Contributor contact details .................................. xiii
Series introduction ........................................... xix
Volumes in the EFC series ..................................... xxi
Foreword .................................................... xxvii
Preface ...................................................... xxix
1 Examination and conservation of historical and
archaeological metal artefacts: a European overview .......... 1
C. Degrigny, ICOM-CC Metal Working Group, France
1.1 Introduction ............................................ 1
1.2 How scientific examination and archaeometric studies
receive most of the funding ............................. 2
1.3 The necessity for research on conservation of
historical and archaeological artefacts ................. 6
1.4 Training in conservation science: a chance for better
recognition of the discipline? ......................... 10
1.5 Pro-active responsibilities for conservators ........... 11
1.6 Networking ............................................. 12
1.7 Conclusion ............................................. 13
1.8 References ............................................. 13
2 Corrosion behaviour of low-alloy steels: from ancient
past to far future .......................................... 18
G. Santarini, Commissariat à l'Energie Atomique, France
2.1 Introduction ........................................... 18
2.2 Uniform corrosion and localized corrosion .............. 18
2.3 Atmospheric corrosion .................................. 21
2.4 Corrosion in soils ..................................... 23
2.5 Corrosion in cementitious environments ................. 28
2.6 Conclusion ............................................. 28
2.7 Acknowledgements ....................................... 29
2.8 References ............................................. 29
3 Archaeological metal artefacts and conservation issues:
long-term corrosion studies ................................. 31
R. Bertholon, Université Paris 1, Panthéon-Sorbonne,
France
3.1 Introduction ........................................... 31
3.2 The artefact's history and its material condition ...... 31
3.3 The limit of the original surface ...................... 34
3.4 Locating the limit of the original surface ............. 35
3.5 Conclusion ............................................. 39
3.6 References ............................................. 40
4 Contribution of iron archaeological artefacts to the
estimation of average corrosion rates and the long-term
corrosion mechanisms of low-carbon steel buried in soil ..... 41
D. Neff, E. Vega, P. Dillmann and M. Descostes, Commissariat
à l'Energie Atomique, France and L. Bellot-Gurlet, Université
Pierre et Marie Curie Paris, France and G. Béranger,
Université de Technologie de Compiègne, France
4.1 Introduction ........................................... 41
4.2 Literature review ...................................... 42
4.3 Characterisation of corrosion layouts and mechanisms ... 43
4.4 Average corrosion rate estimation ...................... 59
4.5 Conclusion ............................................. 73
4.6 Acknowledgements ....................................... 74
4.7 References ............................................. 74
5 Electrochemical study of steel artefacts from World War I:
Contribution of A.C. impedance spectroscopy and
chronoamperometry to describe the behaviour of the
corrosion layers ............................................ 77
E. Pons, C. Lemaitre and D. David, Université de
Technologie de Compiègne, France and D. Crusset, ANDRA,
France
5.1 Introduction ........................................... 77
5.2 Objective and experimental methods ..................... 77
5.3 Specific electrochemical behaviour depending on the
corrosion layers ....................................... 80
5.4 Advanced electrochemical study of the internal
corrosion layer ........................................ 82
5.5 Conclusion ............................................. 90
5.6 References ............................................. 90
6 Species transport in the corrosion products of ferrous
archaeological analogues: contribution to the modelling
of long-term iron corrosion mechanisms ...................... 92
E. Vega, P. Dillmann and P. Berger, Commissariat
à l'Energie Atomique, France and P. Fluzin, Laboratoire
Métallurgies et Cultures, France
6.1 Introduction ........................................... 92
6.2 Analysed corpus and experimental methods ............... 94
6.3 Results and discussion ................................. 96
6.4 Corrosion rates evaluation ............................ 100
6.5 Conclusion ............................................ 107
6.6 References ............................................ 107
7 Long-term behaviour of iron embedded in concrete: from
the characterisation of archaeological analogues to the
verification of the oxygen reduction as the limiting step
for corrosion rate ......................................... 109
W.-J. Chitty, B. Huet, P. Dillmann and V. L'Hostis,
Commissariat à l'Energie Atomique, France and
