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Atmospheric corrosion of copper and copper-based alloys in architecture: from native surface oxides to fully developed patinas
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Surface and Corrosion Science.
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Copper and copper-based alloys are commonly used in both ancient and modern architecture. This requires an in-depth fundamental and applied understanding on their atmospheric corrosion behavior at different climatic, environmental and pollutant levels and how these parameters influence e.g. corrosion initiation, patina characteristics, aesthetic appearances, corrosion rates, and runoff rates. This doctoral thesis elucidates the role of native surface oxides on the corrosion performance, corrosion initiation, formation and evolution of corrosion products from hours to months, years and even centuries, to diffuse dispersion of metals from Cu metal/Cu alloy surfaces focusing on the roles of alloying elements, microstructure, and deposition of chlorides. In-depth investigations have been performed at both laboratory and field conditions on commercial Cu metal and copper-based alloys of a golden alloy (Cu5Zn5Al1Sn) and Sn-bronzes (Cu4Sn, Cu6Sn). Patina characteristics and relations to the presence of microstructural inclusions have in addition been investigated for historic patinas of Cu metal roofing of different age and origin, highlighted with data for a 400 years old Cu patina exposed at urban conditions.

A multi-analytical approach comprising microscopic, spectroscopic and electrochemical methods was employed for in-depth investigations of surface characteristics and bulk properties. Electron backscattered diffraction (EBSD) was utilized to characterize the microstructure. Auger electron spectroscopy (scanning-AES), X-ray photoelectron spectroscopy (XPS), glow discharge optical emission spectroscopy (GDOES) were employed for surface chemical compositional analysis, and atomic absorption spectroscopy (AAS) to assess the amount of metal release from the patinas. Cathodic reduction (CR) and electrochemical impedance spectroscopy (EIS) were used to assess the amount and corrosion resistance of corrosion products formed at laboratory conditions. Confocal Raman micro-spectroscopy (CRM), infrared reflection absorption spectroscopy (IRAS) and grazing incidence X-ray diffraction (GIXRD) were used to identify the phases of corrosion products. Colorimetry was used to assess surface appearances.

Cu5Zn5Al1Sn and Cu4Sn/Cu6Sn exhibit favorable bulk properties with respect to corrosion in terms of smaller grain size compared with Cu metal and show non-significant surface compositional variations. The presence of multi-component native oxides predominantly composed of Cu2O enriched with Sn-oxides on Cu4Sn/Cu6Sn, and with ZnO, SnO2 and Al2O3 on Cu5Zn5Al1Sn, improves the barrier properties of the native surface oxides and the overall corrosion resistance of Cu4Sn/Cu6Sn and Cu5Zn5Al1Sn. The formation of Zn/Al/Sn-containing corrosion products (e.g. Zn5(CO3)2(OH)6 and Zn6Al2(OH)16CO3·4H2O) significantly reduces the corrosion rate of Cu5Zn5Al1Sn in chloride-rich environments. Alloying with Sn reduces the corrosion rate of Sn-bronze at urban environments of low chloride levels but results in enhanced corrosion rates at chloride-rich marine conditions.

A clear dual-layer structure patina was observed for centuries-old naturally patinated copper metal with an origin from the roof of Queen Anne's Summer Palace in Prague, the Czech Republic. The patina comprises an inner sub-layer of Cu2O and an outer sub-layer of Cu4SO4(OH)6/Cu3SO4(OH)4. Abundant relatively noble inclusions (mainly rosiaite (PbSb2O6)) were observed and incorporated in both the copper matrix and the patina. The largest inclusions of higher nobility than the surrounding material create significant micro-galvanic effects that result in a fragmentized patina and large thickness ratios between the Cu4SO4(OH)6/Cu3SO4(OH)4 and the Cu2O sub-layer, investigated via a statistical analysis of inclusions and patina characteristics of eight different historic urban copper patinas.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2018. , p. 74
Series
TRITA-CBH-FOU ; 2018: 54
National Category
Corrosion Engineering
Research subject
Chemical Engineering
Identifiers
URN: urn:nbn:se:kth:diva-238715ISBN: 978-91-7729-994-3 (print)OAI: oai:DiVA.org:kth-238715DiVA, id: diva2:1261909
Public defence
2018-11-30, F3, Lindstedtsvägen 26, Stockholm, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20181109

