, and we would like
to thank the instructor, Dr Vandana Singh, for her
guidance and in-depth knowledge. Our thanks also go
to the conservation team at the Mehrangarh Art Conser-
vation Centre – Mr Sunil Laghate, head of department,
Mr Vikram Rathore, the manager, the conservators Mr
Surender Singh, Mr Achal Shekhawat, Mr Ajay Vyas,
Figure 11. Course participants
identifying a sampling spot
on the elephant necklace for
XRF analysis and a technician
performing the analysis on
the verso of the medallion. An
average of four sampling spots
 were analysed
306  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Mr Harender Singh, Ms Nisha Poonia and Ms Komal
Joshi, the mount section supervisor, Mr Zakir Belim,
the senior computer operator, Mr Dilip Dave, and
the senior attendant Mr Dhirendra Singh – for their
enthusiastic participation and support. We extend our
thanks to the Tata Trusts Art Conservation Initiative
team for their insights.
Notes
1
C onservation of heritage structures performed by
MMT: www.mehrangarh.org/research-conservation/
architectural-conservation-projects/
2
 he Tata Trusts is a charitable organisation duly regis-
T Jasol, K.S., P.A. Andrews, R. Elgood, C. Glynn, and A.D.
tered under Maharashtra Public Trusts Act, 1950. The
Tata Trusts Art Conservation Initiative proposes to
establish, develop and strengthen art conservation
centres in five zonal locations across India and create
a cohort of trained conservators. www.tatatrusts.org/
our-work/arts-and-culture/conservation/art-conser-
vation-initiative
3
 he XRF analysis was performed using a handheld
T
portable XRF spectrometer belonging to the company
Elvatech LTD, Ukraine. The model was a Prospector 2
and the elemental concentrations were provided by the
analysis algorithms based on ‘standardless’ fundamental
parameters and empirical (regression) calibration. The
software used was Windows-based and compatible with
ElvaX™ PC software. The X-ray was used for a maximum
of 15 s at a voltage of 40 kV, and an SDD X-ray detector
with a maximum energy resolution of < 165 eV.
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atomic database for X-ray spectroscopic calculations.
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and their armoury at Jodhpur Fort, vol. I. New Delhi:
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Delhi: Niyogi Books.
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0307.12236
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Raimon, and E. Guilminot. 2021. Use of gels for the
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52: 73–83. https://doi.org/10.1016/j.culher.2021.08.014
Jhala. 2018. Peacock in the desert: The royal arts of Jodhpur,
India. New Haven: Yale University Press.
Pena-Serna, C. and L.F. Restrepo-Betancur. 2020. Chem-
ical, physicochemical, microbiological and sensory char-
acterization of cow and buffalo ghee. Food Science and
Technology 40(suppl. 2). https://doi.org/10.1590/fst.32219
Singh, V. 2014. Linking heritage conservation with
cultural revitalisation. In Building Strong Culture through
Conservation: ICOM-CC 17th Triennial Conference
Preprints, Melbourne, 15–19 September 2014, ed. J.
Bridgland, art. 0906, 6 pp. Paris: International Council
of Museums. Available at www.icom-cc-publications-on-
line.org/
Authors
Sahitya Raja is a conservation scientist currently
working as a conservator-restorer at the Mehrangarh
Museum Trust in Jodhpur. She has an MSc in conser-
vation and restoration of cultural heritage from the
University of Bologna and completed her experimental
thesis at the University of the Basque Country, which
focused on the use of multi-analytical instrumentation
for the conservation and restoration of the Punta Begoña
Galerias, a historic building located in Getxo in Spain.
Her ongoing projects include the spectroscopic analysis
of the wall paintings at Mehrangarh Fort and the conser-
vation of the metallic heritage of Rajasthan.
Sunayana Rathore, PhD, is currently deputy curator
of the Mehrangarh Museum Trust in Jodhpur. She has
worked in the areas of creative exhibition planning,
design and display and preventive care and storage of
museum objects. She has a master’s degree in heritage
management with a specialisation in conservation from
CONSERVATION OF COPPER AND COPPER ALLOY OBJECTS: A TRAINING PROGRAMME CONDUCTED AT THE MEHRANGARH MUSEUM TRUST, JODHPUR 307

Sophia College. She qualified the National Eligibility Test

(NET) by the University Grants Commission (UGC)
for a lecturer’s position in museology and conservation
in 2004 and was awarded a Junior and Senior Research
fellowship by UGC for her PhD in museology from the
National Museum Institute. A native of Rajasthan, she
is interested in preserving its tangible and intangible
heritage.
Keeping it Kosher: The Care and Treatment of the Judaica
Collection at the Israel Museum, Jerusalem
Jessica Lewinsky* Hadas Seri
The Israel Museum, Jerusalem The Israel Museum, Jerusalem
Jerusalem, Israel Jerusalem, Israel
jessicale@imj.org.il hadasse@imj.org.il
www.imj.org.il/en www.imj.org.il/en
Abstract
The Metals and Organic Materials Conservation Laboratory
serves all departments at the Israel Museum in Jerusalem. As
Israel’s foremost cultural institution, the museum stewards a
remarkable encyclopedic collection. This paper outlines the
bespoke criteria used for the treatment and study of metal
objects in the Jewish Art and Life wing (JAAL). These criteria
guide the conservators’ decisions for each task or challenge,
and differ from those used for other collections, such as pieces
from the contemporary art collection and archaeological
metals. They take into account the scope of the collection, the
needs of the objects, and the needs of the visitors. Through
them, conservators can also become aware of how their own
identities and trajectories can affect how and what objects are
treated. Five different customized criteria are identified that
directly affect the conservation care and treatment of JAAL’s
living collection: (i) Life in a Jewish country implies that every
year object treatment, display, and research is influenced by the
Jewish calendar. (ii) The aesthetics of the objects contributes to
Introduction
The Israel Museum in Jerusalem (IMJ), established in
1965, is Israel’s foremost cultural institution respon-
sible for stewarding a unique encyclopedic collection.
Its comprehensive holdings cover thousands of years,
regions, themes, and materials. The collection is taken
care of, studied, and exhibited in four wings: Archaeology,
Fine Arts, Youth Art Education, and Jewish Art and Life.
This paper addresses the conservation criteria tailored to
suit the treatment and study of the Jewish Art and Life
wing. It focuses on the extensive metals collection and
how the conservation criteria differ from those used on
objects in the other museum wings.
The “Jack, Joseph, and Morton Mandel Wing for Jewish
Art and Life” (JAAL) (Figure 1) includes over 30,000 items
Maya Delano Irit Lev Beyth
The Israel Museum, Jerusalem The Israel Museum, Jerusalem
Jerusalem, Israel Jerusalem, Israel
mayade@imj.org.il conschem@imj.org.il
www.imj.org.il/en www.imj.org.il/en
*Author for correspondence
their symbolism and reinforces the codes that convey a deeper
understanding of the Jewish culture. (iii) The historical repairs,
marks of usage, inherent flaws, wear, and secondary use of
these unique objects explain their story and value. (iv) Added
materials and marks of usage that properly convey the values,
uses, narratives, and timelines associated with the objects must
be dealt with, respected, and preserved. (v) Many historical
sensitivities converge in one object, and it is important to
validate these different narratives and explore them further. This
paper is an invitation to continually reexamine conservation
practices and raise awareness of how to deal with specific
collections. Having clear principles, guidelines, and criteria is a
way to ensure that the conservators’ perspective enriches the
relationship with material culture.
Keywords
conservation, Judaica, historiographic metal collections,
museum preservation
Figure 1. A general overview of the Hanukkah lamp wall at the JAAL
galleries, The Israel Museum, Jerusalem. Photo by Elie Posner. © The
Israel Museum, Jerusalem
KEEPING IT KOSHER: THE CARE AND TREATMENT OF THE JUDAICA COLLECTION AT THE ISRAEL MUSEUM, JERUSALEM
in storage, archive, display, and on-site in four original
reconstructed synagogue interiors. The collection and its
comprehensive display explore and reflect the depth and
beauty of Jewish material culture and creativity. It illustrates
the aesthetic and stylistic influences of other cultures in
communities and places where Jews once lived as well as
present, living communities. The objects are imbued with
our values, points of view, a religious spirit, zeitgeist, and
multiple memories. They showcase a vivid cultural tapestry
weaving together the individual and the communal, the
sacred and the secular, the awe-inducing and the mundane,
and the heritage of the past and creative innovations of the
present. The display enlightens visitors about the Jewish
culture, but also provides tools and introspective moments
for any visitor to address their own identity.
The Metals and Organic Materials Conservation Labo-
ratory studies and cares for the objects from the JAAL
collection. This work is done in the knowledge that the
conservation treatment and understanding of an object
can bring forth and clarify a lot of information as well as
reassess the values associated with the collection.
Currently, the team is composed of four Jewish Israeli
female conservators. Each comes from a different Jewish
background, community, and level of religious practice.
Being both immersed in the culture as well as treating
the objects has enriched the conservators’ practice; there
is an awareness of the pros and cons. On the one hand,
there is an innate understanding of the objects and their
uses/traditions. On the other, the conservators can be
captives of their own perceptions, unable to look at
objects or situations inertly. Rather than treating ethno-
graphic objects from other cultures based on reading
and hearing about them from an expert, for example,
the conservators actually experience them in one way
or another. Talking to experts involves a double-sided
exchange in which first-hand accounts can be recounted,
shaping the perception and treatment of the object. This
open conversation is welcome where it serves to pursue
as many of the museum’s aims as possible.
The discussions amongst the conservators and curators
are in-depth, and it is imperative that the decision-making
process and all its considerations are explained. There
is an awareness of bias and “professional deformations.”
It is always personal in some respects. Individual expe-
riences and familiarity with Judaica objects, combined
with knowledge of past and present methods, philoso-
phies, and a dynamic ever-developing profession, has
309
greatly influenced the creation of the JAAL’s tailor-made
conservation criteria.
Bespoke criteria
The bespoke criteria stem from the team’s professional
conservation principles. Over the years, it was noticed
that the approach would differ if the object to be treated
was archaeological, an artwork, or an object from the
JAAL collection, especially since there is an effort to
showcase the values and sentiments the objects elicit as
fully as possible.
The criteria used are collection-, object-, and people-
driven.
In the first case (collection-driven), the wide variety and
unique study opportunities this collection provides are
taken into account and this serves as a form of measure-
ment and comparison. The criteria consider the wide
scope of materials and periods, and attempt to unify the
objects from the same perspective during conservation.
The sheer volume of objects at the JAAL wing facilitates
the identification of patterns and comparisons in material
culture. The types of materials, periods, shapes, and main
and secondary uses are taken into account to compre-
hend when an object is unique, out of the ordinary, or
reveals a clear distinction between the awe-inspiring
and the mundane.
In the second case (object-driven), decisions are based on
the particular needs of the object and take into account
the historical background, context, aesthetic tastes, and
materials. The object is treated rather than just the mate-
rial. The conservators’ point of view can enrich many
of the other tasks carried out in the museum, such as
research, display, and education. The approach is inclu-
sive and considers many of the cultural and historical
values and external factors that affected the item and
prompted its re-appreciation, display, and narrative
within the museum.
In the third case (people-driven), the end goal of the
conservation process is to share and display the object
with visitors and communities.
These criteria have facilitated the decision on which
treatments to apply, bringing awareness to many of the
underlying assumptions the conservators face. It is impor-
tant to note that many of the objects in the collection
would be used in religious ceremonies in their original
310  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
context in synagogues and Jewish homes. However, in the
museum, they are detached from their ritual functions.
The question of “holiness” is a complex one and not the
topic of this paper. The museum objects are awe-inspiring
but not sanctified or holy, in the sense that Jewish law
(Halakha) limits their functions and imposes restrictions
as to how they can be displayed. The gender, religious
affiliation, or belief of the conservator do not affect the
museum’s practices. The primary exception in Jewish
law regards the written word. However, even there, the
objects exhibited are those that are no longer deemed to
be kosher for use as prayer.
Living within the Jewish context and calendar
As a Jewish state, Israel adheres to the Jewish calendar
along with the Gregorian one. This fact is essential to
our working rhythm in the laboratory, affecting many
of the treatment decisions, priorities, and timeframes.
The regular use of objects in special displays relating
to Jewish holidays reinserts the objects into circulation
every year and makes the collection a truly living one. The
treatment and display contribute to the reinterpretation
of meaning, traditions, and questions regarding Jewish
identity. There is an awareness of how being immersed
in the culture changes understanding of these ritual and
traditional objects.
Before the celebrations for Hanukkah, for example, it has
become customary to treat large numbers of Hanukkah
lamps. These lamps are used in many exhibits in and
outside the museum and commemorate, celebrate, ques-
tion, interpret, and internalize the values of this holiday.
One such lamp is the one lit every year by the president
of Israel. For this lamp, separation babettes (sconces)
were built that allow the lamp to be used as intended
and not just displayed. Furthermore, attention was given
to its function as a symbol of state and diplomacy. The
object must look pristine, stable, and regal for any photo
request with emissaries and prime ministers.
Aesthetics
Most Judaica metal objects are highly polished for use in
Jewish life and tradition, and are also kept in the same
condition in daily life in Jewish homes. A well-polished
set of Shabbat candlesticks, for example, is also a symbol
of status, respect, Jewish values, and even good house-
keeping.
CONSERVATION PRACTICES
In general, polishing metal objects is performed only
when absolutely necessary, as the conservators are deeply
aware that this action changes the object’s surface and
patina and also removes original material. Conser-
vation training and knowledge does not stipulate the
requirement to exhibit these objects in line with their
true aesthetics. That is why, more often than not, unlike
metal objects from other collections at the IMJ wings,
Judaica is regularly polished.
To prolong the life of objects while maintaining their
pristine appearance, routine procedures have been set up
to delay patina formation and extend periods between
polishing:
• Periodic surveys to document changes in object
condition with follow-up measures for unstable items,
treating only what is necessary.
• Application of microcrystalline wax coatings after
treatment to postpone re-tarnishing.
• Storage of polished objects in transparent airtight,
anti-tarnish polypropylene bags embedded with
copper nanoparticles (Figure 2). The bags are marked
with the date they were heat-sealed for monitoring.
• Monitoring of the environmental conditions (relative
humidity, temperature, and air quality) by the preven-
tive conservator. By reviewing this data, very stable
environments have been created that help care for the
collections throughout the museum.
Other aesthetic considerations go beyond how polished
or shiny a metal object looks. When possible and conven-
ient, objects that can be dismantled are taken apart to
allow access for cleaning, ensuring mechanisms work
Figure 2. Judaica objects on storage shelves, some sealed in
polypropylene anti-tarnish bags, Jerusalem, 2021. Photo by Hadas
Seri. © The Israel Museum, Jerusalem
KEEPING IT KOSHER: THE CARE AND TREATMENT OF THE JUDAICA COLLECTION AT THE ISRAEL MUSEUM, JERUSALEM 311

and preserving their kinetic properties and alignment.

This has led sometimes to the storage of the polluting
elements separately to delay the corrosion process or
chemical reactions. An added advantage of doing so is that
hidden hallmarks, original assembly instruction marks,
and other details and surprises have often been found that
have contributed to knowledge about the objects and their
correct display based on taste at the time of their creation.
For example, an alteration to a late-19th-century Russian
tin Hanukkah lamp defaced by adherents of iconoclastic
ideologies was only noticed while being examined in the
conservation laboratory (Figure 3).

Figure 3. Defaced late-19th-century Russian cast lead and tin Hanukkah

lamp, accession number B08.0790. Photo by Elie Posner. © The Israel
Museum, Jerusalem

Historical repairs, marks of usage, wear, and

secondary use
Many Judaica objects in the IMJ’s collection were in heavy
use in their respective communities for generations. As
such, it is common for the objects to have undergone
different kinds of repairs, had new elements added, and
become strange hybrids. Many of these additions and
omissions are part of the story and values of the object.
They might indicate how the object was created, used,
repaired, or adapted during its lifetime.

Historical repairs are not altered, since they denote the

care and relationship that existed with their users. That
is to say great efforts were taken to salvage and repair