G. Béranger, Université de Technologie de Compiègne,
France and H. Idrissi, INSA de Lyon, France
7.1 Introduction .......................................... 109
7.2 Characterisation of long-term corrosion layout of
iron embedded in old binders .......................... 111
7.3 Proposition of a modelling approach for the
corrosion of iron in concrete ......................... 122
7.4 Conclusion ............................................ 128
7.5 Acknowledgements ...................................... 129
7.6 References ............................................ 129
8 Study of the atmospheric corrosion of iron by ageing
historical artefacts and contemporary low-alloy steel in
a climatic chamber: comparison with mechanistic modelling .. 131
L. Maréchal, S. Perrin, P. Dillmann and G. Santarini,
Commissariat à l'Energie Atomique, France
8.1 Introduction .......................................... 131
8.2 Atmospheric corrosion of iron ......................... 132
8.3 Experimental ageing of historical artefacts ........... 139
8.4 Results and discussion ................................ 144
8.5 Conclusion ............................................ 148
8.6 References ............................................ 149
8.7 Appendix: Table of symbols and values ................. 151
9 The corrosion of metallic artefacts in seawater:
descriptive analysis ....................................... 152
J.B. Memet, Laboratoire Arc'Antique, France
9.1 Introduction .......................................... 152
9.2 Brief description of the seawater environment ......... 153
9.3 Corrosion of iron-based artefacts ..................... 156
9.4 Marine corrosion of copper alloys ..................... 164
9.5 Seawater corrosion aspects of lead- and tin-based
'white' metals ........................................ 164
9.6 Knowledge of the degradation state of metallic
artefacts ............................................. 165
9.7 Conclusion ............................................ 167
9.8 References ............................................ 167
10 Contribution of local and structural characterisation for
studies of the corrosion mechanisms related to the
presence of chlorine on archaeological ferrous artefacts ... 170
S. Réguer and P. Dillmann, Commissariat à l'Energie
Atomique, France and F. Mirambet, Laboratoire de
Restauration des Monuments Historiques, France and
J. Susini, European Synchrotron Radiation Facility, France
10.1 Introduction .......................................... 170
10.2 Experimental corpus of archaeological artefacts ....... 172
10.3 Methodology: cross-section characterisation ........... 174
10.4 Results ............................................... 176
10.5 Discussion ............................................ 184
10.6 Conclusion ............................................ 187
10.7 Acknowledgements ...................................... 187
10.8 References ............................................ 188
11 A proposal to describe reactivated corrosion of
archaeological iron objects ................................ 190
M.A. Loeper-Attia, National Institute of Heritage,
France
11.1 Introduction .......................................... 190
11.2 Giving a name to this type of corrosion ............... 191
11.3 Forms of corrosion .................................... 192
11.4 Diagnostics ........................................... 200
11.5 Perspectives .......................................... 200
11.6 References ............................................ 201
12 Simulation of corrosion processes of buried archaeological
bronze artefacts ........................................... 203
E. Angelini, F. Rosalbino and S. Grassini, Politecnico di
Torino, Italy and G.M. Ingo and T. de Caro, Istituto per
lo Studio dei Materiali Nanostrutturati (ISMIN-CNR),
Italy
12.1 Introduction .......................................... 203
12.2 Materials and methods ................................. 205
12.3 Results and discussion ................................ 207
12.4 Conclusions ........................................... 216
12.5 References ............................................ 217
13 Corrosion patina or intentional patina: contribution of
non-destructive analyses to the surface study of copper-
based archaeological objects ............................... 219
F. Mathis, J. Salomon, S. Pagès-Camagna, M. Dubus,
D. Robcis and M. Aucouturier, Centre de Recherche et de
Restauration des Musées de France, France and S. Descamps
and E. Delange, Louvre Museum, France
13.1 Introduction .......................................... 219
13.2 The objects ........................................... 220
13.3 Instrumentations and methods for analyses ............. 222
13.4 Results ............................................... 223
13.5 Discussion ............................................ 232
13.6 Conclusions ........................................... 235
13.7 Acknowledgements ...................................... 236
13.8 References ............................................ 236
14 Tin and copper oxides in corroded archaeological bronzes ... 239
