Corrosion of metallic heritage artefacts : investigation, conservation and prediction of long term behaviour

415 Pages·8.038 MB·xxx, 378 p. : ill\415

by  P Dillmann, et al

European Federation of Corrosion Publications
NUMBER 48
Corrosion of
metallic heritage
artefacts
Investigation, conservation
and prediction for long-term
behaviour
Edited by
P. Dillmann, G. Béranger, P. Piccardo and
H. Matthiesen
Published for the European Federation of Corrosion
by Woodhead Publishing and Maney Publishing
on behalf of
The Institute of Materials, Minerals & Mining
CRC Press
Boca Raton Boston New York Washington, DC
W
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Contents
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
vi Contents
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
Contents vii
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
viii Contents
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
Contents ix
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
x Contents
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. SJÖGREN, 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
Contents xi
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 Supérieure 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
Preface
For several decades, researches have been performed on heritage artefacts (both
archaeological and historical) in order to determine the ancient smelting
processes and methods of thermomechanical manufacture from the ore to the
final object. Moreover, these approaches have provided much information on
corrosion mechanisms over long periods. The results are also interesting in the
field of conservation of heritage artefacts. The main aim of such studies is on
the one hand to set up efficient conservation treatments but also, on the other
hand, to give tools to the restorers to retrieve information concerning the
corroded artefacts, such as the ancient shape, linked to the original surface. In
parallel, in many European countries and especially in France, the need to
predict in a reliable way the corrosion mechanisms of metallic materials that
will be used for several hundred years, and even several thousand years in
specific contexts such as the storage of nuclear wastes, requires the study of
archaeological artefacts considered as analogues. For this reason, the nuclear
industry, and especially Working Party 4 of the EFC, have encouraged these
studies to provide new and significant findings concerning the corrosion of
complex systems in which the thick layers of corrosion products play an
important role. Indeed, studies on archaeological analogues submitted to
corrosive environments in soils, water, atmospheres, binders and concretes
during multi-secular periods are the only way to control the exact role of very
long time periods in corrosion kinetics. This kind of approach needs great care
in comparing the new materials and their corroding environment with those of
the chosen analogues. This needs knowledge of corrosion science and various
parallel disciplines such as electrochemistry, characterisation techniques, soil
science, archaeological science, metallurgy, etc. Thus, for several years, with
the help of joint programmes related to this very interdisciplinary field, some
new and interesting results have been available for both conserving heritage
artefacts and predicting material degradation in the future.
This book is based on papers presented at Eurocorr’2004 during the
‘Corrosion of Heritage Artefacts’ workshop and the common session with the
2nd workshop on ‘Prediction of Long Term Corrosion Behaviour in Nuclear
Waste Systems’. It includes also other papers and reviews from specialists in