Figure 4. Torah shield with changeable plaques by Cornelius Poppe,

Augsburg, Germany, 1695–1700, accession number B50.02.0227.
Silver, repoussé, engraved, and partly gilt. Received through the Jewish
Restitution Successor Organization (JRSO). (a) Front, (b) back and detail
of back. Photo by Hadas Seri. © Israel Museum, Jerusalem
312  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
rather than discard. The museum, therefore, only treats
the structural instabilities with reversible procedures.
Missing elements are usually replaced using different
materials to give the impression of the object’s full shape
or by displaying a drawing or photograph of what the
object would have looked like originally. For example,
Torah shields (Tas Torah) (Figure 4a, 4b) often have
different removable plaques to indicate holy days in the
Jewish year. Years of placing and removing these plaques
during the lifetime of the object in the community creates
deep scratches and dents. These marks are left to indicate
the high usage of the object as well as give an idea of the
hidden mechanism. By leaving these marks, the curator
can better tell the story of these Jewish communities.
Another example is a pair of Torah finials (rimonim).
During the Simchat Torah celebration, the Torah is
removed from the Ark in the synagogue and marched
ceremoniously along the streets of the town. This is an
extremely joyous occasion. The Torah passes from man
to man during dancing in a usually very crowded space.
Often, metal adornments on the finials (Figure 5) fall
off, break, get deformed, etc. This damage is frequent in
our finial collection and more often than not the dents,
losses, and deformations are not repaired.
Figure 5. Torah finials surmounted by double-headed eagles by
Fredericus Becker senior, Pressburg, Austria-Hungary, 1813, accession
number B50.02.0706 (a–b). Silver, repoussé, pierced, chased, and
machine turned. Received through JRSO. The double-headed eagle on
one finial and most of the bells are missing. Photo by Yair Hovav. © The
Israel Museum, Jerusalem
CONSERVATION PRACTICES
There are many challenges associated with objects given
a secondary use. Beyond recycling and reuse consider-
ations, the mindset associated with their creation needs
to be understood. A case in point are the flower vases
created by artisans at Bezalel, the first school of arts and
crafts founded in Jerusalem in 1905. Student artisans
pressed, engraved, and stamped brass bomb shells and
embellished them with silver and copper damascene
(Figure 6). The transformation of the ammunition shells
suggests hope, as metal was a scarce commodity and
material. Time and money were invested in this trans-
formation as a call for peace after the military conflicts.
By leaving the shell shape recognizable in the flower vase,
the artisans were making a statement about laying down
weapons and ensuring the people and the land had an
opportunity to flourish.
Figure 6. Artillery shell
adorned with images
of holy sites in Israel by
Avraham Asher Baradon,
Bezalel School of Arts
and Crafts, Jerusalem,
1920, accession number
B11.1189. Brass, pressed,
engraved, and stamped
with silver and copper
damascene work.
Photo by Elie Posner.
© The Israel Museum,
 Jerusalem
Composite and mixed-media objects by use
Historical objects consist of a wide range of organic and
inorganic materials. Often, they are fragile because of this
combination, and at times show a more advanced state
of degradation. Moreover, many of their materials were
not used during the creation of the object but instead
incorporated over time by its use within the community,
converting them into mixed media. These materials have
now become an integral part of the object and therefore
KEEPING IT KOSHER: THE CARE AND TREATMENT OF THE JUDAICA COLLECTION AT THE ISRAEL MUSEUM, JERUSALEM
cannot be dissociated from it, even when this combina-
tion of materials sometimes creates a new problem for
the conservation of the object.
Examples of composite or historical mixed-media objects
include books and parchment scrolls with metal cases,
mezuzot, amulets, dresses with charms, and metallic
ornaments. Considerations have to be given to how
materials included in mixed-media objects are handled,
such as feathers in kits to search for leavened bread the
night before Passover or candlesticks with wax or oil
remnants, information currently being gathered for
research at the JAAL wing.
Since each material has specific requirements, it is a
preventive conservation challenge to maintain stable
storage and display conditions. Decision-making is
supported by prioritizing the likelihood of risk to any
one of the elements. That is to say, a risk-based approach
informs the treatment. For example, in the case of a
Havdalah set (Figure 7)––which includes two handheld
spice containers stored in a silver ornamented, textile-lined
box, probably a secondary use of the box––, many acetate
corrosion products staining the lining were found during
treatment and considered to be the result of the odorous
cloves kept inside the spice containers. The cloves were
removed from the containers and placed inside poly-
ethylene zip-top bags and returned to the interior of the
containers. The complexity of these objects makes each
treatment a mental exercise that takes into account many
aspects that are both material and intangible.
Figure 7. Two Havdalah spice boxes, unknown provenance, 1877,
accession number B97.0445 (a–b). One is dismantled for cleaning with
the cloves contained inside in the center. The silver container in the lower
part of the photo probably had another purpose originally. Photo Jessica
Lewinsky. © The Israel Museum, Jerusalem
313
Historical sensitivities
As mentioned, the IMJ in its encyclopedic universal
vision explores and celebrates the experiences, accom-
plishments, richness, and spirit of Jewish identity.
Pogroms, persecution, ostracism, genocide, and the
Holocaust are only one aspect of Jewish history and
identity. Objects that have survived traumatic historical
events have a much more complicated relationship with
both the people who experienced the events and the
visitors who experience the displayed objects in the
museum. The objects have narrative and symbolic qual-
ities that facilitate ethical and critical relations between
museumgoers and traumatic histories. The museum’s
job is ​​to make certain that any intervention prioritizes
their stabilization but does not erase or diminish the
marks conveying their story.
It is essential to remark that treating these objects requires
conservators to be mentally prepared and to have a
certain mindset. Personal family histories, experiences,
and sensitivities affect not only the treatment of the object
but also the trajectory of our staff. Some staff members
find it harrowing and draining to work on objects that
stem from trauma, while others perceive it as a fulfilling
honor. It is an opportunity to remark on our collective
history and to address injustices in society.
The “Kiddush cup from Munich” (Figure 8) in Germany
is a testimony to the vandalism and hatred that took place
across Germany during the Kristallnacht pogrom. This
object, as well as two others displayed in the same vitrine,
was left disfigured, discolored, warped, broken, and
melted. From a conservation point of view, they were left
mostly untouched. Their display acknowledges hatred,
past and present, and invites meaningful discussion.
Marks that are often documented and examined in the
conservation lab are those on objects brought to Israel
by Jewish refugees. These objects were smuggled out
of places ridden with discrimination and antisemitism
that ultimately eradicated peoples’ communities in the
Diaspora. The damages we see on these objects represent
how emotional and difficult forced immigration can
be. When these objects are brought to the workbench it
can be heartbreaking, because they reveal the struggles
and sacrifices made not only to escape but also to bring
these remnants of a life left behind. Deciding to bring a
family heirloom, rather than another piece of bread, is
a difficult choice to make.
314  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Figure 8. Kiddush cup that survived the Kristallnacht pogrom in 1938,
Munich, Germany, 20th century, accession number B50.04.2556,
133/040. Silver, repoussé. Photo by Laura Lachman on deposit from Yad
Vashem (The Holocaust Martyrs and Heroes Remembrance Authority).
© The Israel Museum, Jerusalem
The museum is a caretaker, memorial, and repository
for many “orphaned” objects. Many of the objects with
gaps in their provenance, origin, and ownership are
connected to the Holocaust. During World War II,
Jews were subjected to mass extermination and their
personal objects, sacred objects, books, and art collections
were confiscated, stolen, re-appropriated, hidden, and
discarded. After the war, the US army created special
units in charge of discovering, collecting, cataloging,
and returning these objects to individuals, communities,
and Jewish institutions. Only a minority of objects were
identified and restored to their rightful owners, and most
were given to museums around the world, including
the IMJ, for safekeeping. The IMJ takes an active part
in the restitution process worldwide. Every once in a
while the museum has the honor to repatriate objects to
their rightful heirs. In 2016, a modest pewter jug with
personal initials was returned to its owners following
lengthy research and due diligence. The conservators are
closely involved in identifying materials, stamps, taking
detailed condition reports, and handling instructions that
help return these objects safely to their rightful owners.
CONSERVATION PRACTICES
Conclusion
The Metals and Organic Materials Conservation Labo-
ratory provides its services to all departments of the
Israel Museum in Jerusalem regardless of the cultures
or periods they study. The care and treatment of objects
contribute to the permanence, dissemination, display,
study, and enjoyment of the collections. The proliferation
of metal objects in the collections reflects important
aspects of the world of material culture.
This paper outlines the bespoke criteria created for the
treatment and study of metal objects in the Jewish Art
and Life wing. The criteria used help to decide how to
approach each task or challenge. These guidelines are
collection-driven, object-driven, and people-driven.
Collection-driven because it is a unified collection.
Viewing the wide variety of objects together is a unique
study opportunity that serves as a reference and compar-
ison. Object-driven because the item is treated rather
than the material. The guidelines are based on what the
objects convey and mean and their inherent character.
Lastly, people-driven because the conservation process
is inscribed in Jewish society. Although neutrality
is the goal, the conservator’s point of view can both
enrich the understanding of the object and be limited
by personal bias.
Five different customized criteria were identified that
directly affect the conservation care and treatment of
this living collection. Life in a Jewish country affects
the timeframe of when objects are treated, based on the
Jewish calendar used by the state. As a result, objects are
put back into circulation every year. Via their treatment,
they are appreciated, reinterpreted, and experienced by
visitors.
The objects in the museum have certain aesthetics, and
their appearance is one part of their symbolism and the
codes that convey a wider understanding of the past.
By properly displaying these objects, the collection is
represented and shared in ideal condition, regardless of
whether it is exhibited in the galleries, catalogs, or on
social media.
The material complexity of some objects prompts outside-
the-box thinking to create custom-made solutions that
guarantee the dissemination of the values, ideas, and
materials to future generations. At times, added materials,
marks of usage, and compositions tell a new story about
an object’s use, history, and associated values.
KEEPING IT KOSHER: THE CARE AND TREATMENT OF THE JUDAICA COLLECTION AT THE ISRAEL MUSEUM, JERUSALEM
Recounting history is a responsibility the museum takes
seriously. It is imperative to be aware that many stories
and historical sensitivities converge in one object, and
it is important to validate these different narratives. An
inviting environment must be created where topics can
be discussed openly.
The different experiences, awareness, and knowledge
gained over the years by the members of the conservation
laboratory helped to form these bespoke criteria. In a
practical sense, it has also led to routine conservation
treatments for the Judaica collection. These include
sealing silver objects in anti-tarnish bags, sometimes
adding a protective coat to objects on loan, and making
sure an object is displayed in a polished manner, since
this is how it would have been presented in its original
context. Likewise, it also entails leaving damages on the
object when justified, since their presence enhances the
historic and symbolic value of the object.
One of the most valuable tools a museum has is the
dialogue between curators and colleagues. Every day,
it is apparent how our own identities and trajectories
affect which objects are treated and how. The aim is not
to become creatures of habit but to question constantly
the practices used. Every conservation treatment involves
much consideration and dialogue. The focus is placed on
important questions such as the best possible treatment,
the methods inherited from previous conservators at the
IMJ, established traditions at the lab, and whether our
identity as Jews, Israelis, and conservators changes with
every object we treat.
Glossary
Babette (sconce): Part of a candlestick where the candle
is attached.
Hanukkah: The Festival of Lights, a Jewish celebration
commemorating the re-dedication of the Second Temple
in Jerusalem in the 2nd century BCE.
Havdalah: A Jewish religious ceremony that marks the
symbolic end of Shabbat and ushers in the new week. The
ritual involves lighting a special candle with several wicks,
blessing a cup of wine, and smelling sweet spices. Shabbat
concludes with a verbal announcement that separates it
from the mundane weekday that follows.
Israeliana: A term that refers in a broad sense to the set
of things that are specifically identified with Israel or the
315
Land of Israel. The concept, whose coining occurred in
similar terms to “Americana,” initially referred to the
collected materials produced at the Bezalel Academy
of Art. However, today, it includes the paraphernalia
produced since the 1920s.
Judaica: Historical, literary, ritual, or artistic objects
relating to Jewish life and the customs of the Jewish faith.
Kosher: A word in Hebrew that literally means “fit” and
refers to the preparation of food and utensils following the
requirements of Jewish law. The term is nowadays used
more widely as a synonym of “above-board,” acceptable,
genuine, or legitimate.
Mezuzah (plural mezuzot): A piece of parchment
inscribed with religious texts and affixed in a case to the
doorpost of Jewish homes. Written on the parchment is
the Jewish prayer Shema Yisrael.
Rimonim (Torah finials): Pair of ornaments inserted at
the top ends of the rollers of a Torah scroll. Very often
they are made of precious metals and adorned with bells.
Shabbat: The Jewish day of rest. It begins at sundown
on Friday and ends at sundown on Saturday when a new
week begins. Shabbat is a day of abstention and prayer
for observant Jews.
Simchat Torah: A Jewish holiday that celebrates the
conclusion of the annual cycle of public Torah readings
and marks the beginning of a new one.
Tas Torah (Torah shield):  An ornament, usually
composed of precious metal suspended by chains on
the front of the Torah case.
Torah: The compilation of the first five books of the
Hebrew Bible: Genesis, Exodus, Leviticus, Numbers,
and Deuteronomy.
Yom Hashoah: “Holocaust and Heroism Remembrance
Day” known colloquially as Yom Hashoah is observed
as Israel’s day of commemoration for the approximately
six million Jews murdered by the Nazi regime during
World War II. The day focuses on learning about Jewish
heroism in the face of inhumanity as well as exploring
the roots of racism, genocides, and antisemitism. Unlike
the International Holocaust Day commemorated on
January 27, Yom Hashoah is held on the 27th day of Nisan
(which falls in April or May), unless the 27th would be
adjacent to the Jewish Sabbath, in which case the date
is shifted by a day.
316  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND CONSERVATION PRACTICES

Acknowledgments
We would like to thank the staff at the JAAL wing: Chief
Curator Dr. Rachel Sarfati, Miki Joelson, Gioia Perugia,
and Sharon Weisser.

Authors
Jessica Lewinsky is a preventive conservation officer
and object conservator at the Metals and Organic Mate-
rials Conservation Laboratory at the Israel Museum,
Jerusalem. She has a BSc in art and heritage conservation
(2010) from the Escuela de Conservación y Restauración
de Occidente in Guadalajara, Jalisco, Mexico, and an MA
in art theory and policy (2016) from Bezalel Academy
of Art and Design in Jerusalem, Israel.

Hadas Seri is an object conservator at the Metals and

Organic Materials Conservation Laboratory at the Israel
Museum, Jerusalem. She has an MA in art conservation,
objects stream (2010), from Queen’s University, King-
ston, Ontario, Canada, and an MA in art history and
BSc in chemistry and art history, both from the Hebrew
University, Jerusalem, Israel.

Maya Delano is object conservator at the Metals and

Organic Materials Conservation Laboratory at the Israel
Museum, Jerusalem. She completed art and archaeolog-
ical conservation studies in 2012 at Istituto per l’Arte e il
Restauro, Palazzo Spinelli, Florence, Italy, and has a BA
in art and archaeology (2010) from Tel Aviv University.

Irit Lev Beyth has been head of Metals and Organic

Materials Conservation at the Israel Museum, Jerusalem
since 2015, where she has been an object conservator
since 1998. She has a BA in museum studies (1989)
from Baylor University, Texas, USA, and an MA in
art conservation, objects stream (1994), from Queen’s
University, Kingston, Ontario, Canada.
 Young Conservation Professional

Commercially Available Vacuum Chambers as an

Alternative in the Deoxygenated Desalination Treatment
of Archaeological Iron
Aleksi Pienimäki
Kiruna Centre for Conservation of Cultural Property
Kiruna, Sweden
aleksi.pienimaki@sfmv.se

Abstract
This study examined the feasibility of commercially available
vacuum chambers in the deoxygenated desalination treatment
of archaeological iron objects. Stainless steel chambers with
acrylic lids and silicone gaskets were shown to perform
well when used with alkaline desalination solutions. The
performance of the chambers was then tested by desalinating
samples of terrestrial archaeological iron nails in alkaline sulfite
(ASvac: 0.5 M NaOH + 0.05 M Na2SO3) and sodium hydroxide
(NaOHvac: 0.5 M) solutions. The control treatments were carried
out using similar solutions in non-vacuum polypropene boxes
(ASamb and NaOHamb). Dissolved oxygen (DO) levels, measured
weekly using a luminescent dissolved oxygen probe, did not
significantly differ between the NaOHvac and ASamb treatments,
but the oxygen concentrations in the ASvac treatment were
lower. However, care should be taken when interpreting the
results, as DO levels alone provide no information about the
reaction types or the dynamics of chloride extraction.
Keywords
archaeological iron, desalination, dissolved oxygen, partial
vacuum

Introduction
The post-excavation corrosion of archaeological iron
objects is a major issue in the conservation of archae-
ological metals. This type of corrosion is driven by the
aggressive ions, especially chloride, trapped inside the
corrosion layers (Turgoose 1985, Selwyn et al. 1999).
Accordingly, the removal of these ions through desal-
ination is a significant part of the routine workflow in
many conservation laboratories.
Desalination is usually carried out by immersion in alka-
line fluids. Deoxygenated treatment solutions have been
employed since the mid-1970s, after the introduction of
the alkaline sulfite (AS) treatment (North and Pearson
1975). During subsequent decades, the effectiveness of
this treatment was attributed to the presence of sulfite
ions, which function as oxygen scavengers (Gilberg and
Seeley 1982, Turgoose 1985). Physical deoxygenation of
the treatment solutions followed, with promising results
(Al-Zahrani 1999, Rimmer 2010).
Laboratory-grade vacuum chambers have been used to
deoxygenate treatment solutions (Schmutzler 2012), but
these are expensive and their use is restricted in routine
treatment. However, an increasing assortment of vacuum
chambers has become commercially available in recent
decades. As a simple potential method of deoxygena-
tion, they present an attractive option for desalination
treatments.
This study examined the feasibility of these chambers in
deoxygenating the desalination solutions used for archae-
ological iron. Evaluating the effectiveness of desalination
treatments is complicated, as discussed in detail elsewhere
(Watkinson 2010). In this study, the treatment solutions
were compared based on dissolved oxygen (DO) levels,
according to two basic assumptions:
1. A dilute sulfite concentration of 0.05 M (Schmidt-Ott
and Oswald 2006) was shown to perform as well as
the more concentrated version originally suggested
(North and Pearson 1975).
2. In this setting, the sulfite ion has no other function
except as an oxygen scavenger (Gilberg and Seeley
1982, Turgoose 1985, Watkinson et al. 2013).
If the DO levels achieved with NaOHvac and ASamb are
comparable, then the desalination performance should
be similar as well. Nonetheless, it must be noted that
318  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND CONSERVATION PRACTICES

DO levels do not provide insight into the reactions taking

place during treatment and the exact role of sulfite cannot
be defined with certainty.

The test material

Chambers supplied by VacuumChambers.eu were used
(Figure 1).

Figure 2. Example of the one-litre IKEA 365+ polypropene box with a

silicone gasket and locking lid, used in non-vacuum control batches in
the study

set at 0.8 L. The object weight:solution volume ratio was

about 1:5 in all batches.

Table 1. The treatment batches used in the study. d = treatment

duration in days, n = number of DO measurements carried out on
treatment batch

Batch Solution Start Finish d n

1 ASvac
11.3.2021 30.8.2021 162 19
9 ASvac 11.3.2021 30.8.2021 163 18
14 ASvac
11.3.2021 30.8.2021 162 19
4 NaOH vac
11.3.2021 21.9.2021 193 22
8 NaOHvac 11.3.2021 11.1.2022 291 34
11 NaOH vac
11.3.2021 18.1.2022 298 35
7 ASamb 11.3.2021 30.8.2021 162 19
12 AS amb
11.3.2021 28.7.2021 130 18
13 AS amb
11.3.2021 30.8.2021 162 19
6 NaOHamb 11.3.2021 21.9.2021 193 22
10 NaOH amb
11.3.2021 21.9.2021 174 22
16 NaOHamb 11.3.2021 23.11.2021 248 31

Figure 1. The one-litre vacuum chamber (from VacuumChambers.eu)

used in the study
The test chambers had a capacity of 1 L but chambers
with capacities as high as hundreds of litres are available.
The performance of the vacuum chambers was tested
against a control group of non-vacuum polypropylene
boxes with locking lids (Figure 2).
Test specimens consisted of 96 dry archaeological nails
from a terrestrial site. These were divided into 12 batches
of eight nails, each batch with an average mass of about
160 g. Six randomly chosen batches were treated under
partial vacuum, while six were used as non-vacuum
controls (Table 1). The treatment solution volume was
Methodology
The tested solutions were AS (0.5 M NaOH + 0.05 M
Na2SO3) and sodium hydroxide (0.5 M NaOH). The
sodium hydroxide concentrations in desalination treat-
ments usually range between 0.1 and 0.5 M. A concen-
tration of 0.5 M was chosen as some studies stress the
importance of maintaining a high hydroxide ion concen-
tration (Pelé et al. 2010, Schmutzler 2012, Coelho et al.
2014). The original concentration for sulfite (North and
Pearson 1975) was 0.5 M, but concentrations as low as
0.05 M were subsequently recommended (Schmidt-Ott
and Oswald 2006) and shown to suffice for the deoxygen-
ation of solutions in closed containers. A concentration
of 0.05 M was therefore chosen for this study.
COMMERCIALLY AVAILABLE VACUUM CHAMBERS AS AN ALTERNATIVE IN THE DEOXYGENATED DESALINATION TREATMENT OF ARCHAEOLOGICAL IRON 319

The partial vacuum inside the chambers reached an
average of 10 kPa, with a fluctuation of less than ± 5 kPa.
Average leakage was < 10 kPa during the week-long
measurement interval. All treatments were carried out
at ambient temperature.
The treatments were completed between March 2021
and January 2022. DO levels were determined weekly
using a luminescence dissolved oxygen probe (Hach
Lange LDO101 probe connected to a Hach Lange
HQ440D laboratory meter), except during a 4-week
period between 2 and 29 August 2021.
The stability criterion was set to 0.05 mg/L/min. When
this criterion was met, the measurement usually drifted
towards a lower value, but this drift could be ignored.
Note that the treatment chambers had to be opened and
the solutions exposed to atmospheric oxygen during
measurement.
A positive systematic error in the measurements was
likely. Nonetheless, the achieved precision and the large
number of readings allowed a meaningful comparison
of the solutions.
Results
There was no statistically significant difference in the DO
levels in the ASamb and NaOHvac treatments. However,
the DO levels in the ASvac treatment were the lowest
(Figure 3, Table 2)
Discussion
Care needs to be taken in the interpretation of DO
readings, as they do not provide insight into the reac-
tions taking place during treatment. Further research is
needed on the differences between physical and chemical
deoxygenation methods.
Schmutzler (2012, 64–78) investigated the role of sulfite,
by applying it to physically deoxygenated solutions,
but obtained mixed results. Although no clear pattern
emerged, the results questioned the expectation that
deoxygenated solutions outperform oxygenated ones.
Al-Zahrani (1999, 137–8) compared the desalination
efficiency of deionised water deoxygenated using sulfite
with deionised water deoxygenated using nitrogen and
found that the latter was more efficient in removing
chlorides. The reason for the difference in performance
could not be identified, but the author suggested that
physical and chemical methods of deoxygenation are
not necessarily comparable.
Coelho et al. (2014) tested dilute and concentrated AS
on marine archaeological cast iron and found out that
the concentrated solution outperformed the dilute one.
How far these results can be generalised and whether the
observed difference could be attributed to the sulfite or
hydroxide ion remain uncertain.

Rimmer (2010, 81) reported lower, more consistent

DO levels in ASamb treatments than were measured in
this study. This could be due to differences in treatment
vessels or the measurement method.

Deoxygenation is usually assessed qualitatively rather

than quantitatively. This study does not support this
approach, as DO levels over a wide range could be
measured.
Figure 3. Box and whisker graph of DO levels measured in the test solutions

Conclusion
Table 2. Statistical summary of the DO measurements of the test
solutions. All values in mg/L
Judging by the DO levels, NaOHvac was comparable to
Solution n Average Median SD ASamb. Thus, no difference is to be expected between the
AS amb
56 0.78 0.62 0.50 use of a vacuum chamber versus dilute sodium sulfite
NaOHamb 75 6.14 5.69 0.99 as a method of deoxygenation, assuming that the sulfite
ASvac
56 0.45 0.46 0.17 ion does not serve other purposes than that of an oxygen
NaOHvac 91 0.83 0.78 0.35
scavenger.
320  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
If the deoxygenation levels achieved with ASamb are
deemed sufficient, NaOHvac is a valid substitute for this
solution. If the aim is to reach consistently low DO levels,
better results are achieved using ASvac.
The sulfite ion often complicates chloride determinations.
Thus, physical deoxygenation simplifies both chloride
determination and the disposal of the used solution
(North 1987; Wang et al. 2008; Scott and Eggert 2009,
141). The use of vacuum chambers is simpler than deox-
ygenation with nitrogen.
Significant differences in the performance of ASamb versus
NaOHvac could arise despite the comparable DO levels
measured in these solutions.
Acknowledgements
The author would like to thank his supervisor, Stavroula
Golfomitsou, from the University of Gothenburg for
her advice and support and John Lagerstedt from the
Finnish Heritage Agency/Archaeological Field Services
for providing the test material. This work was financially
supported by the Märta, Gunnar and Arvid Bothéns Trust.
References
Al-Zahrani, A.N. 1999. Chloride ion removal from
archaeological iron and ß-FeOOH. PhD dissertation,
University of Wales, UK.
Coelho, J.C., C.M. Oliveira, M.D. Carvalho, and I.T.E.
Fonseca. 2014. The efficiency of electrochemical methods
for the removal of chloride ions from iron marine
archaeological objects: A comparative study. Materials
and Corrosion 65(1): 38–44.
Gilberg, M.R. and N.J. Seeley. 1982. The alkaline sodium
sulphite reduction process for archaeological iron: A
closer look. Studies in Conservation 27(4): 180–4.
North, N.A. 1987. Conservation of metals. In Conser-
vation of marine archaeological objects, ed. C. Pearson,
207–52. Bodmin: Butterworth & Co. Ltd.
North, N.A. and C. Pearson 1975. Alkaline sulfite
reduction treatment of marine iron. In ICOM-CC 4th
Triennial Meeting Preprints, Venice, 13–18 October 1975,
75133-1-75133-14. Rotterdam: Bouwcentrum (Impr.)
[for] the International Council of Museums. Available
at www.icom-cc-publications-online.org/
Pelé, C., S. Lemoine, and E. Guilminot. 2010. Evolution
of pH in the solutions of dechlorination. In Archaeo-
CONSERVATION PRACTICES
logical Iron Conservation Colloquium 2010 Extended
Abstracts, Stuttgart, 24–26 June 2010, eds. G. Eggert and
B. Schmutzler, session 4. Stuttgart: State Academy of Art
and Design Stuttgart.
Rimmer, M.B. 2010. Investigating the treatment of chlo-
ride-infested archaeological iron objects. PhD disserta-
tion, Cardiff University, UK.
Scott, D.A. and G. Eggert. 2009. Iron and steel in art:
Corrosion, colorants, conservation. London: Archetype
Publications Ltd.
Schmutzler, B. 2012. Rettung vor dem Rost: Die Weiter-
entwicklung der Eisenentsalzung nach der Alkali-Sulfit-
Methode zur Erhaltung großer Fundmengen. Rahden:
Verlag Marie Leidorf Lmt.
Schmidt-Ott, K. and N. Oswald. 2006. Neues zur
Eisenentsalzung mit alkalischem Sulfit. Beiträge zur
Erhaltung von Kunst- und Kulturgut 2: 126–34.
Selwyn, L.S., P.J. Sirois, and V. Argyropoulos. 1999. The
corrosion of excavated archaeological iron with details
on weeping and akaganéite. Studies in Conservation
44(4): 217–32.
Turgoose, S. 1985. The corrosion of archaeological iron
during burial and treatment. Studies in Conservation
30(1): 13–18.
Wang, Q., S. Dove, F. Shearman, and M. Smirniou. 2008.
Evaluation of methods of chloride ion concentration
determination and effectiveness of desalination treat-
ments using sodium hydroxide and alkaline sulphite
solutions. The Conservator 31(1): 67–74.
Watkinson, D. 2010. Measuring effectiveness of washing
methods for corrosion control of archaeological iron:
problems and challenges. Corrosion Engineering, Science
and Technology 45(5): 400–406.
Watkinson, D., M.B. Rimmer, and F. Kergourlay. 2013.
Alkaline desalination techniques for archaeological
iron. In Corrosion and conservation of cultural heritage
metallic artefacts, eds. P. Dillmann, D. Watkinson, E.
Angelini, and A. Adriaens, 407–33. Cambridge: Wood-
head Publishing Ltd.
Author
Aleksi Pienimäki has a BA in archaeology from the
University of Helsinki and a BA in objects conserva-
tion from Helsinki Metropolia University of Applied
Sciences. Since 2017, he has been enrolled in the Master’s
COMMERCIALLY AVAILABLE VACUUM CHAMBERS AS AN ALTERNATIVE IN THE DEOXYGENATED DESALINATION TREATMENT OF ARCHAEOLOGICAL IRON 321

Programme in Conservation at the University of Goth-

enburg. Since 2019, he has been employed as a conser-
vator of archaeological metals at the Kiruna Centre for
Conservation of Cultural Property.