Available from: 2018-11-09 Created: 2018-11-08 Last updated: 2018-11-09Bibliographically approved
List of papers
1. The golden alloy Cu-5Zn-5Al-1Sn: A multi-analytical surface characterization
Open this publication in new window or tab >>The golden alloy Cu-5Zn-5Al-1Sn: A multi-analytical surface characterization
2018 (English)In: Corrosion Science, ISSN 0010-938X, E-ISSN 1879-0496, Vol. 131, p. 94-103Article in journal (Refereed) Published
Abstract [en]

The golden alloy Cu-5Zn-5Al-1Sn has found many applications because of its appearance and resistance to tarnishing. The microstructure and multi-component surface oxide of Cu-5Zn-5Al-1Sn have been investigated through a multi-analytical approach. Compared to commercial Cu metal, Cu-5Zn-5Al-1Sn has significantly smaller grains and higher fraction of coherent twin boundaries. The 5-10 nm thick oxide formed after diamond polishing has four identified sub-oxides all contributing to the overall corrosion resistance. Cu2O is mainly located in the outer part, followed by ZnO, SnO2 and Al2O3 closer to the alloy substrate. The latter three possess barrier properties, while Cu2O exhibits a more complex structure.

Place, publisher, year, edition, pages
Elsevier, 2018
Keywords
Copper alloy, Cathodic reduction, GDOES, XPS, Atmospheric corrosion
National Category
Metallurgy and Metallic Materials
Identifiers
urn:nbn:se:kth:diva-223276 (URN)10.1016/j.corsci.2017.11.014 (DOI)000423649800009 ()2-s2.0-85033800421 (Scopus ID)
Note

QC 20180219

Available from: 2018-02-19 Created: 2018-02-19 Last updated: 2018-11-08Bibliographically approved
2. The golden alloy Cu5Zn5Al1Sn: Patina evolution in chloride-containing atmospheres
Open this publication in new window or tab >>The golden alloy Cu5Zn5Al1Sn: Patina evolution in chloride-containing atmospheres
Show others...
2018 (English)In: Corrosion Science, ISSN 0010-938X, E-ISSN 1879-0496, Vol. 133, p. 190-203Article in journal (Refereed) Published
Abstract [en]

The influence of chloride deposition on the formation, evolution and barrier properties of the patina formed on CuSZn5Al1Sn used for architectural cladding is explored via long-term marine field exposures and laboratory investigations. The presence of Cu2O, ZnO, Al2O3 and SnO2 within the inner part of the patina and intercalation of SnO2, Zn-5(CO3)(2)(OH)(6), Zn6Al2(OH)(16)CO3 center dot 4H(2)O, Zn-5(OH)(8)Cl-2 center dot H2O within its outer part, predominantly composed of Cu-2(OH)(3)Cl, significantly reduce the chloride-induced corrosion compared with Cu metal. The intercalation of zinc-rich corrosion products within the patina and not at the top-surface explain their marginal influence on the runoff process that mainly occurs at the outmost surface.

Place, publisher, year, edition, pages
Elsevier, 2018
Keywords
Cu alloy, Atmospheric corrosion, runoff, Patina evolution, corrosion product characterization
National Category
Metallurgy and Metallic Materials
Identifiers
urn:nbn:se:kth:diva-226775 (URN)10.1016/j.corsci.2018.01.027 (DOI)000429764100018 ()2-s2.0-85041138972 (Scopus ID)
Note

QC 20180504

Available from: 2018-05-04 Created: 2018-05-04 Last updated: 2018-11-08Bibliographically approved
3. The role of Sn on the long-term atmospheric corrosion of binary Cu-Sn bronze alloys in architecture
Open this publication in new window or tab >>The role of Sn on the long-term atmospheric corrosion of binary Cu-Sn bronze alloys in architecture
(English)Manuscript (preprint) (Other academic)
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-238725 (URN)
Note