P. Piccardo, Università di Genova, Italy and B. Mille,
Centre de Recherche et de Restauration des Musées de
France, France and L. Robbiola, ENSCP, France
14.1 Introduction .......................................... 239
14.2 Materials and methods ................................. 243
14.3 Characterisation of the internal corrosion layers
containing oxides ..................................... 244
14.4 Discussion: tin oxide, copper oxide and 'type 2'
corrosion ............................................. 254
14.5 Conclusions ........................................... 259
14.6 Acknowledgements ...................................... 260
14.7 References ............................................ 260
15 Corrosion problems and reconstruction of the copper roof
on Queen Anna's Summer Palace, Prague ...................... 263
K. Kreislova, D. Knotkova and V. Cihal, SVUOM Ltd, Czech
Republic and J. Had, VSCHT, Czech Republic
15.1 Introduction .......................................... 263
15.2 Survey of corrosion products and damage to copper
roofs and claddings in Prague ......................... 263
15.3 Corrosion damage on copper roof of Queen Anna's
Summer Palace ......................................... 264
15.4 Reconstruction of the copper roof ..................... 265
15.5 Artificial patinas .................................... 267
15.6 Study of behaviour of artificial patinas in
atmospheric conditions ................................ 268
15.7 Conclusions ........................................... 270
15.8 Acknowledgement ....................................... 270
15.9 References ............................................ 271
16 Long-term corrosion of iron at the waterlogged site of
Nydam in Denmark: studies of environment, archaeological
artefacts and modern analogues ............................. 272
H. Matthiesen, D. Gregory and B. Sørensen, National
Museum of Denmark and L. R. Hilbert, Technical University
of Denmark
16.1 Introduction .......................................... 272
16.2 Study site ............................................ 272
16.3 Methods ............................................... 273
16.4 Results ............................................... 279
16.5 Discussion ............................................ 288
16.6 Conclusions ........................................... 290
16.7 Acknowledgements ...................................... 291
16.8 References ............................................ 291
17 On-line corrosion monitoring of indoor atmospheres ......... 293
L. Sjogren, Corrosion and Metals Research Institute,
Sweden and N. Le Bozec, Institut de la Corrosion, France
17.1 Introduction .......................................... 293
17.2 Experimental .......................................... 293
17.3 Results and discussion ................................ 297
17.4 Conclusions ........................................... 306
17.5 Acknowledgement ....................................... 306
17.6 References ............................................ 306
18 Corrosion inhibitors for metallic artefacts: temporary
protection ................................................. 308
E. Rocca, Université Henri Poincaré, France and
F. Mirambet, Laboratoire de Recherche des Monuments
Historiques, France
18.1 Introduction .......................................... 308
18.2 State of the art inhibitors ........................... 309
18.3 New anti-corrosion formulations: sodium carboxylates .. 314
18.4 Conclusions ........................................... 331
18.5 References ............................................ 333
19 Surface characterisation of corrosion inhibitors on
bronzes for artistic casting ............................... 335
A. Galtayries, A. Mongiatti and P. Marcus, Ecole
Nationale Superieure de Chimie de Paris, France and
C. Chiavari, Università di Ferrara, Italy
19.1 Introduction .......................................... 335
19.2 Experimental .......................................... 336
19.3 Results ............................................... 337
19.4 Discussion ............................................ 346
19.5 Conclusions ........................................... 350
19.6 References ............................................ 350
20 Influence of microstructure and composition on corrosion
of lead-rich organ pipes ................................... 352
C. Chiavari, C. Dinoi, C. Martini, D. Prandstraller,
Università di Bologna, Italy and G. Poli, Università di
Modena, Italy
20.1 Introduction .......................................... 352
20.2 Experimental .......................................... 353
20.3 Results ............................................... 357
20.4 Discussion ............................................ 362
20.5 Conclusions ........................................... 366
20.6 Acknowledgements ...................................... 366
20.7 References ............................................ 366
Index ......................................................... 368
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