Materials list
Sodium hydroxide (AnalaR NORMAPUR®)
Sodium sulfite anhydrous (AnalaR NORMAPUR®)
VWR International/Avantor
www.vwr.com

Hach Lange HQ440D laboratory meter

Hach Lange LDO101 probe
Hach Lange GmbH
www.hach.com

IKEA 365+ Food container with lid, rectangular/plastic 1.0 L

IKEA Group
www.ikea.com

Vacuum chamber 1.0 L, stainless steel VC0918SS

VacuumChambers.eu
www.vacuumchambers.eu
POSTER SESSION
324  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND POSTER SESSION

Subcritical Fluids in the Conservation of Archaeological

Iron Objects: From Experiments to Permanent Practice

Aki Arponen* Anna Hyppönen Petri Kilpeläinen Kalle Kaipanen

The National Museum of Finland
Finnish Heritage Agency
Helsinki, Finland
aki.arponen@kansallismuseo.fi
The National Museum of Finland
Finnish Heritage Agency
Helsinki, Finland
anna.hypponen@kansallismuseo.fi
Natural Resources Institute Finland
(Luke)
Helsinki, Finland
petri.kilpelainen@luke.fi
Natural Resources Institute Finland
(Luke)
Helsinki, Finland
kalle.kaipanen@luke.fi
*Author for correspondence

Subcritical fluids are an efficient approach to the conser-
vation of archaeological iron objects but their use has
been limited by the costs of the required device. In 2020,
the National Museum of Finland began negotiations with
the Natural Resources Institute Finland (Luke) to test
the subcritical processing of archaeological iron objects
using the Institute’s devices. Testing was conducted with
the aim of developing the method so that it could be
introduced on a permanent basis. The first processing
test was performed in February 2021 with a small device
and 11 objects. Each object was placed in stainless steel
mesh and then transferred to a 3-litre tank. After 10
days of processing, all items were undamaged and there
was no evident activation of corrosion during the obser-
vation period of several weeks. Hematite accumulated
on the surface of the objects, but it was easily removed
with glass-bead micro-air abrasion. Use of a stainless
steel mesh, however, is not advised because the folded
rigid mesh may harm the objects and the sharp edges of
the mesh caused injuries to the handler. In the second
processing test, in November 2021, a larger and more
advanced device was used. The 300-litre tank held 70
objects, each sewn into a PTFE mesh and attached with
stainless steel wire to stainless steel chains. The chains
were attached to a steel plate that was lifted into the
tank. Again, processing did not damage the objects,
hematite was easily removed and no corrosion occurred.
Sewing the pouches for each object, however, was time
consuming and the mesh broke down easily when it
caught on a sharp edge. Moreover, as the mesh is non-re-
cyclable, the method is both costly and non-ecological.
The third processing test was conducted in February 2022
using the same device. However, the objects were not
placed in mesh but in stainless steel baskets that in turn
were placed on stainless steel shelves in the tank. Some
of the baskets were custom made for this purpose, and
others were bought ready-made. As in the previous tests,
no problems emerged with respect to the objects or the
results, but processing with the baskets proved to be both
time saving and object friendly. The National Museum
of Finland will continue developing this subcritical
processing method in collaboration with Luke until the
end of 2023. The goal in 2024 is for the Finnish Heritage
Agency’s Collection and Conservation Centre to acquire
its own device such that the subcritical processing of
archaeological iron objects will be a permanent practice.
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND
When Corrosion is Useful: Absolute Dating of Metals by
the Radiocarbon Method
Lucile Beck*
LMC14 National Laboratory, Laboratory of Climate and Environmental Sciences
(LSCE), French Alternative Energies and Atomic Energy Commission (CEA)
Saclay, France
lucile.beck@cea.fr
The radiocarbon dating method is usually applied to
organic materials – wood, charcoal, bone, etc. – which
absorb radioactive carbon through photosynthesis
or ingestion. However, a few studies have shown that
radiocarbon dating can also reveal the age of inorganic
manufactured materials. Lead carbonates cerussite
(PbCO3) and hydrocerussite (2PbCO3Pb (OH)2) were
used as white pigment or cosmetics from the 4th century
BC to the 20th century. They were formed by the corro-
sion of metallic lead by vinegar and horse manure. These
organic materials release carbon dioxide (CO2), and it
has been recently demonstrated that this CO2 has been
incorporated into the corrosion products, meaning that
the carbonate function of the lead carbonates carries a
14
C signature corresponding to the organic matters used.
Therefore, lead white pigment and cosmetics produced
as a result of this corrosion process can be dated by the
POSTER SESSION  325
Cyrielle Messager
LMC14 National Laboratory, Laboratory of Climate and Environmental Sciences
(LSCE), French Alternative Energies and Atomic Energy Commission (CEA)
Saclay, France
cyrielle.messager@cea.fr
*Author for correspondence
radiocarbon method. In order to better understand
the incorporation mechanism of 14C in cerussite and
hydrocerussite, lead carbonates were produced by the
corrosion process under various monitored experi-
mental conditions. Lead carbonates were obtained using
two types of acid (vinegar containing 14C vs 14C free
acetic acid) and three types of CO2 sources (atmospheric
air, horse manure containing 14C and 14C free fossil
CO2 gas). Twelve different conditions were tested and
the results show the production of lead acetates when
CO2 is absent and the production of cerussite when
CO2 is present. Cerussite incorporated 14C when horse
manure was used. These results confirm the action of
vinegar/acetic acid as a precursor and horse manure
as a reagent to produce carbonates carrying 14C, which
allows the absolute dating of lead carbonates using the
radiocarbon method.
326  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Corrosion, Communication, and Comparison:
Collaborative Conservation Approaches Towards Two
Medieval Axes from Norfolk, England
Kate Berlewen*
Royal Albert Memorial Museum
Exeter, UK
kate.berlewen.18@ucl.ac.uk
Two Medieval axes from Norfolk, England, required
stabilisation before display due to active corrosion and
illegibility of features of interest. A uniform final appear-
ance was desired, both to clarify the nature of the objects
and because both axes would likely be displayed together.
This posed challenges as the two axes, both casual finds
from different sites, had undergone diverse historic
treatments and been stored for varying lengths of time,
leading to very different states of conservation. Further
challenges were encountered, as each object was worked
on as an individual student project and the treatments
took place over a year of lockdowns with intermittent
laboratory access. Three key aims were identified for the
treatments, which needed to respond sensitively to the
structure and distribution of corrosion products, features
of interest, and stability of each object: (i) the removal of
corrosion products allowing legibility of the axe typology
and features of interest, including pseudomorphic corro-
sion patterns; (ii) appropriate stabilisation and protection
of the objects from further corrosion; and (iii) a final
cohesive appearance of the colour and reflectivity of
any coatings or passivation films on both objects, to aid
their legibility. A process of collaborative working was
adopted between the students, making use of in-person
laboratory work whenever possible. When it was not
possible to work together, recorded video updates and
shared documentation, including photography, research
POSTER SESSION
Reed Hudson
University College London
London, UK
reed.hudson.18@ucl.ac.uk
*Author for correspondence
notes, and written records, were utilised to communicate
the progression of decision-making and treatments.
Documentation and research were shared through
the file-sharing platforms Dropbox, WeTransfer, and
WhatsApp. These methods also helped mitigate working
patterns being broken by lockdowns, providing continuity
through well-documented thought processes and stages
of treatment. The techniques and materials used included:
(i) mechanical removal of previous conservation mate-
rials and corrosion products through air abrasion and
hand tools; (ii) reconstruction using Paraloid B-48N
(methyl methacrylate and butyl acrylate copolymer) in
acetone; (iii) application of supportive gap fills using
iron powder, glass micro balloons, and fumed silica with
Paraloid B-48N in industrial methylated spirits/acetone;
(iv) passivation with tannic acid (C76H52O46) in deionised
water; and (v) coating with low concentration Paraloid
B-44 (methyl methacrylate and ethyl acrylate copolymer)
in toluene, bulked with fumed silica as a mattifying
agent. While both axes were conserved using a different
combination of these techniques and materials tailored
to their specific needs, the collaborative decision-making
process ensured a cohesive final appearance and state
of conservation for the axes as a pair. The flexible and
cooperative approach also ensured the adaptability and
resilience of the project, enabling each student to work
when it was safe and accessible to them.
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND
Atmospheric Particulate Matter: How to Include it in
Artificial Ageing?
Elena Bernardi* Cecilia Velino
Department of Industrial Department of Industrial
Chemistry, University of Bologna Chemistry, University of Bologna
Bologna, Italy Bologna, Italy
elena.bernardi@unibo.it cecilia.velino2@unibo.it
Carla Martini Cristina Chiavari
Department of Industrial Department of Cultural Heritage,
Engineering, University of Bologna University of Bologna
Bologna, Italy Bologna, Italy
carla.martini@unibo.it cristina.chiavari@unibo.it
Corrosion phenomena occurring on outdoor-exposed
metallic artefacts have been the subject of several
studies, but relatively few of them have investigated or
attempted to artificially reproduce the specific effects
induced by atmospheric particulate matter (PM). Beside
natural ageing, reliable artificial ageing procedures are
key to corrosion mechanism studies, as well as to repro-
duce representative corroded substrates and complex
environmental conditions to assess the effectiveness
of protective products. PM, unlike gaseous pollutants
and rain, is not often included in accelerated ageing
methods for cultural heritage materials, and generally,
when considered, only single salts or a simple mix of
salts are used. This is due to several problematic aspects
related to appropriate PM sampling and effective repro-
ducibility of real PM compositions. In order to develop
new coatings, the lack of a suitable ageing procedure
that includes PM (and its potentially synergic inter-
action with UV) can produce discrepancies between
the predicted behaviour of protective treatments in
traditional ageing tests and real-world performance:
coatings with successful results under laboratory condi-
tions fail under real conditions. To solve these issues,
several actions were carried out: a wide literature survey
followed by data elaboration and a preliminary formula-
tion of synthetic PM; the set-up of an accelerated ageing
cycle in a climatic chamber and of a methodology to
POSTER SESSION  327
Ivano Vassura
Department of Industrial
Chemistry, University of Bologna
Bologna, Italy
ivano.vassura@unibo.it
*Author for correspondence
analyse the effect of PM on bronze specimens. To obtain
ambient PM-induced corrosion patterns to validate the
complete artificial ageing procedure (from PM formu-
lation to ageing), ambient PM was collected through an
ad hoc accelerated sampling system on bronze substrates
(Cu-5Sn-5Zn-5Pb). The ionic composition of the PM
was determined and the specimens were exposed to
accelerated ageing in a climatic chamber (simulating
daily variations of T, RH% and UVA irradiation,
according to the cycle previously defined). Two seasonal
campaigns were performed to collect the widest range
of PM composition/concentration. The specimens were
periodically observed by optical microscopy and, at
the end of the ageing process, were characterised using
different techniques (optical microscopy, field emission
gun-scanning electron microscopy, energy-dispersive
X-ray spectroscopy, infrared spectroscopy, Raman
spectroscopy and UV-Vis spectrophotometry for colour
analysis). The corrosion products were then removed
to determine their metal content as well as mass loss
and changes in the surface profile. The qualitative and
quantitative results identified the main relationships
between the ambient PM composition/concentration
and surface evolution. The results obtained so far are
very promising for the development of a protocol for
reproducible accelerated ageing tests that include PM
as a corrosive factor.
328  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Study and Restoration of the Trajan’s Column
Electrotypes at the National Museum of Archaeology of
Saint-Germain-en-Laye
Isabel Bonora Andujar* Antoine Amarger
Musée d’Archéologie nationale Independent conservator
Saint-Germain-en-Laye, France Paris, France
isabel.bonora@culture.gouv.fr antoine.amarger@orange.fr
Julia Jouet Brittany Branche
Independent conservator Independent conservator
Paris, France Vitry-sur-Seine, France
julia.jouet@gmail.com brittany.branche@outlook.com
In 1861, the French Emperor Napoleon III obtained
permission from Pope Pius IX to make a plaster replica
of Trajan’s Column. A few months later, the 450 molds
were exhibited in Paris at the Palace of Industry, where,
for the first time, all of the bas-reliefs on the column,
which is almost 40 meters high, could be admired and
studied. Concerned about the durability of the molds,
and in order to erect a similar column to that of Napo-
leon I in Place Vendôme, the emperor sent them to the
industrialist Léopold Oudry to make copper electrotypes,
during which process the molds were mostly destroyed.
In 1864, the electrotypes were successfully exhibited at
the Louvre Museum, and, in 1872, were permanently
transferred to the National Museum of Archaeology in
Saint-Germain-en-Laye, where the first section has been
exhibited in the castle moat ever since. Electrotyping, an
innovative technique for its time, was used in the field of
statuary for only a short time. To study this little-known
technique, it was necessary to collect information on the
manufacturing parameters, analyze the observed altera-
tions, and develop treatment recommendations. At the
request of the museum, and while keeping in mind the
desire to continue to exhibit all of the electrotypes, the
first phase of study consisted of a technical analysis of
the pieces (a description of the manufacturing process,
POSTER SESSION
Anouk Molineri
Independent conservator
Paris, France
anoukmolineri.cr@gmail.com
*Author for correspondence
analysis of the present elements by portable X-ray fluo-
rescence, and identification of subsequent interventions),
their state of conservation, and the establishment of a
restoration protocol allowing the surface and structure of
the electrotypes to be treated and their presentation in an
exhibition space. Because of their varied state of conser-
vation, the project was quite complex. The bas-reliefs have
very different surface aspects, which are linked to the
conditions of conservation as well as the manufacturing
process. Some of the electrotypes are particularly fragile,
because they are cracked, fragmented, and sometimes
incomplete. To establish a protocol adapted to the casts
as a whole, and so that the results were representative,
the study phase was carried out on eight casts in various
states of conservation. As far as the structural aspect was
concerned, consolidation tests were carried out to define
the most suitable materials to meet the criteria of revers-
ibility, support compatibility, durability, shaping, and
mechanical strength. Tests focused on modern synthetic
materials to create removable reinforced resin shells. For
the surface, the choice of most suitable treatment was
dependent on future conservation conditions and had to
consider the problems of mass treatment and structural
fragilities. To meet these constraints, selective cleaning
tests, by spraying plant abrasives, were first carried out.
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND
Acoustic Emission Techniques for the Detection and
Monitoring of Corrosion Phenomena
Laura Brambilla*
Haute Ecole Arc Conservation-restauration (HE-Arc CR), HES-SO University of
Applied Sciences and Arts Western Switzerland
Neuchâtel, Switzerland
laura.brambilla@he-arc.ch
Brice Chalançon
Association de Gestion du Musée National de l’Automobile
Mulhouse, France
b.chalancon@museedelauto.org
In the field of cultural heritage, the use of non-inva-
sive techniques to diagnose and monitor artefacts is of
utmost importance in order to avoid surface changes
and damages to the materials. However, detection of
ongoing corrosion phenomena in closed environments
is still a challenge. This poster presents the results
from applying acoustic emission (AE) techniques to
non-invasive detection and monitoring of ongoing
corrosion inside the cooling systems of historical vehicle
engines. The study was conducted within the framework
of the ACUME_HV project. The main objective was to
develop a technique for monitoring engine mechanisms
during their reactivation. As part of the monitoring
process, an engine was initially emptied of its cooling
liquid and lubricants for preliminary measurements.
An inspection of the cooling system, made of cast iron,
using an endoscope revealed the presence of extended
corrosion and thick patinas. The cooling liquid was
then re-introduced into the system and AE sensors,
placed in contact with the external surface of the engine,
recorded intense and frequent hits over a 24-hour
period. The origin of these signals was hypothesised
to be related to the onset of a new corrosion process in
POSTER SESSION  329
Alejandro Roda-Buch
Tribology and Interfacial Chemistry Group, École polytechnique fédérale de
Lausanne (EPFL)
Lausanne, Switzerland
alejandro.rodabuch@epfl.ch
Stefano Mischler
Tribology and Interfacial Chemistry Group, École polytechnique fédérale de
Lausanne (EPFL)
Lausanne, Switzerland
stefano.mischler@epfl.ch
*Author for correspondence
the wet environment of the cooling system. To confirm
this hypothesis, an experimental setup, mimicking the
cooling system under investigation, was developed. An
electrochemical cell was assembled using specific glue to
mount PVC tubes on iron coupons, and AE sensors were
installed on the external part of the coupons. A classic
three-electrode electrochemical cell was then created
on the internal part of the coupons. This setup allowed
the correlation between electrochemical measurements,
typically used for corrosion monitoring, to be assessed
invasively and for non-invasive AE measurements to be
taken. The iron coupons were initially pre-corroded.
According to the protocol, the corrosion layers were
first left to dry and subsequently the cell was filled
again with electrolyte, in order to simulate the process
observed previously in the engine’s cooling system. The
correlation of electrochemical and AE measurements
revealed that a new ongoing corrosion process did
indeed exist and therefore it was possible to conclude
that AE was a promising method, even in the case of
closed systems that cannot be accessed for inspection
with standard tools or by any other monitoring methods
known (spectroscopic, electrochemical, etc.).
330  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
The Bronze Hand of Prêles: Protecting a Valuable
Archaeological Object Using 3D Techniques
Sabine Brechbühl
Archaeological Service Bern
Bern, Switzerland
sabine.brechbuehl@be.ch
For conservators, dealing with a unique object of high
value and renown presents numerous challenges.
However, 3D techniques can be used to reduce the many
stresses to which such objects are frequently exposed. In
2017, metal detector searches resulted in the discovery
of ‘the bronze hand of Prêles’, which was subsequently
brought to the Archaeological Service of Bern. This
object, which dates to the Middle Bronze Age, is the
oldest metallic representation of a human body part
thus far known in Europe. The hand is a massive casted
bronze object partly plated with a decorated gold foil.
Given its high value for archaeological research, it is in
steady demand for analyses, exhibition, documentation
and study. However, climatic changes, manipulation,
transport and mountings are major sources of stress to
archaeological objects and endanger their preservation
and integrity. These risks must be balanced against the
need to examine the objects to determine their cultural
and historical meaning. A method that allows essential
activities while minimising the exposure and manipu-
lation of fragile objects is therefore needed. In the case
of the bronze hand, after its age, provenance and hence
POSTER SESSION
importance were established, its documentation was
completed with 3D scanning, which provided a true-
to-scale backup of the shape and colour of the hand
that could be used for a multitude of purposes. For
example, a 3D print was made that was used in defining
and planning interventions as well as in discussions of
typological details and the manufacturing process. In
addition, the necessary mountings for tomographic
analyses, for sampling the metal or for exhibition could
be produced without ever having to touch the original.
The 3D data were also used to plan the packing of
the object. Ethafoam was milled according to the 3D
data and two shells with the exact shape of the hand
were produced, thus providing accurate support and
cushioning from all sides. Currently, tests are being
conducted to produce a high-quality copy of the hand.
A high-resolution scan and print will be manually
coloured and gilded. Although the precision is not
yet at quite the same level as that of moulds realised
with silicone rubber, the 3D print nonetheless avoids
subjecting the original object to possible contamination
and other potential sources of damage.
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND POSTER SESSION  331

Corrosion of Strings on Musical Instruments

Vera de Bruyn-Ouboter* Andreas Erbe Erlend Flø Gustad

Ringve Music Museum/Rockheim,
The Museums of Southern
Trøndelag (MiST)
Trondheim, Norway
vera.de.bruyn.ouboter@mist.no
https://ringve.no/en
https://mist.no/en
Department of Materials Science
and Engineering, Norwegian
University of Science and
Technology (NTNU)
Trondheim, Norway
andreas.erbe@ntnu.no
www.ntnu.edu/ima
Department of Materials Science
and Engineering, Norwegian
University of Science and
Technology (NTNU)
Trondheim, Norway
erlendfg@stud.ntnu.no
*Author for correspondence

In the collections at the Ringve Music Museum, Trond-
heim, Norway, a range of stringed musical instruments
exhibit contact corrosion. This affects the metal strings
of stringed instruments as well as keyboard instruments
such as pianos. The critical point is where a metal string
is attached to the sounding body. When in contact with
other materials, such as felt, leather or plastic, the string
tends to corrode and crack. This type of corrosion has
been observed over the course of several years. Simple
attempts have been made to isolate the materials from one
another, but the problem reoccurs. The relative humidity
and temperature in storage are controlled and the air
quality has been analysed for the presence of formic
acid, acetic acid, nitrogen dioxide and ozone, but the
amounts are lower than critical threshold values. In labo-
ratory model experiments, low-alloyed steel sheets were
cleaned in sodium hydroxide and exposed for 30 days
in contact with cotton and wool piano textile fabric.
Analysis of the surface by grazing incidence infrared (IR)
reflectance absorbance spectroscopy (time-dependent),
X-ray photoelectron spectroscopy (XPS) and secondary
ion mass spectrometry showed typical signals for the
presence of long-chain carboxylic acids on the metal
surface. The characteristic absorbance in IR increased
over time. The decomposition of cellulose through
reaction with oxygen can in part explain the presence of
carboxylates but not the presence of all detected signals.
Interestingly, in contrast to the samples in contact with
the fabric, lab-exposed reference samples that had not
been in contact with the textile fabric showed clearly
visible signs of corrosion. The same metal sheets were
exposed inside a square piano (ca. 1825, Scandinavia)
for 30 days. Surface analysis also indicated the pres-
ence of carboxylates in these samples, but with shorter
hydrocarbon chains compared to the samples exposed
in lab conditions. XPS analysis indicated the presence of
bromine, possibly stemming from the textile dye or other
textile treatment. Scanning electron microscopy with
energy-dispersive X-ray analysis was used to investigate
the composition of the piano strings. The results shed
more light on the challenges in understanding contact
degradation processes at the atomic-scale and nanoscale,
and in developing appropriate conservation-compatible
mitigation strategies.
332  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND POSTER SESSION

Do the Lubricating Oils Used in Scientific-Technological

Objects Protect Metals Against Corrosion?