QC 20181109

Available from: 2018-11-09 Created: 2018-11-09 Last updated: 2018-11-09Bibliographically approved
4. Analysis of historic copper patinas. Influence of inclusions on patina uniformity
Open this publication in new window or tab >>Analysis of historic copper patinas. Influence of inclusions on patina uniformity
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2017 (English)In: Materials, ISSN 1996-1944, E-ISSN 1996-1944, Vol. 10, no 3, article id 298Article in journal (Refereed) Published
Abstract [en]

The morphology and elemental composition of cross sections of eight historic copper materials have been explored. The materials were taken from copper roofs installed in different middle and northern European environments from the 16th to the 19th century. All copper substrates contain inclusions of varying size, number and composition, reflecting different copper ores and production methods. The largest inclusions have a size of up to 40 μm, with most inclusions in the size ranging between 2 and 10 μm. The most common element in the inclusions is O, followed by Pb, Sb and As. Minor elements include Ni, Sn and Fe. All historic patinas exhibit quite fragmentized bilayer structures, with a thin inner layer of cuprite (Cu2O) and a thicker outer one consisting mainly of brochantite (Cu4SO4(OH)6). The extent of patina fragmentation seems to depend on the size of the inclusions, rather than on their number and elemental composition. The larger inclusions are electrochemically nobler than the surrounding copper matrix. This creates micro-galvanic effects resulting both in a profound influence on the homogeneity and morphology of historic copper patinas and in a significantly increased ratio of the thicknesses of the brochantite and cuprite layers. The results suggest that copper patinas formed during different centuries exhibit variations in uniformity and corrosion protection ability.

Place, publisher, year, edition, pages
MDPI AG, 2017
Keywords
Antlerite, Atmospheric corrosion, Bilayer, Brochantite, Cuprite, Historic copper, Inclusions, Micro-galvanic effect, Patina, Volta potential, Antimony, Copper corrosion, Corrosion, Lead, Metallic matrix composites, Ores, Substrates, Bi-layer, Galvanic effect, Copper
National Category
Corrosion Engineering
Identifiers
urn:nbn:se:kth:diva-207437 (URN)10.3390/ma10030298 (DOI)000400863500081 ()2-s2.0-85015630454 (Scopus ID)
Note

QC 20170523

Available from: 2017-05-23 Created: 2017-05-23 Last updated: 2018-11-08Bibliographically approved
5. Characterisation of a centuries-old patinated copper roof tile from Queen Anne's Summer Palace in Prague
Open this publication in new window or tab >>Characterisation of a centuries-old patinated copper roof tile from Queen Anne's Summer Palace in Prague
Show others...
2017 (English)In: Materials Characterization, ISSN 1044-5803, E-ISSN 1873-4189, Vol. 133, p. 146-155Article in journal (Refereed) Published
Abstract [en]

This paper presents an in-depth characterisation study of the patina formed on a copper tile taken from the roof of Queen Anne's Summer Palace in Prague after > 300 years of exposure to the action of the atmosphere. A wide variety of techniques have been used, including metallographic and chemical analysis (electrogravimetry, AAS, XRF) of the copper matrix, and spectroscopic and microscopic investigations (GIXRD, FTIR, TEM/EDS and SEM/ EDS) to determine the composition and structure of the patina. The major conclusions of the study are: (a) the base copper contains abundant inclusions mainly of rosiaite (PbSb2O6); (b) the patina is formed by an inner sublayer of cuprite (Cu2O) and an outer sublayer of brochantite [Cu4SO4(OH)(6)] and antlerite [Cu3SO4(OH)(4)] and traces of azurite [Cu-3(CO3)(2)(OH)(2)]; and (c) the brochantite/antlerite crystals are randomly doped with Fe and C.

Place, publisher, year, edition, pages
ELSEVIER SCIENCE INC, 2017
Keywords
Copper tile, Atmospheric corrosion, Characterisation, Patina, Queen Anne's Summer Palace
National Category
Metallurgy and Metallic Materials
Identifiers
urn:nbn:se:kth:diva-217414 (URN)10.1016/j.matchar.2017.09.034 (DOI)000413881500018 ()2-s2.0-85030706571 (Scopus ID)
Note

QC 20171121

Available from: 2017-11-21 Created: 2017-11-21 Last updated: 2018-11-08Bibliographically approved

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