Emilio Cano*
National Centre for Metallurgical
Research, Spanish National
Research Council (CENIM–CSIC)
Madrid, Spain
ecano@cenim.csic.es
Blanca Ramírez Barat
National Centre for Metallurgical
Research, Spanish National
Research Council (CENIM–CSIC)
Madrid, Spain
blanca.ramirez@csic.es
Joaquina Leal
National Museum of Science and
Technology (MUNCYT)
Alcobendas, Spain
joaquina.leal@muncyt.es
María Teresa Molina
National Centre for Metallurgical
Research, Spanish National
Research Council (CENIM–CSIC)
Madrid, Spain
mt.molina@cenim.csic.es
*Author for correspondence

One of the challenges in the conservation of scientific
and technological heritage objects is their use and
operation, which distinguishes them from works of
artistic heritage and complicates the establishment of
conservation criteria with respect to their maintenance,
restoration and valorisation. Moreover, these objects are
often machinery made up of several materials, including
those related to their operation and mechanisms, such as
greases, waxes and lubricating oils, whose preservation,
renewal or elimination must be decided upon. The aim
of this work was to evaluate whether the lubricating oils
in scientific-technological objects, given their ageing and
lack of use, have a corrosive or protective effect on the
objects’ metals. In this work, inspired by David Hallam’s
research, several original oils were evaluated using elec-
trochemical impedance spectroscopy (EIS). Samples of
lubricating oils were taken from different objects from the
National Museum of Science and Technology (Madrid).
The objects have not been in use since the end of their
service life and still retain their original materials. Steel
and brass were selected as the test metals in accordance
with their abundance in the collection of the museum. In
light of the difficulties reported by Hallam et al. in their
work (Metal 04), refinements to their methodology for
performing EIS were introduced. Working electrodes
were prepared with the rods of each metal, embedded
in epoxy resin, attached to a copper wire for electrical
contact, and the flat cross-section left exposed. This side
was dipped in the oils chosen for testing and positioned
horizontally in the electrochemical cell. Once the oils
had been evaluated by EIS to determine their protective
properties, they were further analysed by external reflec-
tion Fourier transform infrared spectroscopy (ER-FTIR).
This methodology resulted in more homogeneous and
reproducible oil layers. The differences in the protective
properties of the oils were large, with variations in the
impedance modulus at low frequencies of several orders
of magnitude, depending on the composition of the
sample and its contamination from previous use. Two
new oils used in preservation/restoration were examined
as well: of note, one of them had a high protective capacity
and the other none at all. Evidence of the contamination
and ageing of the oils was obtained using ER-FTIR, which
revealed peaks indicative of oxidation, nitration and
water. The presence of these impurities has been shown
to affect the reproducibility of EIS measurements.
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND
The Bluish Green and the Greenish Blue
Mariana Cardoso
Independent conservator
Lisbon, Portugal
marianacardosometal@gmail.com
Is it blue? Is it green? Is it grey? I see red! I see brown!
No, it’s reddish brown. Or maybe, brownish red. Perhaps
yellowish brown. I think it’s opaque. No, dull. Normally
it’s translucent. But can be also vitreous. It’s homogeneous,
but sometimes heterogeneous. I know it as a deep colour.
Heavily saturated. Almost black. I heard it is pale. I heard
it is light. My poster will be designed as a simple board
game allowing the participation of many conference
attendees. Rectangular sheets of paper will be distrib-
uted during the conference and coloured pencils will
be made available. The attendees will be asked to draw
the colour of certain corrosion products (e.g. nantokite,
atacamite, cuprite and paratacamite) and to provide a
written description of the colour underneath. At the
POSTER SESSION  333
Poster Session, all the coloured cards will be added to the
poster, finally completing it. The purpose of the game
is to highlight the fact that the description of corrosion
products in many publications and other texts can
vary widely. With the contributions of a large number
of professionals, the game is therefore a good exercise
in developing a consensus description of corrosion
products based on colour and other features. Diver-
gences and similarities in colour perception and in the
colour-based descriptions of the most common copper
corrosion products will also be revealed. Participation
in the game will encourage discussions of the work
experiences of colleagues in the areas of copper objects
conservation and related topics.
334  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Heritage Biota and Bronze Patina Composition:
A Correlation?
Cristina Chiavari* Carla Martini
University of Bologna University of Bologna
Bologna, Italy Bologna, Italy
cristina.chiavari@unibo.it carla.martini@unibo.it
Andrea Timoncini* Elena Bernardi
University of Bologna University of Bologna
Bologna, Italy Bologna, Italy
andrea.timoncini2@unibo.it elena.bernardi@unibo.it
Epilithic bacteria play a fundamental role in the conser-
vation of cultural heritage materials in the outdoor
environment. Bacterial communities cause stone and
metal degradation by the chemical dissolution/precip-
itation of substrate ions, biochemical redox reactions
as well as organic and inorganic acid release, resulting
in discolouration of the surface and physical alteration.
However, in some cases, bacteria exert bioprotective
actions. For bronze statues in non-buried conditions,
few studies have examined the associated biota or the
possible correlation between the chemical profile of the
patina (i.e. pale green, black crusts) and the bacterial
community. Moreover, the changing environment, such
as decreased SO2 concentrations, relative enrichments
of NOx, O3 and particulate matter, and, more generally,
local variations in multi-pollutants combined with
climate change effects, creates new, mostly aggressive
scenarios that impact the decay of cultural heritage mate-
rials and therefore their bacterial communities as well.
POSTER SESSION
Federica Costantini
University of Bologna
Bologna, Italy
federica.costantini@unibo.it
*Author for correspondence
The aims of the present study were to: (i) characterise the
bacterial community on bronze statues by conducting
DNA analysis based on the 16S RNA gene, and specifi-
cally using samples obtained from sheltered/unsheltered
areas on the surfaces of monuments in three Italian cities
(Rimini, Ravenna and Bologna), in order to generate a
bacterial library; (ii) determine the correlations between
chemical profiles and the biological characteristics
of the patina; (iii) obtain insights into the relation
between climate and heritage biota. The next step of
this research will consist of laboratory studies of the
degradation of bronze fostered by biota communities
and climate change and investigations of the underlying
mechanisms. This will be pursued through accelerated
ageing tests, including the use of artificial acid rains, the
composition of which is formulated through updated
environmental monitoring data, and bacterial commu-
nities selected on the basis of data obtained from actual
statues (bacterial library).
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND
Testing Silver Lacquers: What about Agateen #27?
Gerhard Eggert* Gregory Dale Smith
State Academy of Art and Design Indianapolis Museum of Art at
Stuttgart, Germany Newfields
gerhard.eggert@abk-stuttgart.de Indianapolis IN, USA
gdsmith@discovernewfields.org
Materials for storage and display are nowadays routinely
Oddy-tested to avoid corrosive emissions harming objects
in closed cases. Conservation materials (adhesives,
consolidants, coatings) which are permanently attached
to objects must of course meet the same standard. Cellu-
lose nitrate products fail the Oddy test, which has been
confirmed for the British silver lacquer Frigilene. Lead,
copper and the silver coupon were clearly corroded, and,
surprisingly, a cyanide compound (AgCN·2AgNO3) was
detected by Raman spectroscopy and powder diffrac-
tion in tests performed in Stuttgart and presented at
Metal 2019 (Neuchâtel, 2–6 September 2019). In the
US, Agateen #27 is frequently used by conservators.
However, as it is not on sale in or shipped to Germany, it
could not be included in the Stuttgart tests. A test at the
Indianapolis Museum of Art at Newfields yielded extreme
corrosion and discolouration on all coupons, and the test
beaker exploded a few days into the run. In a repetition
experiment in milder conditions (40 instead of 60 °C)
using only 0.5 g fully dried Agateen film (4 years old), a
yellow-brown tarnish with black spots on the silver foil
was analysed after 159 days of exposure. The formation
of at least two cyanide compounds could be confirmed
with Fourier transform infrared (FTIR) spectroscopy
and Raman spectroscopy by the distinctive C≡N stretch
vibrations between 2000 and 2200 cm−1: an unknown
POSTER SESSION  335
Michael J. Samide
Butler University
Indianapolis IN, USA
msamide@butler.edu
*Author for correspondence
cyanide on brown sites and AgCN·2AgNO3 on black
sites, the latter supported by scanning electron micros-
copy–energy-dispersive X-ray spectroscopy (SEM-EDX)
elemental mapping. The unusual reaction might have
been driven by the extreme insolubility of silver cyanide
and the availability of reactive carbon and nitrogen
compounds from the decomposition of cellulose nitrate:
Ring-CH2-O-NO2 → Ring· ·CH2-O· ·NO2 → Ring· + CH2=O + ·NO2
CH2O + 3NO2 + 3 Ag → AgCN·2AgNO3 + H2O
In addition to the Oddy test, Agateen #27 was analysed
by direct thermal desorption–gas chromatography–mass
spectrometry (GC–MS) for volatile emissions. A number
of compounds of concern were detected: NO, acetic
acid, formaldehyde and other aldehydes, and various
alkylnitrates. Although no unequivocal evidence for
the formation of cyanide on lacquered silver objects was
found, it also cannot be ruled out. The release of NOx
and its effect on other sensitive materials alone is reason
enough to discard cellulose nitrate products as conser-
vation materials. Unfortunately, if silver lacquering is
needed, there is no good replacement available today with
a stable material that has all the advantages of cellulose
nitrate coatings. New research with modern coatings is
urgently needed.
336  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Possibilities for Implementing Aesthetic Unity,
Reversibility and Distinctiveness: Two Conservation Case
Studies
Eszter Tóth
Hungarian National Museum
Budapest, Hungary
toth.eszter@hnm.hu
Two prominent weapons from the armoury collection in
the Hungarian National Museum were subject to conser-
vation before display in the permanent exhibition to
present the evolution of weaponry in Hungarian history.
Conservation was undertaken using traditional principles
(distinctiveness, aesthetic unity, reversibility, minimum
intervention) and was used for educational purposes as
part of the Applied Arts Object Conservation Program
organized jointly by the Hungarian National Museum and
the Hungarian University of Fine Arts. The first weapon
was a wheellock pistol from Nürnberg (16th century)
with gilded steel parts and a wooden body decorated
with engraved inlays made of mother-of-pearl and bone.
Originally, both inlay materials were carved and filled
in with a black substance. The missing inlays were made
of the same material in accordance with the originals.
Gluing of the supplements without any decoration was
not considered an acceptable solution, since their plain
white surfaces were conspicuous and confusing from an
aesthetic point of view. After studying the decoration
pattern on the original parts and consulting museologists,
the supplements were engraved using traditional gold-
POSTER SESSION
smithing techniques. The engravings were emphasized
with black paint rather than black substrate infilling to
make the replaced pieces more distinguishable. The other
weapon, a sword that is presumed to have belonged to
the Hungarian king Matthias Corvinus (1458–1490), is
presumably a copy from the 17th century, but has a Latin
text etched on the blade that refers to the ruler. The grip
is decorated with a gilded copper filigree braid consisting
of twisted and straight wires. Partially broken and incom-
plete, this filigree decoration has diminished the aesthetic
unity. However, in the absence of comparable examples,
the reconstruction plan was developed by museologists.
The plan seemed to be in jeopardy due to the fact that
the wood grip was originally covered with a textile, so
fixing the new wires caused further difficulties. A crack
on the wooden part of the grip served as a fixing point
for the complementing patinated copper wire used as a
supplement for the heavily worn gilded copper filigree.
The copper wires were affixed only to the wooden infill
of the grip with epoxy resin, while the original broken
filigree pieces were joined without adhesive and merely
stitched under the undamaged braids.
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND POSTER SESSION  337

Supercritical Carbon Dioxide: Cleaning and Stabilization Tests

for Copper Alloys and Iron Keys from a Scientific Collection of
the Centro Hospitalar Conde de Ferreira (Porto, Portugal)
Catarina Figueiredo* Carlo Bottaini Inês Silva Eduarda Vieira
School of Arts, Universidade HERCULES Laboratory, Centre for Biotechnology and Fine Research Centre for Science and
Católica Portuguesa Universidade de Évora Chemistry – Associate Laboratory Technology of the Arts (CITAR),
Porto, Portugal CityUMacau Chair in Sustainable (CBQF), Faculty of Biotechnology, School of Arts, Universidade
catarinacostafigueiredo@gmail.com Heritage, Universidade de Évora 8 Universidade Católica Portuguesa Católica Portuguesa
Évora, Portugal Porto, Portugal Porto, Portugal
Nuno Camarneiro carlo@uevora.pt s-ivmsilva@ucp.pt evieira@ucp.pt
Research Centre for Science and
Technology of the Arts (CITAR), Rui Bordalo Marta Duarte *Author for correspondence
School of Arts, Universidade Research Centre for Science and Centre for Biotechnology and Fine
Católica Portuguesa Technology of the Arts (CITAR), Chemistry – Associate Laboratory
Porto, Portugal School of Arts, Universidade (CBQF), Faculty of Biotechnology,
ncamarneiro@ucp.pt Católica Portuguesa Universidade Católica Portuguesa
Porto, Portugal Porto, Portugal
rbordalo@ucp.pt s-msmduarte@ucp.pt

An increasing number of eco-friendly nanotechnologies
for the conservation of cultural heritage materials are
becoming available. These include supercritical carbon
dioxide (scCO2), which has proven to be a viable green,
non-flammable, and ecological method. While previ-
ously tested and now widely used in the pharmaceutical
and food industries, scCO2 has recently been applied
in the conservation of cultural heritage objects, and
specifically for their cleaning, consolidation, and stabili-
zation. Experience has shown that scCO2 is a promising
alternative to conventional toxic organic solvents for
the removal of organic materials, such as oils, grease
deposits, and active corrosion products. In this study,
we tested and applied scCO2 as a cleaning and stabiliza-
tion agent on two coils of copper and silk textile wires
used in the electrical induction mechanism of a faradic
machine and on an iron key from a set of handcuffs.
Both objects come from a set of psychiatric instruments
and equipment dating from the 19th to the mid-20th
century that now form part of the scientific collection
of the Centro Hospitalar Conde de Ferreira, which
belongs to Museu da Misericórdia do Porto, Portugal.
Portable X-ray fluorescence was carried out before
and after scCO2 treatment to determine the elemental
composition of the metal alloys and the effectiveness
of the cleaning process. Before the objects were treated,
scCO2 was tested on eight samples of similar material
and degradation pathologies. Comparative experiments
were performed with and without the addition of a
co-solvent to scCO2. The co-solvents included ethanol,
hydrogen peroxide, ethylenediaminetetraacetic acid
(EDTA), and sodium hexametaphosphate. Different
temperatures, reaction times, and pressures were eval-
uated. Cleaning efficiency was assessed by the visual
examination of dirt removal, material stabilization,
oxidation stain removal, fiber mechanical strength,
and dye loss. The results revealed that scCO2 without
the addition of a co-solvent did not have a significant
impact on the samples compared to when it was applied
with ethanol or EDTA, which as co-solvents improved
cleaning and stabilized the corrosion products. The
respective formulations proved to be suitable alter-
natives for the treatment of metal artifacts as well as
objects composed of different materials.
338  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND POSTER SESSION

A Simple Treatment System for the Deaerated

Desalination of Archaeological Iron

Jacob Frydendahl* Trine Wiinblad Delphine Neff Henning Matthiesen

The Royal Danish Academy –
Conservation
Copenhagen, Denmark
jacob-frydendahl@hotmail.com
Lars Brock Andersen
Centre for Preservation of Cultural
Heritage
Vejle, Denmark
lba@konsvejle.dk
The National Museum of Denmark
Lyngby, Denmark
trine.wiinblad@natmus.dk
Charlotte Carré
LAPA NIMBE – IRAMAT, CEA/
CNRS/U P Saclay, UMR 3685
Gif-sur-Yvette, France
cha03.carre@gmail.com
LAPA NIMBE – IRAMAT, CEA/ The National Museum of Denmark
CNRS/U P Saclay, UMR 3685 Lyngby, Denmark
Gif-sur-Yvette, France henning.matthiesen@natmus.dk
delphine.neff@cea.fr
*Author for correspondence
Philippe Dillmann
LAPA NIMBE – IRAMAT, CEA/
CNRS/U P Saclay, UMR 3685
Gif-sur-Yvette, France
philippe.dillmann@cea.fr

Deaerated alkaline desalination is a well-established,
highly effective treatment for archaeological iron as
it prevents further corrosion and induces the trans-
formation of chlorinated phases while avoiding the
precipitation of green rust. Deaeration is most often
achieved by the addition of the oxygen scavenger
sodium sulfite. However, the use of sulfite has raised
concerns because of the potentially harmful effects of
sulfate remnants in the treated objects. The problem can
be avoided by purging with inert gas instead, but this
requires a specialized treatment set-up, which until now
has limited its use. We developed a simple, inexpensive,
and robust treatment method that relies on oxygen
displacement by N2 gas and allows the simultaneous
treatment of several objects in separate containers.
Monitoring over the last 1.5 years has shown that stable
anoxic conditions can be obtained even at very low
N2 flow rates, thus minimizing both the cost and the
environmental impact of treatment. A similar system
for small-scale treatment can easily be constructed as
well, using the materials on hand at most conservation
workshops. The method is not limited to the use of
alkaline solutions, as treatment can also be performed
at neutral pH if the right combination of solution
and gas is used. Chloride release during treatment in
0.5 M NaOH and 0.01 M NaHCO3 was measured for
12 samples of archaeological iron excavated from a
chlorinated terrestrial soil environment as well as for
samples of pure akaganeite. In addition, selected samples
were assessed by scanning electron microscopy with
energy-dispersive spectroscopy, Raman spectroscopy,
and total chloride measurements. The results suggest
that a very high chloride extraction efficiency can be
reached using our gas-based method.
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND POSTER SESSION  339

Metals Conservation Teaching at University Level in

Greece and the Cultural Vision of EYDAP S.A.

Maria Giannoulaki* Christina Panagiotopoulou Sofia Tzimopoulou Vasilike Argyropoulos

Department of Conservation
of Antiquities and Works of Art,
University of West Attica
Athens, Greece
mgiann@uniwa.gr
www.uniwa.gr
Division of Communication
and Corporate Affairs, EYDAP’s
Historical Archive, EYDAP S.A.
Athens, Greece
xrpana@eydap.gr
www.eydap.gr
Division of Communication
and Corporate Affairs, EYDAP’s
Historical Archive, EYDAP S.A.
Athens, Greece
tzimo@eydap.gr
www.eydap.gr
Department of Conservation
of Antiquities and Works of Art,
University of West Attica
Athens, Greece
bessie@uniwa.gr
www.uniwa.gr
*Author for correspondence

This study looked at the integration of the conservation
of a significant historic metals collection with training at
university level through collaboration between the Metals
Conservation Laboratory and Research Laboratory
for the Study & Conservation of Ancient and Modern
Cultural Properties (CULTLAB) at the University of
West Attica and the Historical Archive of the Athens
Water Supply and Sewerage Company (EYDAP S.A.).
Through its aim to improve the lives of individuals and
to aid the development and prosperity of society, EYDAP
supports initiatives and actions based on social engage-
ment and the promotion of culture. Its historical archive
is responsible for compiling, storing, managing, and
promoting a collection of tools and machinery used for
the construction of the Marathon Dam, a technological
achievement in the 1920s that serves as a major symbol
of the modernization of Greece. These objects, which are
of various types, such as tools and machinery, lighting
and heating equipment, measuring instruments, pumps,
typewriters, and calculators, are exhibited at EYDAP’s
Marathon Museum. The objects are mainly made of
iron and copper alloys and other metals. Many of them
are composite metal objects, comprising metal and
inorganic materials, such as glass, or organic materials,
such as wood, leather, fabric, plastic, or paper. Some have
coatings or are painted. They are important documents
of technological history and, along with photographic
archives, a snapshot of the period, where a prosperous
and self-sufficient settlement for workers grew up around
the museum. For the exhibition to mark the 90th anni-
versary of the building of the dam, EYDAP assigned
CULTLAB the project to conserve 64 selected objects.
A joint decision was made to integrate the conservation
of the collection with the educational work of the Metals
Conservation Laboratory, giving students the opportu-
nity to develop practical skills, scientific documentation,
and decision-making in the aim to limit corrosion and
preserve and highlight the technological information and
values of the objects as museum exhibits and witnesses
of technological achievement and progress.
340  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
A Lacquer to Dye For! Exploring a UV Fluorescent Additive
for Coating Applications in Silver Conservation
Rosie Grayburn*
Winterthur Museum, Garden & Library
University of Delaware Art Conservation Department
Winterthur DE, USA
rgrayb@winterthur.org
The conservation and scientific analysis departments
at Winterthur Museum have developed a silver coating
program over 40+ years. Our last phase of research
occurred in 2016–2019. Building on research from
colleagues at MFA Houston and Colonial Williamsburg,
we refined our Agateen Lacquer #27 recipe—unmodi-
fied, non-plasticized, high-molecular-weight cellulose
nitrate derived from cotton linters and dissolved in
butyl acetate, butanol, toluene, ethanol, and isopropanol
(manufactured by Agate Lacquer Tri-Nat, LLC and avail-
able from manufacturer and at conservation suppliers,
including Talas)—by the addition of the UV-fluores-
cent dye Coumarin 6 (3-(2-benzothiazolyl)-N,N-di-
ethylumbelliferylamine), CAS # 38215-36-0, available
from Sigma Aldrich). When applied to silver, the dye
contained in the lacquer is not detectable in visible light
but fluoresces bright yellow-green at long-wave UV.
The fluorescence enables conservators to immediately
assess the coating application process, by observing
lacunae, thin spots, or other flaws. Nonetheless, it was
important to understand the long-term effects of this
additive, whose properties were desirable for only a
small duration of the coating lifetime. Fluorescence
images of a coated silver tray were captured soon after
treatment and again after one year under ambient
conditions. Images were obtained using a Nikon D850
POSTER SESSION
Lauren Fair
Winterthur Museum, Garden & Library
University of Delaware Art Conservation Department
Winterthur DE, USA
lfair@winterthur.org
*Author for correspondence
camera with a 20 mm lens, a Peca 918 filter, a UV filter
(similar to the Kodak Wratten 2E gel filter), a 30 s
integration time, and a 365 nm UV light source. The
empirical data clearly showed that the fluorescence
wanes after exposure under ambient conditions. More-
over, there was a clear shift in the visible spectrum, as
the coating became more yellow in select areas of the
tray after one year of ambient exposure. To understand
the dye-coating interaction at a molecular level, a more
controlled experiment was designed using mock-ups.
Thin films of Agateen containing a range of Coumarin
6 concentrations were applied to glass slides by brush in
the same manner that the coatings would be applied to
objects: two coats with a 50 min drying time in between.
The films were aged at 70°C and 55% RH for 400 h.
Absorbance and fluorescence spectra were collected
before and after thermal aging to gauge the lifetime of
the useful optical properties of the dye. Fourier trans-
form infrared spectra were obtained to gauge polymer
deterioration patterns. The glass transition temperature
was also measured before and after aging to assess the
effect of the dye on film porosity and to understand
whether the dye would act as a plasticizer over time.
The aim of this research was to determine the long-term
aesthetic and performance effects of application-focused
additives for silver lacquer.
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND
Port-Jeanne-d’Arc: Is Conservation of an Isolated Site
Possible?
Marie Grima
Terres Australes et Antarctiques Françaises (TAAF)
Saint-Pierre, La Réunion, France
mariegrima@outlook.fr
Port-Jeanne-d’Arc was the only French whaling station
and it remains one of the rare examples of industrial
seal activity in the sub-Antarctic. The aim of a mission
undertaken between October 2020 and April 2021
was to diagnose the condition of Port-Jeanne-d’Arc’s
metallic structure. Located in Kerguelen, in the French
sub-Antarctic, Port-Jeanne-d’Arc was built in 1908 by
the Norwegian company Storm, Bull & Co., on the
orders of France’s Bossières brothers. From the station,
sea mammals were hunted, mainly elephant seals but
also whales. The oil thus produced was used for street
lighting in Europe and North America. However, the
overall yield of the project was poor and the station was
closed in 1926. In conservation terms, Port-Jeanne-
d’Arc, despite the uniqueness of its heritage, raises
several issues, some of which overlap with those of
classic, industrial heritage: (i) the site has typical conser-
vation problems, including its destruction due to the
natural degradation of its materials, accelerated by the
aggressive environment, and to looting and vandalism;
POSTER SESSION  341
(ii) the lack of continuity in the heritage missions within
the French Southern and Antarctic Lands (TAAF)
complicates research and follow-up; (iii) the station is
located on a natural reserve classified as an UNESCO
World Heritage Site, which raises the question whether
this isolated site, with limited visitor numbers (less
than 50 tourists per year), should or can be enhanced,
as large-scale operations would imply significant logis-
tics and thus the need for efforts to ensure a minimum
environmental impact; finally, (iv) the remoteness of the
territory makes it difficult to implement conservation
operations. Promotion of the heritage of the Austral
Islands may require that the conservation of the respec-
tive materials be abandoned. We thus recommend that
Port-Jeanne-d’Arc be examined in all its aspects before
its final disappearance, including through the use of
alternative tools such as 3D scanning. Specific lines of
research have been initiated, including investigations
of the behaviour of puddled iron, a material extensively
used in the base construction of the station.
342  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Evaluation of the Impact of Dechlorination Treatments on
the Organic Parts of Composite Objects
Elodie Guilminot*
Arc’Antique Laboratory, Grand patrimoine de Loire-Atlantique (GPLA)
Nantes, France
Elodie.Guilminot@Loire-Atlantique.fr
Charlène Pelé-Meziani*
Arc’Antique Laboratory, Grand patrimoine de Loire-Atlantique (GPLA)
Nantes, France
Charlene.PELE-MEZIANI@loire-atlantique.fr
Ferrous objects can be effectively stabilised by chemical
or electrochemical dechlorination. However, the treat-
ment of objects composed of both ferrous and organic
elements is challenging, because chemicals may adversely
affect the latter. In this study, the impact of a range of
dechlorination treatments on bone, wood, horn, ivory
and leather, as representative organic materials, was
assessed. Two samples and one reference sample per
material were immersed in one of six chemical solu-
tions selected through bibliographical research and/
or following experimental treatments: NaOH/Na2SO3
(20 g/L–10 g/L, pH 13.6), Na2SO3 (0,5% w/w, pH 9.1),
sodium sesquicarbonate (5.6 g/L­–4.5 g/L, pH 10.0),
NH2OH (2.5% v/v, pH 13.1), KNO3 (1.0% w/w, pH 6.7) and
NH4OH (1.0 mol/L, pH 11.7). The samples were analysed
by Fourier transform infrared (FTIR) spectroscopy after 4
and 37 weeks of immersion. The initial results ruled out
the use of certain chemical solutions, based on the visible
appearance of the samples. For example, horn and leather
immersed in NaOH/Na2SO3 became gelatinous such that
FTIR analysis was impossible. By contrast, the appearance
of the same materials after 1 month in NH2OH (pH 13)
was nearly unchanged. FTIR analyses showed a marked
decrease only in the intensity of bonds corresponding to
bands at 1080 cm−1 (attributed to dC-H, C-H3ro/?C-N
amide I/polysaccharide bonds). For the other samples,
despite bacterial growth in the solutions, there was no
visible alteration in their appearance or their resistance
to mechanical handling. Based on these experiments
and the FTIR data, a table summarising the treatments,
parameters of interest (pH, volume, solution composition)
and the results for each organic material was established.
The information can be cross-referenced with data on
the dechlorination of an object’s ferrous parts. Wood:
No visible degradation in colour or mechanical strain
occurred, irrespective of the treatment. However, FTIR
POSTER SESSION
Sylvie Labroche
Arc’Antique Laboratory, Grand patrimoine de Loire-Atlantique (GPLA)
Nantes, France
Sylvie.labroche@loire-atlantique.fr
*Author for correspondence
analysis showed a degradation of carbohydrates at neutral
and slightly alkaline pH (KNO3, Na2SO3, sesquicarbonate).
Lignin degradation started at pH > 11.5 and increased
in higher-pH solutions (NaOH/Na2SO3 from the first
month and NH4OH, NH2OH more visible 9 months
later). Leather: After one month, samples in solutions with
pH > 13 (NH2OH and NaOH/Na2SO3) had degraded and
degradation continued during the entire 9-month period.
Samples immersed in NaOH/Na2SO3 completely jellified.
In sesquicarbonate and KNO3, both the volume and
delamination increased. FTIR analysis showed a degra-
dation of amide I and II bonds at pH < 12; at higher pH
(> 12), the polysaccharide bonds underwent degradation.
Bone: There was no visible degradation except for samples
immersed in NaOH/Na2SO3, which became greyer than
the reference. FTIR analysis revealed bone mineral
degradation, especially in Na2SO3. Degradation became
apparent within the first month and continued thereafter.
Horn: Samples immersed in NaOH/Na2SO3  became
completely gelatinous within the first month whereas
samples immersed in NH2OH became soft and grey. In
solutions with a pH > 12, FTIR analysis showed degrada-
tion of the cysteine/cystic acid bonds. Lower-pH solutions
chemically impacted the amide bonds, especially Na2SO3
(80%). Ivory: The colour and mechanical strain of samples
immersed for 1 month remained stable. However, samples
immersed in NaOH/Na2SO3 were completely delaminated
and bleached. FTIR analysis showed stable ratios, indi-
cating similar level of organic and mineral degradation.
Except for those immersed in sesquicarbonate, all samples
displayed dark stains that could not be removed by rinsing.
FTIR analysis showed the chemical stability of the mineral
part, with a significant increase in the ratio of amide bonds
in samples immersed in KNO3 and NH2OH. The amide
bonds of samples immersed in Na2SO3, sesquicarbonate
or NH4OH were slightly degraded.
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND
Historical Repairs on Ancient Chinese Bronzes:
Identification and Conservation Issues
Ke-Shiuan (Tracy) Han
Rijksmuseum
Amsterdam, The Netherlands
ks.tracy.han@gmail.com
This project examined the historical restoration of
Chinese bronzes to identify conservation risks and the
types of intervention that can improve preservation,
contributing to the historical discussion on the conser-
vation of ancient Chinese bronzes in international
collections. Since the late 19th century, ancient Chinese
bronzes dating from 2000–221 BCE have been collected
and exported around the world, and they reveal signif-
icant variations in conservation. What explains this? If
materials added to the original object during repair are
unstable, to what extent is removal appropriate? Tradi-
tional restoration techniques for ancient Chinese bronzes
have been used since antiquity and were particularly
popular in the 15th–19th century. These treatments, such
as surface patination, often altered the original appear-
ance of the object, reflecting changing historical styles
and tastes in restoration in China. The challenge facing
conservators who now deal with these bronzes is that
no technical research on traditional Chinese restoration
practices has been carried out. This gap in knowledge
makes it difficult to treat these objects, as there exists no
reference framework for preservation or intervention.
The research therefore aimed to examine traditional
restoration techniques – including rejoining methods,
POSTER SESSION  343
the reproduction of missing elements, and the use of
patinas resembling corrosion layers and incrustations –
referred to in various expert texts from the 12th to the
18th century. Traditional restoration materials consisted
of organic binding media, salts, and metal infills. Cast
bronze sheet composed of 80% Cu, 15% Sn, and 5% Pb
was therefore artificially corroded and the reconstructed
surface visually characterized and documented, followed
by artificial aging in a climate chamber. X-ray diffraction
(XRD) and Fourier transform infrared (FTIR) spectros-
copy were conducted to understand the material property
changes. Aging the reconstructed samples artificially
allowed changes in the material to be observed and
the preservation issues caused by old treatments to be
determined. The data collected will be used to create a
database and a reference framework within which to
recognize alterations in ancient Chinese bronzes and
examine the intentions behind the treatment of these
historical objects. Furthermore, it will help to identify
broader conservation risks within the collections where
intervention can improve preservation. More generally,
the project will contribute to the historical discussion on
the conservation of ancient Chinese bronzes in interna-
tional collections.
344  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Microclimates for Marine Archaeological Iron Artillery:
Three Case Studies in Treatment, Storage, and Display
Laurie King* Erik Farrell
The Mariners’ Museum and Park The Mariners’ Museum and Park
Newport News VA, USA Newport News VA, USA
lking@marinersmuseum.org efarrell@marinersmuseum.org
*Author for correspondence
The unstable nature of marine archaeological iron is of
primary concern to its conservation. It often contains
trapped chloride species even after desalination, driving
future corrosion. Limiting this corrosion process
within an aerobic atmosphere requires desiccation to
a relative humidity (RH) of less than 12%. Small iron
objects can be sealed in anything from Tupperware
to barrier films, using silica gel to create a desiccated
microclimate. Artillery, however, is large, heavy, and
difficult to contain, and the hollow bore can develop a
different microclimate than the exterior surface. These
challenges impact the conservation of marine archaeo-
logical iron artillery during interventive treatment, both
in storage and while on display. This poster illustrates
conservation problems at these three different stages of
artifact care and conservation, providing a case study
for each. In active treatment, environmental control is
vital during drying; a longer time at higher RH increases
the formation of akaganeite, leading to less desirable
long-term outcomes. A system implemented at the
Queen Anne’s Revenge Conservation Laboratory (QAR
Lab) in North Carolina, USA, used a Lexan box, large
enough to hold artillery, and a recirculating ducted
POSTER SESSION
dehumidifier to quickly dry artillery after desalination
treatment. The second case study focuses on storage,
where a maintenance environment is required that can
maintain low RH in a large air volume with minimal
active input. A method used at The Mariners’ Museum
and Park in Virginia, USA, involved lining a wooden
crate with Marvelseal to create a storage environment
that would experience minimal environmental change,
using silica gel to control RH. The third case study
revolves around display, where environmental condi-
tions are similar to those for storage but with added
aesthetic requirements to accommodate exhibit design
decisions. A system developed by QAR Lab illustrates
a unique solution to microclimate desiccation in cases
where exhibit designs impose significant constraints.
The outcome was the creation of segmented tubes that
can hold enough desiccant to control the microclimate
and be easily inserted into artillery barrels with limited
space in front of the muzzle. In demonstrating how these
three solutions have evolved iteratively, this poster is
intended to provide ideas for solutions and to spark a
broader discussion on how archaeological artillery is
conserved and maintained.
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND
Results of Research on 17th–19th-Century Coffin
Portraits in the Collection of the National Museum in
Krakow
Maria Labut* Julio del Hoyo-Meléndez
National Museum in Krakow National Museum in Krakow
Krakow, Poland Krakow, Poland
mlabut@mnk.pl jdelhoyo@mnk.pl
Aldona Stępień Michał Obarzanowski
National Museum in Krakow National Museum in Krakow
Krakow, Poland Krakow, Poland
astepien@mnk.pl mobarzanowski@mnk.pl
The project’s main goal was to research the techniques
and technology used to create the coffin portraits in
the National Museum in Krakow’s collection. Coffin
portraits are a unique example of Polish cultural
heritage popular in the 17th and 18th centuries. They
were common amongst the Polish nobility who cele-
brated funerals with great ceremony and spectacle and
at which portraits were used to evoke the impression
of the deceased’s presence. They were painted very
realistically on a metal sheet and attached to the shorter
side of the coffin, so they were usually hexagonal or
octagonal in shape. The coffin portraits were studied
with a combination of analytical tools. Visual examina-
tion by VIS, IR, UV and RTG camera and microscopic
observation of cross-sections allowed their stratigraphy
to be established. The cross-sections were additionally
examined using scanning electron microscopy with
energy-dispersive X-ray spectroscopy. The paint layers
were examined using micro and macro X-ray fluores-
cence (XRF) spectrometry. The analysis confirmed the
presence of elements associated with pigments known
POSTER SESSION  345
Paulina Krupska Maria Goryl
National Museum in Krakow Faculty of Conservation and
Krakow, Poland Restoration of Works of Art,
pkrupska@mnk.pl Academy of Fine Arts
Krakow, Poland
Katarzyna Stefańczyk mgoryl@asp.krakow.pl
Research and Development Centre
for Renovation and Conservation *Author for correspondence
Nysa, Poland
katarzyna.stefanczyk@pwsz.nysa.pl
to have been used from the 17th to the 19th century
when the portraits were made. The pigments identified
included lead white and orpiment. Other pigments
that help to establish a potential date of production,
such as lead-tin yellow, Prussian blue and Ba and Zn
white, were also identified. Fourier transform infrared
spectroscopy was employed to identify the organic
compounds present in the portraits and confirmed
the presence of oil and proteinaceous components as
the paint binders. The composition of the metal alloys
used for the supports was identified by portable XRF
spectrometry, which revealed that four of them were
made of copper and the remaining seven of binary
alloys such as Sn-Pb, Cu-Zn and Ag-Cu. Voltam-
metry of immobilised particles was used to investigate
corrosion samples at the nanogram level to discern
between regions with different types of alterations. The
identification of corrosion products and knowledge of
the range of secondary layers from later restorations
enabled the selection of the most appropriate conser-
vation materials.
346  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Examination of an Unusual Apulian-Corinthian Helmet
Using X-Ray and Computed Tomography
Manuel Leroux*
Centre for Research and Restoration of the Museums of France (C2RMF)
Paris, France
manuel.leroux@culture.gouv.fr
A preliminary study was conducted at the Centre for
Research and Restoration of the Museums of France
(C2RMF) on a partially preserved Apulian-Corinthian
helmet with a surviving inlaid eye belonging to the Musée
départemental des Antiquités of Rouen in Normandy,
France. Computed tomography (CT) and X-radiog-
raphy were used to help solve a mystery surrounding the
helmet. A comparison with similar bronze helmets and
prometopidia (armor that protected a horse’s forehead)
with inlaid bone eyes indicates that the Rouen helmet
was made in southern Italy during the 5th century
BC. However, the curious shape of the helmet has no
known equivalent. The examination and analysis of
this unusual artifact revealed that the original shape
had been extensively altered and reinterpreted during
restoration in 1965. The combination of X-ray and CT
examination, supported by scanning macro X-ray fluo-
POSTER SESSION
Elsa Lambert
Centre for Research and Restoration of the Museums of France (C2RMF)
Paris, France
elsa.lambert@culture.gouv.fr
*Author for correspondence
rescence and micro gas chromatography combined with
mass spectrometry, provided a precise understanding of
the previous restoration. Many original fragments were
included in a large modern polyester putty reconstruc-
tion incorporating large and small fragments as a filling.
In some instances, modern brass powder was mixed
with the polyester filling causing corrosion, probably
due to the presence of chlorides in the mixture. The CT
cross-sectional images of the helmet allowed a better
understanding of the multilayered restoration work but
also highlighted its original fabrication. CT examination
also helped understand how the surviving polychromed
eye was attached as well as the method of assembly of
the crest using rivets. The objective of this poster is to
highlight the critical role that examination techniques
routinely used at C2RMF play in the interpretation of
artifacts.
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND
Diagnostic, Restoration and Maintenance of Outdoor Bronze
Artworks: Investigating Patinas in Marine Environments and
Their Stabilisation with Low Environmental Impact Treatments
Paola Letardi*
Institute for the Study of Anthropic Impacts and Sustainability in the Marine
Environment, National Research Council (IAS–CNR)
Genoa, Italy
paola.letardi@ias.cnr.it
The conservation of outdoor bronze artworks is chal-
lenging because of the need to consider the highly
complex system of alloy+patina/coating/environment.
Despite the numerous reports on bronze conservation
published in the scientific literature, in most cases
the studies have been limited to model surfaces and
laboratory-based investigations. Among the issues that
remain to be addressed in detail are: (i) the corrosion
of outdoor bronze surfaces in a changing environment,
especially the marine environment, with respect to
bronze disease; (ii) the value of the different surface
products, in order to better evaluate the effectiveness
of different cleaning methods; and (iii) the morpho-
logical properties of corrosion products with respect
to the behaviour of protective treatments (inhibi-
tors, coatings). Insights into the complex interactions
underlining these issues can only be obtained through
carefully designed experiments. In heritage science, the
multi-analytical in situ approach offered by non-de-
structive testing (NDT) allows the properties of heritage
objects, such as visual appearance, chemical composi-
tion, corrosion rate and surface texture, to be investi-
POSTER SESSION  347
Giulia Monari
Institute for the Study of Anthropic Impacts and Sustainability in the Marine
Environment, National Research Council (IAS–CNR)
Genoa, Italy
gm.monari@gmail.com
*Author for correspondence
gated in detail. Thus, with the goal of more successful
conservation treatments of outdoor bronze monuments,
we conducted multi-analytical NDT measurements of
marine-weathered coupons and then compared the
results to those obtained with several bronze artworks,
mainly from the 19th and 20th centuries, in the Stag-
lieno Monumental Cemetery (Genoa, Italy) and Certosa
Monumental Cemetery (Bologna, Italy). Our primary
objective was to better define the variability ranges of
relevant parameters and the similarities of the surface
morphologies of the coupons and those of the outdoor
metal artworks exposed to different environments.
Moreover, we consider the applications of the avail-
able NDT techniques to better define good practices
for outdoor bronze conservation. Particular attention
was paid to the identification of nantokite, a promoter
of bronze disease, and its uneven distribution within
patinas. We also discuss the results of preliminary tests
directed at the in situ characterisation of traditional
and innovative treatments of patinated bronze surfaces
aimed at inhibiting the cyclic corrosion linked to the
presence of CuCl.
348  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
The Curious Case of Storage at the Petrie Museum of
Egyptian Archaeology
Graeme McArthur* Merry Chow
University College London University College London
London, UK London, UK
graeme.mcarthur@ucl.ac.uk merry.chow.19@ucl.ac.uk
*Author for correspondence
Following safe storage during the Second World War,
the Petrie Museum’s collection was moved into a former
stable on the University College London campus. Storage
for non-display objects consisted of purpose-built
wooden cupboards containing wooden drawers. Most
of the collection, including metals, remains there to
this day. Very recently it was noticed that the base of
most of the drawers is made from a brown plastic that
probably originates from the 1950s. This immediately
raised concerns about its stability and the potential for
off-gassing. To begin to investigate this problem, an Eltek
pollutant monitor was placed inside one of the cupboards.
It read high levels of volatile organic compounds that
were not present in the air outside. As part of this inves-
tigation, a condition survey of the 7,000+ metal objects
was carried out. Although most of the collection is in
stable condition, some corrosion products of an unusual
appearance were observed. On some bronze objects,
powdery blue corrosion was forming, while others lying
flat in Plastazote cut-outs were found to have a different
corrosion colour on each side. This evidence all pointed
towards the metal objects potentially being affected by
POSTER SESSION
the materials used to build the storage cupboards. Fourier
transform infrared (FTIR) analysis was thus carried out
to identify the plastic used to make the drawers; although
it is certainly cellulose based, an exact match was not
found. Samples of corrosion products analysed with
FTIR and X-ray diffraction (XRD) suggested that the blue
corrosion product was copper chloride acetate, known to
form on copper artefacts in the presence of acetic acid.
Wooden storage often produces acetic acid, but this tends
to diminish over time, so there were concerns that the
plastic was the most likely cause. However, samples of
plastic in a sealed polythene bag produced no changes
in colour to an A-D strip, whereas samples of wood
produced a clear change. From this it was possible to
infer that, despite the age of the cupboards, the wood
was still off-gassing. A dedicated metals storage area has
now been created with Polstore steel cupboards and door
seals to allow some control of the environment via silica
gel. This will allow unstable metal artefacts to be stored
at low levels of relative humidity in a cupboard made
from inert materials, removing them from the vicinity
of inappropriate storage materials.
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND
Comparing Simple Portable XRF with PIXE Analysis for
Archaeological Metal Objects: Suitability, Advantages and
Drawbacks
Eva Menart*
National Museum of Slovenia
Jožef Stefan Institute
Ljubljana, Slovenia
eva.menart@nms.si
Portable X-ray fluorescence spectrometry (pXRF) has
been adopted by many heritage institutions and conser-
vation laboratories, due to its non-invasive nature,
simplicity and relatively low price, at least compared
to more sophisticated analytical instruments. As a
semi-quantitative tool for alloy identification, pXRF
is of particular interest for conservation purposes.
However, more in-depth studies are often left to much
more complicated scientific instrumentation, such as
proton-induced X-ray emission (PIXE) or even the more
invasive laser ablation, coupled with inductively coupled
plasma mass spectrometry. To investigate the semi-quan-
titative nature of pXRF, a series of analyses was carried
out, first on standard materials and then on real archae-
ological objects, to compare the results obtained using
pXRF (Hitachi X-MET 8000 and imbedded software for
spectrum analysis) and PIXE (Tandetron accelerator,
custom-/in-house-made software). Commercial XRF
instruments commonly include a series of calibrations
for the user to select according to the samples. Our
experiments showed that if the calibration is selected
correctly (i.e. without excluding certain elements), the
POSTER SESSION  349
Žiga Šmit
Jožef Stefan Institute
Faculty of Mathematics and Physics, University of Ljubljana (retired)
Ljubljana, Slovenia
ziga.smit@fmf.uni-lj.si
*Author for correspondence
results obtained from pXRF and PIXE match very well
in terms of both the identification and quantification of
different elements. For the main alloy components, the
differences were within reasonable uncertainty ranges,
thus demonstrating that the simpler XRF can safely be
used to determine the elemental concentrations of the
main metal elements. An important advantage of PIXE
is its more accurate determination of low-concentration
or trace elements as well as its lower detection limits
(and smaller measurement spots). While the commer-
cial software of the portable XRF instrument allows
the determination of element-mass concentrations
below 0.1%, in these cases the data must be treated
with caution and confirmed by the source data, i.e. the
spectra. Although the XRF instruments are generally
simple to use, a correct interpretation of the data requires
a certain level of expertise. When investigating metal
objects, pXRF and PIXE data, when analysed correctly,
are comparable and both are accurate enough to avoid
the need for destructive analysis. However, in trace
analysis (e.g. to determine provenance), the use of at
least PIXE is recommended.
350  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Methods of Marking Small Museum Objects: A Joint
Project of the National Museum in Warsaw and the
National Institute of Cultural Heritage in Poland
Anna Mistewicz* Justyna Kwiatkowska
National Museum in Warsaw National Museum in Warsaw
Warsaw, Poland Warsaw, Poland
amistewicz@mnw.art.pl jkwiatkowska@mnw.art.pl
*Author for correspondence
In 2020, the National Museum in Warsaw (NMW) and
the National Institute of Cultural Heritage (NICH) in
Poland initiated a joint project entitled ‘Analysis of
methods of marking artifacts and museum objects with
the use of microtechnology’. Its aim is to analyze the use
of micromarkings to label objects from the collection of
the NMW that cannot be numbered using traditional
methods, due to their size, surface texture, or decora-
tion. This problem mostly concerns small metal objects
such as coins, which comprise roughly one-fourth of the
NMW’s collection. The long-term aim of the project
is to devise an effective and safe method of marking
all museum and heritage objects. The chosen method
should enable clear identification and aid in verifying
an object’s provenance in case of theft or loss. Conse-
quently, it should include an accession number or at least
the museum’s name or a distinguishable owner’s mark.
Desirable features of the marking method are small size,
legibility (detectability), reversibility, durability (long
life), and stability under changing environmental condi-
tions as well as the ability to encode specific information
within the marking. Since applying accession numbers
POSTER SESSION
on large collections made up of thousands of objects is a
time-consuming practice, the proposed method should
also be easy to apply and inexpensive. Five marking
methods have so far been analyzed: microparticles
(microholograms), RFID passive tags, mixtures of phos-
phors invisible to the naked eye that have a particular
glow on exposure to ultraviolet light, QR codes, and
data matrix codes. Several meetings with specialists
from different sectors have taken place. Oddy tests of
some tags and microparticles in resin were conducted
to evaluate the risk of corrosion initiation by the chosen
markers on heritage materials. The microparticle method
(which may include the addition of subsequent infor-
mation, although there is a limit to the total number of
digits) is readable only with the use of a magnifying glass
or microscope. As this method was used experimentally
15 years ago for marking ecclesiastical artifacts against
theft, its legibility, stability, and corrosion resistance were
examined on site. Laboratory tests of methods to remove
this type of numbering were also conducted. The poster
will present the state of progress of the project and the
preliminary results.
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND
Influence of the Application Methodology on the
Performance of Coatings for the Protection of Metallic
Heritage Objects
María Teresa Molina* Blanca Ramírez Barat
National Centre for Metallurgical National Centre for Metallurgical
Research, Spanish National Research, Spanish National
Research Council (CENIM–CSIC) Research Council (CENIM–CSIC)
Madrid, Spain Madrid, Spain
mt.molina@cenim.csic.es blanca.ramirez@csic.es
Acrylic resins and waxes are still the most widely used
coatings for the protection of metallic heritage objects.
However, a literature review shows that the majority of
the research on the performance of coatings for metal
conservation has not paid sufficient attention to the
application methodology, making comparisons of the
results across studies unreliable. In the COMPACT
project, the protective capacity and stability of tradi-
tional coatings for bare steel, i.e. Paraloid B-72, Incralac
and Cosmolloid Wax, were evaluated. These coatings
have been extensively studied over time, but application
variables such as drying time, coating thickness, number
of layers, solvent used and application technique have
been largely ignored. In this project, the influence of
these variables on the corrosion protective capacity of
the coating and the physico-chemical changes resulting
from artificial ageing were studied. Brush was selected
as the method of application and acetone, xylene and
white spirit as the solvents. Different numbers of layers
were applied to bare steel samples, with each layer
allowed to dry for different times and the thickness
of the layer thus obtained then determined. The fully
coated samples were left to dry for 3 days to 5 weeks.
Accelerated ageing tests were carried by exposing the
POSTER SESSION  351
Emilio Cano
National Centre for Metallurgical
Research, Spanish National
Research Council (CENIM–CSIC)
Madrid, Spain
ecano@cenim.csic.es
*Author for correspondence
samples to UVA radiation and condensation cycles. The
corrosion protection of the coatings during accelerated
ageing was characterised using electrochemical imped-
ance spectroscopy and the coating efficacies compared
using external reflection Fourier transform infrared
spectroscopy. The results showed that the high volatility
of acetone complicated a homogeneous application of
the coating on the sample, producing waves consistent
with solvent evaporation. The number of layers and the
thickness of the coating were not directly related. The
drying time of the coating was found to be one of the
most important variables affecting its protective ability:
After accelerated ageing, for coated steels left to dry for
only 3 days, their impedance modulus at low frequencies
was reduced by a much larger extent than that of samples
dried between 2 and 5 weeks. Infrared analyses showed
chemical changes in the molecular bonds during the
ageing process in most samples. Our results demonstrate
the relevance of controlling the application parameters
when comparing the performances of different coatings
for the conservation of metals. The protection offered
by different coatings depends not only on the product,
substrate and environmental conditions but also on the
application methodology.
352  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Archaeological Tinned-Copper Objects: A Study on
Corrosion and Cleaning Treatments
Mohammad Mortazavi*
Art University of Isfahan
Isfahan, Islamic Republic of Iran
m.mortazavy@aui.ac.ir
www.aui.ac.ir
Hamid Reza Bakhshandehfard
Art University of Isfahan
Isfahan, Islamic Republic of Iran
hr.bakhshan@aui.ac.ir
www.aui.ac.ir
The tinning of copper and copper-based objects has a
long history. This surface treatment, which is responsible
for the silvery appearance of the treated objects, forms a
corrosion-resistant layer and has been a common practice
since antiquity. The long-term burial of tinned-copper
artifacts can lead to the formation of copper and tin
corrosion compounds, which reflect the dissolution of
copper followed by the precipitation of the corrosion
products and their formation as a thick layer on the
surface. In fact, coverage of the surface with corrosion
products disguises the fact that the object had been
tinned. However, cleaning can also dissolve the tin
layer, resulting in the loss of an important part of the
object’s identity and of insights into the manufacturing
process. Consequently, cleaning archaeological artifacts
made using a tinned-copper technique and covered
with corrosion products is a complicated task. In this
study, the corrosion process of historical tinned-copper
objects was examined using scanning electron micros-
copy with energy-dispersive X-ray spectroscopy. The
POSTER SESSION
Abbas Abed-Esfahani
Islamic Azad University – Khorasgan Branch
Isfahan, Islamic Republic of Iran
aabed@khuisf.ac.ir
www.khuisf.ac.ir
*Author for correspondence
effects of chemical reagents commonly used to clean
and remove copper corrosion from tinned surfaces
were also investigated. For this purpose, an artificial
tin oxide was electrochemically formed on the surface
of experimental tinned-copper samples. The effects of
various cleaning reagents—disodium ethylene diamine
tetraacetic acid (Na2-EDTA), sodium tripolyphosphate
(STPP), citric acid, formic acid, and alkaline Rochelle
salt—on the electrochemically produced oxide layer were
then compared. The amounts of dissolved tin that accu-
mulated in the cleaning reagents were determined using
atomic absorption spectroscopy. The results showed that
tinned surfaces were dissolved by all of the tested chem-
ical solutions, but to varying degrees. Tin dissolution
was highest in alkaline Rochelle salt. Although formic
acid was the least aggressive cleaning reagent, it also has
the potential to damage the tin oxide layer beneath the
copper corrosion products and therefore must be used
with caution. Mechanical cleaning, which may also cause
disruption on the surface, is also discussed.
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND
Archaeometallurgical Investigations of a Late Iron Age
Helmet: An Interdisciplinary Approach
Nataša Nemeček* Lucija Grahek
National Museum of Slovenia Research Centre of the Slovenian
Ljubljana, Slovenia Academy of Sciences and Arts
natasa.nemecek@nms.si Ljubljana, Slovenia
lgrahek@zrc-sazu.si
Tomaž Lazar
National Museum of Slovenia Marijan Nečemer
Ljubljana, Slovenia Jožef Stefan Institute
tomaz.lazar@nms.si Ljubljana, Slovenia
marijan.necemer@ijs.si
In early 2020, a bronze helmet was found in Podzemelj,
southeastern Slovenia, at the newly discovered cemetery
Pezdirčeva njiva. The Slovenian-type Negova helmet
dates to the Late Hallstatt period and Late Iron Age
(500–200 BC) and was ritually damaged before its deposi-
tion. It therefore ranks among the most important archae-
ological finds in Slovenia in recent years. The decision to
submit the helmet to in-depth analyses was dictated by
two factors. First, a better understanding of the helmet’s
composition and state of preservation was needed in
order to determine suitable conservation techniques for
treating the heavily corroded find. Second, it was hoped
that a metallurgical examination of the helmet would
reveal its technological make-up, thus providing valuable
insight into the craftsmanship and skills of the Iron Age
metalworkers and into the manufacturing processes they
employed. Our investigation began with non-destructive
X-ray radiography and X-ray fluorescence analyses. The
latter revealed a high percentage of tin on the surface of
the helmet, consistent with the selective dissolution of
copper from the alloy. Several samples detached from
various sections of the helmet were submitted to metal-
POSTER SESSION  353
Peter Fajfar
Faculty of Natural Sciences and
Engineering, University of Ljubljana
Ljubljana, Slovenia
peter.fajfar@omm.ntf.uni-lj.si
Borut Žužek
Institute of Metals and Technology
Ljubljana, Slovenia
borut.zuzek@imt.si
*Author for correspondence
lographic analyses. Their microstructures showed that
the helmet was made primarily by cold-working. A closer
investigation of the samples confirmed that the metal
is heavily corroded. The stratigraphy of the corrosion
layers was studied in detail using optical microscopy
analyses and scanning electron microscopy with ener-
gy-dispersive spectroscopy. The presence of intergranular
corrosion below the original surface dictated the choice
of conservation treatment, specifically, consolidation with
Paraloid B-72. The initial condition of the artefact was
documented using 3D scanning, which proved instru-
mental over the course of subsequent conservation work.
The applications of the resulting 3D model included the
manufacture of a closely fitting internal frame enabling
the safe long-term display of the helmet. Identification
of the mechanisms and morphology of the corrosion of
archaeological bronze has proved invaluable in helping
conservators to characterise deterioration processes and
take suitable steps to prevent their progression. Once
the conservation work is finished, the helmet will be
included in the new permanent exhibition in the Bela
Krajina Museum in Metlika.
354  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
The Care and Maintenance of Heritage Sample Collections
Peter Northover* Vanessa Cheel
University of Oxford (retired) University of Oxford
Oxford, UK Oxford, UK
peter.northover@retired.ox.ac.uk vanesa.cheel@materials.ox.ac.uk
*Author for correspondence
A century of metallurgical research in cultural heritage,
from the Chalcolithic to contemporary times, has
amassed a collection of many thousands of samples
taken for compositional analysis and metallography. As
new or enhanced methods of analysis and microscopy
develop and become available, these samples provide
an enormous resource for future research and to
protect the original objects from further sampling. The
Archives and Collections Committee of the Historical
Metallurgy Society (HMS) currently curates a small
number of such heritage sample collections left to us
by pioneer researchers in the area. This poster aims to
provide an idea of the practical and ethical questions
we have had to address along the way and to describe
approaches to the management of sample collections in
the future. The first and biggest question is the extent
to which new interventions should be allowed. Where
a collection is sufficiently historically important, for
example the samples prepared in the 1860s by Henry
Clifton Sorby, new interventions may be ruled out and
the samples preserved as they are. At the other extreme,
samples have been consumed for lead isotope analysis in
order to avoid re-sampling an object. (With laser abla-
POSTER SESSION
tion techniques this is now much less of a problem.) The
collections with which we are at present concerned were
deposited with the intention of being loaned for re-use,
and it is our responsibility to ensure that the methods
used are appropriate, typically repolishing and etching
for optical and electron microscopy and for electron
backscatter diffraction, microhardness measurements
and laser ablation. These techniques have a minimal
impact on the sample and the mounts are otherwise
conserved as received. Sometimes the mounts them-
selves are deteriorating. Sixty-year-old epoxy does not
always survive well and then the samples are re-mounted
in the same orientations as before. The availability and
conditions of access to a sample, together with a cata-
logue, are available on the HMS website. The existing
collections have primarily been used for metallography
and compositional data is often lacking. The documen-
tation for future accession will include metallurgical
as well as archaeological data so researchers can more
easily find relevant material. Beyond that, it is our aim
to develop an area on our website where the metadata
for other sample collections will be published, ensuring
that their value is properly realised.
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND
Monitoring the Effect of Humidity on the Tarnishing of
Silver 0.800 by Means of Electrochemical Noise
Janette Ortíz-Corona
National Autonomous University of Mexico (UNAM)
Mexico City, Mexico
jortizcorona@gmail.com
Esteban Miguel García-Ochoa
Corrosion Research Center, Autonomous University of Campeche
Campeche, Mexico
estebangarci@gmail.com
Historical silver artifacts made with silver-copper
alloys tend to tarnish—or corrode—in environments
that contain sulfides, causing changes in aesthetic
appearance and sometimes losses. This represents a
problem in their conservation and restoration, since to
perform an intervention, the corrosion products and
their corrosion mechanisms must be identified. Electro-
chemical techniques that have proven their effectiveness
are required to safeguard the properties, aesthetics,
and original surfaces of these artifacts. Electrochem-
ical noise (EN) is a nondestructive and nonintrusive
technique that has been widely used to understand
the interfacial behavior of electrochemical systems,
as well as to study real surfaces in situ and corrosion
mechanisms. However, it is little known in the field of
conservation and restoration. Therefore, the purpose
of this work was to use EN to monitor the influence
of relative humidity (RH) on the tarnishing process in
silver and to study it in order to identify the corrosion
mechanism. The tarnishing of one of the most common
POSTER SESSION  355
Francisco Javier Rodríguez-Gómez*
Department of Metallurgical Engineering, Faculty of Chemistry, National
Autonomous University of Mexico (UNAM)
México City, Mexico
fxavier@unam.mx
*Author for correspondence
alloys in silver artifacts, silver 0.800, was monitored for
48 hours by EN and under controlled atmospheres. To
simulate the controlled atmospheres, a desiccator and
standard solutions were used to generate RH of 40 and
90%. Electrochemical atmospheric corrosion monitors
(EACM) made of silver plates were used as an electro-
chemical cell in an arrangement of three nominally
identical electrodes. The surfaces of the EACMs were
etched and then contaminated with a 10% v/v solution
of (NH4)2S to form the corrosion or tarnishing layer. To
analyze the time series, a trend removal was performed
and the data were interpreted by direct examination,
statistical analysis, and recurrence of EN. Finally, direct
analysis showed that the transients in most signals were
bidirectional with high frequency, irregular, and low
amplitude oscillations. The increase in humidity favored
greater noise resistance (Rn) and adsorption of H2O and
OH− on the surface, which caused the growth of the
corrosion layer (Ag2S and Cu2S) and thus the formation
of a pseudo-passive layer that protected the surface.
356  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Investigating Precious Artefacts Using Non-destructive FIB
on FEG-SEM: A Case Study of 10th-Century Hollow Gilded
Copper Alloy Pendants (Gombiky) from Prague Castle
Estelle Ottenwelter*
Czech Academy of Sciences, Institute of Archaeology
Prague, Czech Republic
ottenwelter@arup.cas.cz
Claudie Josse
Centre de Microcaractérisation Raimond Castaing (CNRS UAR 3623)
Toulouse, France
claudie.josse@ums-castaing.fr
Focussed ion beam (FIB) mounted on a scanning elec-
tron microscope with a field emission gun (FEG-SEM)
offers new perspectives in studies of soft, multilayered
metal artefacts. In addition to conventional observa-
tion, the system allows cross-sections to be made in situ,
that is, within the SEM chamber, using the FIB to mill
the selected surface and thus obtain a local cross-section
up to 100 to 200 μm wide and 10 to 20 μm deep. This
new method of investigation is of particular interest
in the study of precious cultural heritage artefacts, for
which sampling is often problematic. Unlike classical
metallography, the accurate cross-sections obtained
with FIB on FEG-SEM avoid damage to multilay-
ered materials, as ionic ablation does not deform the
POSTER SESSION
Luc Robbiola
TRACES Laboratory (CNRS UMR5608), Université de Toulouse
Toulouse, France
robbiola@univ-tlse2.fr
*Author for correspondence
soft layers. The technique is therefore particularly
useful for observing and characterising gilded artefacts.
After surface milling, detailed structural information
can be obtained at the nanometre scale and used in
further analyses. Applied here on hollow gilded copper
alloy pendants (known as gombiky) from Prague Castle,
dated from the 10th century AD, FIB on FEG-SEM
yielded new and accurate information regarding the
thickness, porosity, metallurgical structure and general
condition of these complex artefacts. The method aims
to provide new parameters for drawing comparisons
between fine products produced by highly skilled
jewellers and coarse imitations made by less-experi-
enced craftsmen.
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND POSTER SESSION  357

The Enemy Within: Dezincification and Cyclic Corrosion on

a Brass Patinated Equestrian Sculpture

Maria João Pereira* Sara Fragoso Rui Silva Alexandra P. Rodrigues

NOVA School of Science and
Technology, NOVA University
Lisbon
Caparica, Portugal
mjgu.pereira@campus.fct.unl.pt
LAQV–CHARM and CENIMAT/
i3N, Department of Conservation
and Restoration, NOVA School of
Science and Technology, NOVA
University Lisbon
Caparica, Portugal
eslf@fct.unl.pt
CENIMAT/i3N, Department of
Materials Science, NOVA School
of Science and Technology, NOVA
University Lisbon
Caparica, Portugal
rjcs@fct.unl.pt
Department of Conservation
and Restoration, NOVA School of
Science and Technology, NOVA
University Lisbon
Caparica, Portugal
rodrigues.alexandra@gmail.com
*Author for correspondence

In this work, a brass equestrian sculpture (Cu 62.2/
Zn 36.5/Sn 1.3 wt%), in a poor state of preservation due
to localized cyclic corrosion, was assessed with the aim
of developing a strategy for its conservation. Considering
the lack of information regarding the origin, the date
of production, and the history of this object, a stylis-
tic-based contextualization was carried out together
with a literature review of dezincification processes in
chlorine-containing media. To prepare a proposal suited
to the conservation needs of the object, physical and
chemical methods of analysis were used, which provided
essential information regarding the sculpture’s constitu-
tion and composition, corrosion and damage problems,
and their respective causes. The surface examination was
performed by optical microscopy using a stereoscopic
magnifying glass; structural and microstructural analyses
were carried out, respectively, using digital radiography
and metallography, and compositional studies using
energy-dispersive X-ray fluorescence, scanning electron
microscopy and energy-dispersive X-ray spectroscopy
(SEM-EDS), and X-ray diffraction (XRD). The results of
the investigation showed that different parts of the brass
sculpture were cast by sand-casting, subsequently joined
by brazing and then patinated in brown. The presence
of chloride inside the object was determined to be the
main cause of dezincification and autocatalytic corrosion,
which resulted in an aggravated active corrosion process.
Further progression of this process risked causing struc-
tural instability that would jeopardize the handling and
appreciation of the object. It was thus necessary to design
a methodology of investigative cleaning, both mechan-
ical and chemical, of the surface and a pre-stabilization
protocol that followed the criteria of minimum inter-
vention, so as not to compromise the surface decoration
while also promoting the stabilization of the corrosion
layers using a corrosion inhibitor. A methodological
proposal of controlled internal desalination to achieve
chemical stability without affecting the decoration was
also elaborated. As the interior of the sculpture was
inaccessible, a small hole was drilled in a low-visibility
area to allow the extraction of a sample of the ceramic
material used to make the hollow space during the casting
process. Examination of the sample using SEM-EDS
and XRD showed that this material was the origin of
the NaCl contamination. For the desalination process, a
second hole was drilled near the first one, with thin tubes
placed in each one to enable the inflow and outflow of
deionized water and therefore the internal removal of the
salts. This approach also allowed the desalination process
to be monitored without compromising the decorative
patina of the object. The stable packaging of the object
was ensured as well.
358  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND POSTER SESSION

Standardizing Acid Digestion Methodology to Determine

the Chloride Content of Ferrous Corrosion Samples

Kimberly Roche* Johanna Rivera Lisa Arslaner Stephanie Crette

Warren Lasch Conservation Center,
Clemson University
North Charleston SC, USA
roche4@clemson.edu
www.clemson.edu/wlcc
Warren Lasch Conservation Center,
Clemson University
North Charleston SC, USA
jrd123@clemson.edu
www.clemson.edu/wlcc
Warren Lasch Conservation Center,
Clemson University
North Charleston SC, USA
lmkaspr@clemson.edu
www.clemson.edu/wlcc
Warren Lasch Conservation Center,
Clemson University
North Charleston SC, USA
scrette@clemson.edu
www.clemson.edu/wlcc
*Author for correspondence

Acid digestion is a critical step in determining desalina-
tion treatment progress and endpoints for conservation
practitioners. This method quantifies residual chloride
in the corrosion layers of ferrous artifacts in contrast
to indirect chloride concentrations extracted from
desalination solutions. The analytical protocol for this
technique varies by institution and suffers from a lack of
standardization. Sample controls and materials are rarely
reported, making the protocols hard to reproduce with
precision. Conservators often rely upon small quantities
of corrosion powders to analyze chloride content, and
any chloride contamination in the procedure will have
large implications on data output and interpretation.
This study aims to standardize an analytical protocol
for determining chloride content in iron corrosion
samples through acid digestion, with a focus on elimi-
nating or significantly reducing chloride contamination
during each stage. The protocol was divided into five
stages as follows: (1) sample collection; (2) digestion
in concentrated nitric acid; (3) neutralization using
sodium hydroxide; (4) phase separation/filtration; and
(5) chloride analysis with ion chromatography. After a
literature review determined the most common protocol
variations, the variables tested in this study were: the
covering method (watch glass over a flask sealed with
slightly punctured polyethylene film); temperature
(20°C–22°C and 35°C–40°C); time (3, 7, 10, and 14 days);
and phase separation method (no filtration, Celite
filtration aid with qualitative filter paper, Whatman 42
quantitative filter paper, Whatman 542 quantitative filter
paper, and centrifugation). Trials were run using sodium
chloride (NaCl) and synthesized solid-state akaganeite
(b-FeOOH) as the analytes. Three sample replicates and
two procedural blanks were used to test each variable.
The results of the NaCl trials indicated that the covering
method had a negligible effect (less than 0.3% difference)
on chloride readings. Heated NaCl solutions resulted in
greater chloride loss (4.5%) compared to unheated solu-
tions. Nonetheless, heating was found to be necessary,
as heated samples of akaganeite resulted in 25% greater
chloride concentrations, indicating that akaganeite was
not fully digested at room temperature after 7 days. The
chloride yield in the akaganeite samples was highest after
3 days of heating and declined with increased heating
time. The greatest source of chloride contamination and
yield inconsistencies occurred at the separation stage of
the method. An analytical protocol for acid digestion
is proposed that produces the highest theoretical yield
of chloride, the least contamination in the blanks, and
greater precision among the analytes.
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND
Treatment of Two Fanghu Vessels (1st Century BC):
Conservation Issues of Archaeological Painted Bronze
Cristina Scarrone*
Independent conservator
Genoa, Italy
cristinascarrone.restorer@gmail.com
Dominique Maria Scalarone
Department of Chemistry, University of Turin
Turin, Italy
dominique.scalarone@unito.it
Franca Varallo
Department of Historical Studies, University of Turin
Turin, Italy
franca.varallo@unito.it
The conservation of two Chinese fanghu vessels in
painted bronze (1st century BC) from the MAO Museum
of Oriental Art in Turin raised issues concerning archae-
ological bronze painted with tempera but showing a loss
of cohesion and the extensive presence of corrosion prod-
ucts. The opaque paint layer, the type of pigments and the
corrosion products prohibited the use of the materials and
methods normally adopted for archaeological artefacts.
This study focussed on three fundamental phases of the
conservation intervention: pre-consolidation, cleaning
and retouching. For the pre-consolidation of the paint
film, a study was carried out to identify a consolidating
agent that could be applied to metal while leaving the
characteristics of the film unchanged, in particular its
opacity and colour, and at the same time provide adhe-
sion and cohesion. The materials investigated were the
acrylic resin Paraloid B-72, cellulose ethers (Klucel E
and Klucel G), the aliphatic resin Regalrez 1126 and the
urea-aldehyde resin Laropal A81. All were subjected to a
mechanical strength test, optical and autoptic evaluations
and photochemical ageing. The best-performing solution
was Paraloid B-72 at 5% in methyl ethyl ketone, with
a dosage of 2 drops on a surface of 1 cm2. The level of
POSTER SESSION  359
Marco Demmelbauer
Centro Conservazione e Restauro “La Venaria Reale” and SUSCOR, University of
Turin
Venaria Reale, Italy
marco.demmelbauer@centrorestaurovenaria.it
Tommaso Poli
Department of Chemistry, University of Turin
Turin, Italy
tommaso.poli@unito.it
*Author for correspondence
cleaning of the metal surface was a compromise between
conservation and aesthetic requirements. The removal of
unstable corrosion products revealed the metal surface
or a layer of cuprite, the colour of which was, unfor-
tunately, very close to that of the paint film. This layer
was treated mechanically using an ultrasonic scaler to
lower the tone and matt the surface, so that it would not
compete with the decoration. Cleaning was alternated
with retouching measures. Traces of the tempera detach-
ments were visible owing to the surrounding corrosion
products, which had stuck to the surface forming an
outline of the area. Therefore, retouching was carried
out before the corrosion products were removed. After
several tests, it became clear that traditional retouching
techniques, such as veiling or dotting, were not suitable
as they enhanced the lack of homogeneity of the artefacts.
Ultimately, an ultraviolet fluorescent pigment (Kremer
Pigmente #56200), dispersed in a mimetic colour made
with mineral pigments, was used together with a 5%
solution of Paraloid B-67 in ligroin. The fluorescent
pigment is imperceptible at visible light such that it can
be used to create tone-in-tone additions that respect the
recognition criteria of the intervention.
360  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Investigating Three Types of Dry Cell Battery
Deterioration
Meredith Sweeney
Smithsonian National Air and Space Museum
Washington, DC, USA
sweeneym3@si.edu
Electric cells and batteries are found in the collec-
tions of nearly every history museum, but there is no
universal guidance on how to approach these poten-
tially hazardous objects. A 2021 survey of heritage
professionals indicated that half of the respondents
immediately discard batteries when they enter collec-
tions and/or when they show signs of deterioration.
Following an inspection of 32 batteries in the Smithso-
nian National Air and Space Museum (NASM) collec-
tion, three recurring condition issues became apparent:
corrosion occurring within the cell, corrosion occurring
on the external sides of the cell, and electrolyte leakage.
Determining the location of corrosion indicates whether
its development was influenced by the electrolyte or by
external environmental factors. Alkaline electrolyte
leakage can mimic the appearance of zinc corrosion
(a common material found within dry cell batteries),
and differentiating between the two is an imperative
step in determining stability and designing treatment
strategies. This poster discusses three case studies of
POSTER SESSION
dry cell batteries within the NASM collection where
these common condition issues occur. The case study
objects include zinc-carbon WW2 American and Japa-
nese batteries and a nickel-cadmium battery used in
the Apollo 11 cameras. Each case study utilizes various
analytical techniques. X-radiography is used to deter-
mine corrosion location, the loss of internal material,
and the source of any structural deformation. Ultraviolet
photography, portable X-ray fluorescence, and Fourier
transform infrared spectroscopy with attenuated total
reflectance (FTIR-ATR) aid in characterizing the signs
of degradation and differentiating between corrosion
products and leaking electrolyte. This is supported by a
discussion of dry cell battery construction and common
sources of deterioration. Treatment rationale is briefly
explored with the aim of informing collection stew-
ardship practices. The goal of the poster is to inform
conservators on how to characterize and analyse some
forms of battery deterioration and to illustrate that signs
of degradation do not necessitate disposal.
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND
The Complexity of Developing a Restoration Plan for an
18th-Century Cast Iron Fountain
Júlia Tauber
Landesamt für Denkmalpflege im Regierungspräsidium Stuttgart
Baden Württemberg, Germany
Julia.Tauber@rps.bwl.de
Stuttgart’s beautiful cast iron fountain known as the
Marktbrunnen, or Thouret Brunnen, is situated in the
city’s Market Square (Marktplatz). The basin consists of
16 relief plates that vary in their design. The plates were
cast in 1714, with the middle column added in 1804.
However, as the Marktplatz is currently under renovation
to raise its entire surface to the same level, the fountain
must be raised 45 cm higher than its current position.
This manoeuvre has necessitated its restoration. The
fountain has already been moved five times in its history,
including its display in three different squares. Yet moving
and restoring the fountain once more is a complex
process, as the latest move, in the 1970s, compromised
its exterior. Specifically, the fountain was cleaned by air
abrasion and coated with a zinc primer, which caused the
removal of the cast skin, thus exposing the grey cast iron
plates and increasing the risk of corrosion. Construction
of the square is ongoing and is due to be completed by
the end of 2022. This has created pressure to rapidly find
solutions for the fountain’s restoration. Collaboration
between conservators, analytical scientists, architects
POSTER SESSION  361
and structural engineers is required to complete this
complex project. Prior to the restoration, the fountain was
digitised using structure-from-motion photogrammetry.
Preliminary investigations included an analysis of the
coating using an optical microscope, energy-dispersive
X-ray spectroscopy and Fourier-transform infrared
spectroscopy. Trials for removing the current coating are
complete and alternative coating materials have under-
gone adhesive tensile strength tests to determine the most
suitable coating methodology. X-ray imaging was used
to obtain evidence of graphitic corrosion of the plates.
As the relief plates forming the basin are buried 1.5 m
underground, their restoration in situ was enabled by
excavating the installation such that it could be raised in
one piece using hydraulic jacks. This poster describes the
decision-making process employed in the conservation,
which included a methodical approach to investigations,
careful planning and collaboration between disciplines.
Successful restoration of the Marktbrunnen will retain
and enhance the fountain’s natural beauty, allowing its
further appreciation for many years.
362  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
Testing Gap Fillers for Archaeological Metal
Simeon Tsvetkov
AOC Archaeology Group
Loanhead, UK
simeon.tsvetkov@zoho.eu
The headplate of a 4th-century fibula was excavated from
the island of Funen in Southern Denmark. It is an inter-
esting find because of its rarity in the local context, and
because its design and characteristics suggest a foreign
influence or origin. It has a gold leaf decoration with
granulated design, as well as two semi-spherical blue glass
beads and silver wire around the edges. The object was
severely damaged during burial and some of its structural
and decorative elements had broken or fallen off. Whilst
a lot of the fragments could simply be adhered back into
their place, the reattachment of the two glass beads was
more complex due to the fact that the original slots are
partially destroyed and the back plate is fragmented. It
was decided that the best way to reattach the beads would
be to reconstruct the holes and back plate using a gap
filler. Since there is no general consensus in the conser-
vation literature as to the best material for gap filling of
archaeological metal, two experiments were conducted
to determine the most suitable adhesive/solvent combi-
nation (from the ones readily available in the lab) to use
on the fibula. Four adhesives (Paraloid B-72, Vinnapas
POSTER SESSION
B100 SY100, Butvar B-98, and Aquazol 200) were selected
for the experiments. Each one was mixed with different
solvents (ethanol, acetone, and toluene), as well as in
mixtures of them, after which microballoons were added
to create a putty-like gap filler. Two concentrations of each
adhesive/solvent pairing – a low one (20%) and a high one
(40%) – were conducted in order to see how the choice
of solvent and concentration would affect the properties
of the filler. The two experiments aimed to evaluate the
amount of shrinkage, shape retention, adhesive strength,
and working properties of each sample. Several general
trends were observed. The 20% concentration samples of
each adhesive shrank less, retained their shape better, and
were easier to work with, but this was counterbalanced by
the loss of adhesive strength. Paraloid B-72 was the only
adhesive that managed to preserve sufficient strength in
low concentrations and was therefore deemed the most
suitable choice for our case. A 20% solution of Paraloid
B-72 in acetone mixed with microballoons was used to
reconstruct the destroyed parts of the fibula and reattach
the glass beads with good results.
ICOM-CC  |  METAL 2022  |  HELSINKI, FINLAND
The ‘Hallmarks on (Dutch) Silver’ Project:
Where Are We Now?
Ellen van Bork* Robert Erdmann
Rijksmuseum Rijksmuseum
Amsterdam, The Netherlands Amsterdam, The Netherlands
e.van.bork@rijksmuseum.nl r.erdmann@rijksmuseum.nl
www.rijksmuseum.nl www.rijksmuseum.nl
The available information regarding (Dutch) hallmarks
on silver is limited to printed books containing short
descriptions or drawings of known marks, an approach
requiring fundamental contextual knowledge from
the user and access to specific publications. To this
end, funding was sought to create an automated image
recognition system, easily accessible to users, that
would provide a comprehensive and efficient solution.
In January 2019, the ‘Hallmarks on Silver’ project was
launched. In its first phase, a ground-truth database
containing 483 hallmarks from the Rijksmuseum collec-
tion was used to realise an automated methodology
for identifying hallmarks from digital photographs. A
convolutional neural network was trained to classify
images from the database and to report the known
identities of those hallmarks. In the inference phase,
new marks were introduced and the network gave an
estimate of the possible identities of the hallmark, along
with estimates of the certainty of those predictions.
The proof-of-concept network had an overall top-1
accuracy exceeding 99%. To make this tool accessible
to the public, a prototype of an online portal, in which
POSTER SESSION  363
Tamar Davidowitz
Rijksmuseum
Amsterdam, The Netherlands
t.davidowitz@rijksmuseum.nl
www.rijksmuseum.nl
*Author for correspondence
users can upload their own images of hallmarks, was
designed. Hallmarks found on those objects can then be
linked to known hallmarks, including their metadata,
thus aiding in the attribution and dating of silver works
of art. The aims of the second phase of the project,
launched on 1 November 2021, are: to complete the
photography of all hallmarks in the Rijksmuseum’s
collection and to simultaneously characterise the
objects’ alloy composition by gathering X-ray fluores-
cence (XRF) data (acquired in situ with a handheld
XRF analyser, Olympus Delta). The XRF results will be
entered into the Rijksmuseum’s silver alloy composition
database, thereby placing them in a larger context and
enabling comparative analyses. This phase will result in
complete hallmark and composition datasets, a singular
accomplishment for such a vast collection. Subsequent
phases of the project will focus on the continuation and
initiation of collaborations with other museums and
institutes, in an effort to expand the datasets and link
them to the relevant metadata. The final aim is to make
the online portal, and the ever-expanding information
it contains, available to the public.
364  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND POSTER SESSION

Metallotheek: A Collaborative Exploration of Bronze

Patination

Heleen van Santen* Laura van Santen

Museumssenteret i Hordaland
Salhus, Norway
heleen.vansanten@muho.no
www.muho.no
Royal Academy of Art, The Hague
The Hague, The Netherlands
iafd.coordinator@kabk.nl
www.kabk.nl
*Author for correspondence

The concept of ‘patina’ in metal conservation is essen-
tial but often remains enigmatic, and the line between
corrosion and patina can be difficult to discern. Pati-
nation as a finishing technique can be more concretely
defined as a practice involving recipes and techniques
to attain a coloured and textured corrosion product on
metal. Practical experience with patination can therefore
offer insights into the wider concept of patina, allowing
for clearer definition of the term and a better reading
of patinas on objects. The many variables affecting
patina formation prevent an exact documentation of
the patination technique. The conservator’s instinct
to work systematically and repeatably interferes with
an organic approach to learning the craft. Under-
standing patination and how the technique is applied
requires the technical expertise of foundry workers,
craftspeople and artists. Equally important is under-
standing their priorities, decision-making processes and
ways of working. The Metallotheek project sought to
combine the expertise of a designer, a foundry worker
and a metals conservator to expand their knowledge
of patination. This symbiosis brought together the
designer’s eye for aesthetics and focus on applicability
and design communication; the foundry worker’s prac-
tical approach to problem-solving, material knowledge
and experience; and the metals conservator’s chemical
knowledge of metals and corrosion, and experience
with setting-up and documenting experiments. The
work parameters, i.e. choice of patination recipes and
patination techniques, were decided as a team. This
resulted in 81 sample patinas and a wealth of experience.
To communicate this visually interesting experiment to
future makers and the public, a permanent exhibition
of the project was built at the art foundry and a digital
publication created, calling attention to the fascinating
overlap between materials research and art in the hope
of inspiring others to build on the research. As a metals
conservator, the project provided practical knowledge
about a finishing technique that is essential to the field,
allowing an eye for patinas to be cultivated and a clearer
vocabulary for discussing them. This knowledge has
improved the authors’ understanding of the objects
they work with and has informed their conservation
practice. For more information about this project, please
visit the following website: www.makeeindhoven.nl/
knowledgebase/metal/metallotheek/

Author index
A de Bruyn-Ouboter, V.  . . . . . . . . . . . . 331
Abed-Esfahani, A.  . . . . . . . . . . . . . . . . 352
Abu-Baker, A.N.  .. . . . . . . . . . . . . . . . . . 221
Aliyari, A  . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
Amarger, A.  . . . . . . . . . . . . . . . . . . . . . . . . . 328
Andersen, L.B.  . . . . . . . . . . . . . . . . 16, 338
Anusha Kasthuri, K.A.  . . . . . . . . . . 290
Argyropoulos, V.  . . . . . . . . . . . . . . . . . . 339
Arponen, A.  . . . . . . . . . . . . . . . . . . . . . . . . 324
Arslaner, L.  . . . . . . . . . . . . . . . . . . . . . . . . . . 358
B Echerd, J.  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Bahadori, S.  . . . . . . . . . . . . . . . . . . . . . . . . . 231
Bakhshandehfard, H.R.  . . . . . . . . . 352
Balbo, A.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
Beck, L.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
Berlewen, K.  . . . . . . . . . . . . . . . . . . . . . . . . 326
Bernardi, E.  . . . . . . . . . . . . . 78, 327, 334
Beyth, I.L.  . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
Bonora Andujar, I.  . . . . . . . . . . . . . . . . 328
Bordalo, R.  . . . . . . . . . . . . . . . . . . . . . . . . . . 337
Borin, M.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
Bottaini, C.  . . . . . . . . . . . . . . . . . . . . . . . . . . 337
Brambilla, L.  . . . . . . . . . . . 160, 168, 329
Branche, B.  . . . . . . . . . . . . . . . . . . . . . . . . . . 328
Brechbühl, S.  . . . . . . . . . . . . . . . . . . . . . . . 330
Brunet, M.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
C Frydendahl, J.  . . . . . . . . . . . . . . . . . 16, 338
Cagnini, A.  . . . . . . . . . . . . . . . . . . . . . . . . . . 248
Camarneiro, N.  . . . . . . . . . . . . . . . . . . . . 337
Campos, B.  . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Cano, E.  . . . . . . . . . . . . . . . . . 153, 332, 351
Canosa, E.  . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
Cardoso, M.  .. . . . . . . . . . . . . . . . . . . . . . . . 333
Carré, C.  . . . . . . . . . . . . . . . . . . . . . . . . 16, 338
Carvalho, C.  . . . . . . . . . . . . . . . . . . . . . . . . 109
Chalançon, B.  . . . . . . . . . . . . . . . . . 87, 329
Cheel, V.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
Chiavari, C.  . . . . . . . . . . . . . 78, 327, 334
Chow, M.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
Contreras Vargas, J.  .. . . . . . . . . . . . . . 146
Costantini, F.  . . . . . . . . . . . . . . . . . . . . . . . 334
Crette, S.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
Cuvillier, L.  .. . . . . . . . . . . . . . . . . . . . . . . . . . 25
D H
Davidowitz, T.  .. . . . . . . . . . . . . . . . . . . . . 363
ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND  365
Degrigny, C.  . . . . . . . . . . . . 87, 160, 248
del Hoyo-Meléndez, J.  . . . . . . . . . . . 345
Delano, M.  . . . . . . . . . . . . . . . . . . . . . . . . . . 308
Demmelbauer, M.  .. . . . . . . . . . . . . . . . 359
Deshayes, C.  . . . . . . . . . . . . . . . . . . . . . . . . . 78
Dillmann, P.  .. . . . . . . . . . . . . . . . . . . 16, 338
Duarte, M.  .. . . . . . . . . . . . . . . . . . . . . . . . . . 337
Dupuy, V.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
E J
Echinard, J.  . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
Eggert, G.  . . . . . . . . . . . . . . . . . . . . . 194, 335
Emmerson, N.J.  . . . . . . . . 94, 203, 240
Erbe, A.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
Erdmann, R.  . . . . . . . . . . . . . . . . . . . . . . . . 363
F Kaipanen, K.  . . . . . . . . . . . . . . . . . . . . . . . . 324
Fair, L.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340
Fajfar, P.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
Farrell, E.  . . . . . . . . . . . . . . . 114, 281, 334
Fernando, A.  .. . . . . . . . . . . . . . . . . . . . . . . 290
Figueiredo, C.  . . . . . . . . . . . . . . . . . . . . . . 337
Fišer, J.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
Florescu, M.  .. . . . . . . . . . . . . . . . . . . . . . . . 176
Fragoso, S.  . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
G Kwiatkowska, J.  . . . . . . . . . . . . . . . . . . . . 350
Ganesan, S.  . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
García Abajo, Á.E.  . . . . . . . . . . . . . . . . 146
García-Ochoa, E.M.  . . . . . . . . . . . . . . 355
Giannoulaki, M.  . . . . . . . . . . . . . . . . . . . 339
Golfomitsou, S.  . . . . . . . . . . . . . . . . . . . . 176
Gonçalves, M.  . . . . . . . . . . . . . . . . . . . . . . . 50
Goryl, M.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
Grahek, L.  . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
Granget, E.  . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
Grayburn, R.  .. . . . . . . . . . . . . . . . . . . . . . . 340
Grima, M.  . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
Guilminot, E.  . . . . . . . . . . . . . 25, 78, 342
Gustad, E.F.  . . . . . . . . . . . . . . . . . . . . . . . . . 331
Gänsicke, S.  . . . . . . . . . . . . . . . . . . . . . . . . . 272
Haines, L.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
Han, K.-S. (Tracy)  . . . . . . . . . . . . . . . . 343
Harsányi, I.  . . . . . . . . . . . . . . . . . . . . . . . . . . 203
Heinzel, M.  .. . . . . . . . . . . . . . . . . . . . . . . . . 184
Hermerén, K.  . . . . . . . . . . . . . . . . . . . . . . . 176
Hoffman, W.  . . . . . . . . . . . . . . . . . . . . . . . . 281
Hokoi, S.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Horelick, L.  .. . . . . . . . . . . . . . . . . . . . . . . . . . 56
Hudson, R.  . . . . . . . . . . . . . . . . . . . . . . . . . . 326
Hyppönen, A.  . . . . . . . . . . . . . . . . . . . . . . 324
James, S.  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Johnson, S.  . . . . . . . . . . . . . . . . . . . . . . . . . . 261
Joseph, E.  . . . . . . . . . . . . . . . . . . 25, 35, 168
Josse, C.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
Jouet, J.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
K
Kasztovszky, Z.  .. . . . . . . . . . . . . . . . . . . . 203
Kemper, D.  . . . . . . . . . . . . . . . . . . . . . . . . . . 184
Khalil, L.A.  . . . . . . . . . . . . . . . . . . . . . . . . . . 221
Kilpeläinen, P.  . . . . . . . . . . . . . . . . . . . . . . 324
King, L.  . . . . . . . . . . . . . . . . . . . . . . . . 281, 344
Kis, Z.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
Kluge, E.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
Kohdzuma, Y.  . . . . . . . . . . . . . . . . . . . . . . . 40
Krupska, P.  . . . . . . . . . . . . . . . . . . . . . . . . . . 345
Kuhn-Wawrzinek, C.F.  . . . . . . . . . . 194
L
Labroche, S.  . . . . . . . . . . . . . . . . . . . . . . . . . 342
Labut, M.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
Lambert, E.  .. . . . . . . . . . . . . . . . . . . . . . . . . 346
Lang, R.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
Lankester, P.  .. . . . . . . . . . . . . . . . . . . . . . . . 261
Lazar, T.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
Le Goïc, G.  . . . . . . . . . . . . . . . . . . . . . . . . . . 160
Leal, J.  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
Leroux, M.  . . . . . . . . . . . . . . . . . . . . . . . . . . 346
Letardi, P.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
Lewinsky, J.  . . . . . . . . . . . . . . . . . . . . . . . . . 308
Lewis, M.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
Lira Pacheco, D.  . . . . . . . . . . . . . . . . . . . 146
Llop I Bayo, F.  . . . . . . . . . . . . . . . . . . . . . . 146
Llop Álvaro, F.  .. . . . . . . . . . . . . . . . . . . . . 146
366  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
M Ricotta, N.  . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
MacLeod, I.D.  . . . . . . . . . . . . . . . . . . . . . . . 71
Magaña Nieto, F.  . . . . . . . . . . . . . . . . . . 146
Mansouri, A.  . . . . . . . . . . . . . . . . . . . . . . . 160
Martini, C.  . . . . . . . . . . . . . . 78, 327, 334
Matthiesen, H.  . . . . . . . . . . . . . . . . 16, 338
McArthur, G.  . . . . . . . . . . . . . . . . . . . . . . . 348
McGath, M.K.  . . . . . . . . . . . . . . . 114, 281
Meehan, P.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
Meier, J.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
Menart, E.  . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
Messager, C.  . . . . . . . . . . . . . . . . . . . . . . . . 325
Mischler, S.  . . . . . . . . . . . . . . . . . . . . . . . . . . 329
Mistewicz, A.  . . . . . . . . . . . . . . . . . . . . . . . 350
Molina, M.T.  . . . . . . . . . . . 153, 332, 351
Molineri, A.  . . . . . . . . . . . . . . . . . . . . . . . . . 328
Monachon, M.  . . . . . . . . . . . . . . . . . . . . . . 35
Monari, G.  .. . . . . . . . . . . . . . . . . . . . . . . . . . 347
Monticelli, C.  . . . . . . . . . . . . . . . . . . . . . . . . 78
Moreira, P.R.  . . . . . . . . . . . . . . . . . . . 50, 109
Mortazavi, M.  . . . . . . . . . . . . . . . . . . . . . . 352
N Silva, N.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
Neff, D.  . . . . . . . . . . . . . . . . . . . . . . . . . . 16, 338
Nemeček, N.  . . . . . . . . . . . . . . . . . . . . . . . . 353
Nečemer, M.  . . . . . . . . . . . . . . . . . . . . . . . . 353
Northover, P.  .. . . . . . . . . . . . . . . . 212, 354
Nurit, M.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
Nygårds, E.  . . . . . . . . . . . . . . . . . . . . . . . . . . 176
O Sully, D.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
Obarzanowski, M.  . . . . . . . . . . . . . . . . 345
Ogura, D.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Ortíz-Corona, J.  . . . . . . . . . . . . . . . . . . . 355
Ottenwelter, E.  . . . . . . . . . . . . . . . . . . . . . 356
Oudbashi, O.  . . . . . . . . . . . . . . . . . . . . . . . 231
P Thomas, J.-B.  . . . . . . . . . . . . . . . . . . . . . . . 168
Panagiotopoulou, C.  . . . . . . . . . . . . . 339
Passaretti, A.  . . . . . . . . . . . . . . . . . . . . . . . . . 25
Pelé-Meziani, C.  . . . . . . . . . . . . . . . . . . . 342
Pereira, M.J.  . . . . . . . . . . . . . . . . . . . . . . . . . 357
Pienimäki, A.  . . . . . . . . . . . . . . . . . . . . . . . 317
Poli, T.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
Pullano, M.  .. . . . . . . . . . . . . . . . . . . . . . . . . 176
R van Bork, E.  . . . . . . . . . . . . . . . . . . . . . . . . . 363
Raimon, A.  . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Raja, S.  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
Ramírez Barat, B.  .. . . . 153, 332, 351
Rathore, S.  . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
Velino, C.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
Rivera, J.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358 Vieira, E.  . . . . . . . . . . . . . . . . . 50, 109, 337
Robbiola, L.  . . . . . . . . . . . . . . . . . . . . 78, 356 Vyhlídal, T.  . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
Roche, K.  . . . . . . . . . . . . . . . . . . . . . 240, 358
Roda-Buch, A.  . . . . . . . . . . . . . . . . . . . . . 329 W
Rodrigues, A.P.   .. . . . . . . . . . . . . . . . . . . 357 Wakiya, S.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Rodriguez, A.E.  . . . . . . . . . . . . . . . . . . . . . 65 Watkinson, D.  . . . . . . . . . . 94, 203, 240
Rodríguez-Gómez, F.J.  . . . . . . . . . . 355 Wentland, E.  . . . . . . . . . . . . . . . . . . . . . . . . 123
Ruckmal Athukorala, D.  . . . . . . . . 290 Wiinblad, T.  .. . . . . . . . . . . . . . . . . . . 16, 338
Russo, S.  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168 Wilcox, K.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
S X
Samide, M.J.  . . . . . . . . . . . . . . . . . . . . . . . . 335 Xie, H.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Sangouard, E.  .. . . . . . . . . . . . . . . . . . . . . . 281
Scalarone, D.M.  .. . . . . . . . . . . . . . . . . . . 359 Y
Scarrone, C.  . . . . . . . . . . . . . . . . . . . . . . . . . 359 Yanagida, A.  . . . . . . . . . . . . . . . . . . . . . . . . . 40
Schillinger, B.  . . . . . . . . . . . . . . . . . . . . . . . 184 Yasui, H.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Schleid, T.  . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
Seifert, J.H.  . . . . . . . . . . . . . . . . . . . . . . . . . . 240 Z
Seri, H.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308 Žužek, B.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
Siatou, A.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
Silva, I.  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
Silva, R.  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
Singh, V.  .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
Šmit, Z.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
Smith, G.D.  . . . . . . . . . . . . . . . . . . . . . . . . . 335
Stefańczyk, K.  . . . . . . . . . . . . . . . . . . . . . . 345
Stieghorst, C.  . . . . . . . . . . . . . . . . . . . . . . . 184
Stępień, A.  . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
Sweeney, M.  .. . . . . . . . . . . . . . . . . . . 56, 360
T
Takatori, N.  . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Tauber, J.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
Thickett, D.  . . . . . . . . . . . . . . . . . . 253, 261
Thunberg, J.C.  . . . . . . . . . . . . . . 203, 240
Timoncini, A.  . . . . . . . . . . . . . . . . . . . . . . 334
Tréhu, E.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
Tsvetkov, S.  . . . . . . . . . . . . . . . . . . . . . . . . . . 362
Tzimopoulou, S.  . . . . . . . . . . . . . . . . . . . 339
Tóth, E.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
V
van Santen, H.  .. . . . . . . . . . . . . . . . . . . . . 364
van Santen, L.  . . . . . . . . . . . . . . . . . . . . . . 364
Varallo, F.  . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
Vassura, I.  . . . . . . . . . . . . . . . . . . . . . . . . . . . 327

Keyword index
A chalcocite.. . . . . . . . . . . . . . . . . . . . . . . . . . . 194
adsorptive inhibitors.. . . . . . . . . . . . 123
aerobic. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
aerospace. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
aircraft heritage.. . . . . . . . . . . . . . . . . . . . . 78
air quality monitoring. . . . . . . . . . . 176
akaganeite. . . . . . . . . . . . . . . . . . . . . . . . . . . 240
Al cladding. . . . . . . . . . . . . . . . . . . . . . . . . . . 78
alloy identification. . . . . . . . . . . . . . . . . 87
aluminium alloys. . . . . . . . . . . . . . . . . . . 78
aluminum. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
anaerobic. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
analysis.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
anilite. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
antioxidant.. . . . . . . . . . . . . . . . . . . . . . . . . . . 50
archaeological.. . . . . . . . . . . . . . . . . . . . . 240
archaeological copper alloys.. . 231
archaeological iron. . . . . . . . . . 16, 317
archaeology. . . . . . . . . . . . . . . . . . . . . . . . . . . 35
armor. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
artificial coupon.. . . . . . . . . . . . . . . . . . 248
atmospheric corrosion. . . . . . . . . . . . 40
automaton.. . . . . . . . . . . . . . . . . . . . . . . . . . 272
B industrial heritage. . . . . . . . . . . . . . . . 123
baghtar. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
bell frames. . . . . . . . . . . . . . . . . . . . . . . . . . 146
bells. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
benzotriazole (BTA). . . . . . . . . . . . . 132
biocleaning. . . . . . . . . . . . . . . . . . . . . . . . . . . 25
biomineralization. . . . . . . . . . . . . . . . . . . 35
black spots. . . . . . . . . . . . . . . . . . . . . . . . . . 194
bodhisattva. . . . . . . . . . . . . . . . . . . . . . . . . 290
bronze. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
bronze artifact. . . . . . . . . . . . . . . . . . . . . . . 40
bronze disease. . . . . . . 132, 203, 231
Buddha.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
buried environment.. . . . . . . . . . . . . . . 40
C electrochemical impedance
calcium sulfonate. . . . . . . . . . . . . . . . . 123
capacity building. . . . . . . . . . . . . . . . . . 300
car. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
cast. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
cast iron.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND  367
characterization. . . . . . . . . . . . . . . . . . . 203
chitosan. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
chloride. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
coating. . . . . . . . . . . . . . . . . . . . . . . . 103, 109
color. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
colorimetry. . . . . . . . . . . . . . . . . . . . . . . . . . . 94
condition assessment. . . . . . . . . . . . 160
conservation.. . . . . . . . . . . 71, 203, 308
conservation laboratory. . . . . . . . 281
consolidation.. . . . . . . . . . . . . . . . . . . . . . 114
contemporary art. . . . . . . . . . . . . . . . . 176
conversion coating. . . . . . . . . . . . . . . . . 65
cooling system. . . . . . . . . . . . . . . . . . . . . . . 87
copper alloys. . . . . . . . . . 132, 221, 253
copper phosphates.. . . . . . . . . . . . . . . 221
copper sulfide. . . . . . . . . . . . . . . . . . . . . . 194
corrosion. . . . . 25, 56, 71, 103, 153,
176, 221, 231, 240
corrosion inhibitors. . . . . . . . . . . . . . 132
corrosion monitoring.. . . . . . . . . . . 203
covellite. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
craftswomen.. . . . . . . . . . . . . . . . . . . . . . . 140
D information gathering. . . . . . . . . . . 146
dagger. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
decision-making. . . . . . . . . . . . . . . . . . 203
deferoxamine B.. . . . . . . . . . . . . . . . . . . . . 25
dehumidifier. . . . . . . . . . . . . . . . . . . . . . . 261
desalination.. . . . . . . . . . . . . . . . . . . 16, 317
dewatering fluids. . . . . . . . . . . . . . . . . 123
DiscoveryMat. . . . . . . . . . . . . . . . . . . . . . . . 87
dissolved oxygen. . . . . . . . . . . . . . . . . . 317
documentation. . . . . . . . . . . . . . . . . . . . 146
E
efflorescence. . . . . . . . . . . . . . . . . . . . . . . 194
spectroscopy (EIS). . . . . . . . . . . . . . . 94
elemental sulfur. . . . . . . . . . . . . . . . . . . 194
émail champlevé. . . . . . . . . . . . . . . . . . 184
epidemiology.. . . . . . . . . . . . . . . . . . . . . . 253
etching. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
F
feature maps. . . . . . . . . . . . . . . . . . . . . . . . 160
Fourier transform infrared
(FTIR) spectroscopy. . . . . . . . . . . . 50
freeware analytical tool. . . . . . . . . . . 87
G
gilded silver.. . . . . . . . . . . . . . . . . . . . . . . . 272
gloss.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
graphitized. . . . . . . . . . . . . . . . . . . . . . . . . . 114
green chemistry. . . . . . . . . . . . . . . . . . . . . 25
green conservation. . . . . . . . . . . . . . . . . 35
H
heterogeneous tarnish. . . . . . . . . . . 248
Hildesheim. . . . . . . . . . . . . . . . . . . . . . . . . 184
historiographic metal
collections. . . . . . . . . . . . . . . . . . . . . . . . 308
hydrogels. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
I
image analysis.. . . . . . . . . . . . . . . . . . . . . 153
imaging. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
Indonesia. . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
industrial archaeology.. . . . . . . . . . 281
in situ preservation. . . . . . . . . . . . . . . . . 40
in situ treatment.. . . . . . . . . . . . . . . . . . . . 16
interpretation. . . . . . . . . . . . . . . . . . . . . . 212
inventory. . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
iron. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240, 253
iron artifact. . . . . . . . . . . . . . . . . . . . . . . . . . . 40
iron corrosion.. . . . . . . . . . . . . . . . . . . . . . . 35
iron objects. . . . . . . . . . . . . . . . . . . . . . . . . . . 25
iron-reducing bacteria. . . . . . . . . . . . 16
iron uptake.. . . . . . . . . . . . . . . . . . . . . . . . . . . 35
J
Joachim Fries. . . . . . . . . . . . . . . . . . . . . . 272
Judaica. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
K
karigar.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
keris. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
Khirbet Yajuz.. . . . . . . . . . . . . . . . . . . . . . 221
368  ICOM-CC  |  METAL 2022  | HELSINKI, FINLAND
kris. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
L prompt gamma-ray neutron
L-cysteine. . . . . . . . . . . . . . . . . . . . . . . . . . . 132
lead phosphates. . . . . . . . . . . . . . . . . . . 221
linear sweep voltammetry.. . . . . 248
long-term project. . . . . . . . . . . . . . . . . 281
lubricant. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
M radiography.. . . . . . . . . . . . . . . . . . . . . . . . 290
macrostructure. . . . . . . . . . . . . . . . . . . . 212
magnesium. . . . . . . . . . . . . . . . . . . . . . . . . . . 56
magnesium corrosion. . . . . . . . . . . . . 65
mail makers. . . . . . . . . . . . . . . . . . . . . . . . 140
management.. . . . . . . . . . . . . . . . . . . . . . . 203
marine archaeological
conservation. . . . . . . . . . . . . . . . . . . . . 281
marine archaeology. . . . . . . . . . . . . . 114
metal carboxylates. . . . . . . . . . . . . . . . 168
metal conservation. 123, 168, 300
metallography. . . . . . . . . . . . . . . . . . . . . 212
metal soaps. . . . . . . . . . . . . . . . . . . . . . . . . 168
Mewar. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
microstructure.. . . . . . . . . . . . . 212, 221
(micro-X-ray fluorescence)
μ-XRF.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
modern metal conservation. . . . . 65
monitoring.. . . . . . . . . . . . . . . . . . . . . . . . . 153
monitoring cleaning. . . . . . . . . . . . . 160
museum preservation. . . . . . . . . . . 308
N surveys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
natural conservation. . . . . . . . . . . . . . . 16
neutron imaging. . . . . . . . . . . . . . . . . . 184
nickel silver alloys. . . . . . . . . . . . . . . . . . 71
non-invasive analysis. . . . . . . . . . . . 212
O thickener. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Owatrol oil. . . . . . . . . . . . . . . . . . . . . . . . . . 114
oxidation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
oxygen depletion. . . . . . . . . . . . . . . . . . 253
P
painted metals. . . . . . . . . . . . . . . . . . . . . 168
partial vacuum.. . . . . . . . . . . . . . . . . . . . 317
past treatments. . . . . . . . . . . . . . . . . . . . . . 56
phylacterion. . . . . . . . . . . . . . . . . . . . . . . . 184
Pleco®. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
pollutants.. . . . . . . . . . . . . . . . . . . . . . . . . . . 176
pollution. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261 W
preventive conservation. 153, 231 watchmaker. . . . . . . . . . . . . . . . . . . . . . . . 272
wind-up mechanism. . . . . . . . . . . . . 272
activation imaging (PGAI).. 184 wrought iron. . . . . . . . . . . . . . . . . . . . . . . . . 94
protective coatings. . . . . . . . . . . . 78, 94
public art. . . . . . . . . . . . . . . . . . . . . . . . . . . . 109 X
pull-off testing. . . . . . . . . . . . . . . . . . . . . . . 94 X-ray fluorescence (XRF).. 176, 300
R Z
zinc phosphates. . . . . . . . . . . . . . . . . . . 221
reburial.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
reflectance transformation
imaging (RTI). . . . . . . . . . . . . . . . . . . 160
reliquary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
Renaissance.. . . . . . . . . . . . . . . . . . . . . . . . 272
reverse engineering. . . . . . . . . . . . . . 272
riveted rings. . . . . . . . . . . . . . . . . . . . . . . . 140
S
sampling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
shipwrecks. . . . . . . . . . . . . . . . . . . . . 71, 281
showcases. . . . . . . . . . . . . . . . . . . . . . . . . . . 261
siderophores.. . . . . . . . . . . . . . . . . . . . . . . . . 25
silver alloys. . . . . . . . . . . . . . . . . . . . . . . . . 248
soil corrosion.. . . . . . . . . . . . . . . . . . . . . . . . 40
spionkopite. . . . . . . . . . . . . . . . . . . . . . . . . 194
Sri Lanka. . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
stainless steel. . . . . . . . . . . . . . . . . . . . . . . 109
storage.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
sunflower oil. . . . . . . . . . . . . . . . . . . . . . . . . 50
surface documentation.. . . . . . . . . 160
sustainability. . . . . . . . . . . . . . . . . . . . . . . 109
Sweden. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
T
Tara. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
Thiriyaya. . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
traditional coatings.. . . . . . . . . . . . . . 103
traditional craftsmen. . . . . . . . . . . . 140
training programme. . . . . . . . . . . . . 300
Trinkspiel. . . . . . . . . . . . . . . . . . . . . . . . . . . 272
tumulus. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
U
ultraviolet (UV). . . . . . . . . . . . . . . . . . . . . 50
The Metals Working Group is part of the
International Council of Museums – Committee
for Conservation (ICOM–CC).
ISBN: 978-2-491997-61-8