Micro Raman spectroscopy used for the study of corrosion products on copper alloys: study of the chemical composition of artificial patinas used for restoration purposes

Hayez, Valerie; Costa, Virginia; Guillaume, Joseph; Terryn, Herman; Hubin, Annick

doi:10.1039/b419080g

Cited by 64 publications

(82 citation statements)

References 14 publications

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“…We compared the measurements to the results obtained on reference products present in the database we created specifically to study the atmospheric corrosion of copper alloys. 9,14,16 Raman measurements were repeated at several points on the sample's surface. All patinas showed a homogeneous composition, which meant that the same spectrum was recorded over the entire area, independent of the visual aspect of the measurement point.…”

Section: Artificial Patinasmentioning

confidence: 99%

“…Patina D was prepared with an additional ingredient, sodium chlorate NaClO 3 , in comparison to patinas B and C. To verify whether the bands could be due to patination ingredients having crystallized simply on the sample's surface, their positions were compared with those of copper nitrate and sodium chlorate. 9 Only the bands at 962, 936 and 493 cm 1 could be due to traces of sodium chlorate. The remaining unidentified bands could be due to the formation of noncrystalline products.…”

Section: Artificial Patinasmentioning

confidence: 99%

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Study of copper nitrate‐based patinas

Hayez

Segato

Hubin

et al. 2006

J Raman Spectroscopy

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Artificial patination is mostly based on empirical recipes for which the result is difficult to forecast. Little is known about the final corrosion compound formed on the patinated object. Therefore, different patinas based on copper nitrate -an ingredient recurrent in numerous references -were realized according to traditional recipes. Their characteristics of morphology and molecular composition were studied using various methods such as scanning electron microscopy (SEM)-energy dispersive X-ray analysis (EDX), X-ray diffraction analysis (XRD) and Raman spectroscopy (RS). A better understanding of artificial patinas will not only allow developing appropriate methods of conservation and restoration, but also differentiating between natural and artificial patinas. An example of a patina present on an ancient artifact is discussed and compared with the studied artificial patinas.

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Section: Artificial Patinasmentioning

confidence: 99%

Section: Artificial Patinasmentioning

confidence: 99%

Study of copper nitrate‐based patinas

Hayez

Segato

Hubin

et al. 2006

J Raman Spectroscopy

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“…Frost 24 reported a Raman spectrum of natural nantokite, which is strikingly similar to that of quartz; the spectrum was obtained with a 632.8 nm laser. Hayez et al 25 on the contrary, reported that nantokite has a very bad Raman response and thermally degrades under laser light. We were not able to record a Raman spectrum on synthetic nantokite, neither with 514.5 nor with 632.8 nm laser, because of systematic degradation of the product.…”

Section: Raman Analysismentioning

confidence: 99%

Evidence for the degradation of an alloy pigment on an ancient Italian manuscript

Aceto

Agostino

Boccaleri

et al. 2006

J Raman Spectroscopy

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An unusual metallic pigment was identified on an ancient Italian manuscript containing the Homilies on the Gospels of Gregory the Great, belonging to the Archive and Chapter Library of Vercelli (Italy) and datable to the IX century. Green uncial text and part of decoration on this manuscript were described as 'being of golden fashion' in a book written at the beginning of XX century. Investigations carried out with portable XRF and Raman instruments revealed that the green colouration is actually the result of a marked degradation process that has altered the original composition of the pigment, an alloy of copper, lead and zinc. Probably because of the conditions of storage of the manuscript, the pigment tarnished owing a chemical process that could resemble the infamous 'bronze disease': that is, the conversion of metallic copper into inorganic salts. Measurements were performed both in situ, i.e. directly on the manuscript, and on small fragments of ink collected from the page gutters.

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“…Niektoré tími použili aj doplnkovú techniku na odlíšenie minerálov vytvorených na bronze v rôznych prostrediach [86]. Len málo štúdií uvádza Ramanovú spektroskópiu ako jedinú techniku pre charakterizáciu rôznych koróznych produktov na bronze [21,24,[86][87][88][89][90]. De la Roja et al študoval rozdielne zelené patiny, ktoré boli vytvorené na medi a jej zliatinách pomocou zelených pigmentov, tak zvanej medenky [87].…”

unclassified

“…De la Roja et al študoval rozdielne zelené patiny, ktoré boli vytvorené na medi a jej zliatinách pomocou zelených pigmentov, tak zvanej medenky [87]. Existujú rôzne dáta z Ramanovej spektroskopie chloridov a minerálov medi [88,89] a Ramanove spektrá niektorých bežných fáz skorodovanej medi [90]. Ale je pomerne málo štúdií o Ramanových spektrách týkajúcich sa rôznych patín na medi a jej zliatinách [21,24].…”

unclassified

Copper and copper patina

Rak

Bureš

2017

Koroze a Ochrana Materialu

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konektory), ale použitie v iných oblastiach je možné (napr. dekorácie, sochy). Na nechránenej medi sa veľmi rýchlo objavuje čierna vrstvička kupritu Cu 2 O [1]. V priebehu niekoľkých rokov je tento povlak nahradený charakteristickou zelenomodrou vrstvičkou [2, 3]. Toto sfarbenie na bronze alebo iných kovoch je označované ako "patina" [1]. Medené patiny sú priestorovo heterogénne vrstvy, ktoré obsahujú prázdne priestory a dtiny. Pórovitosť môže byť ľahko dokázaná schopnosťou patiny absorbovať veľké množstvo vody [4]. Zlúčeniny patiny sú vytvárané chemickou reakciou medi so stopovými prvkami z atmosféry najmä síranmi a chloridmi [5]. Medená patina väčšinou pozostáva z dvoch odlišných vrstiev, 5-10 µm vrstvy kontinuálnej vrstvy kupritu (Cu 2 O) chrániacej základný materiál a vrchnej pórovitej vrstvy 5-40 µm tvorenej zásaditým síranom meďnatým nazývaným aj brochantit (Cu 4 SO 4 (OH) 6 ) alebo bázického chloridu meďnatého atakamitu (Cu 2 Cl(OH) 3 ). Brochantit sa vyskytuje bežnejšie ako atakamit keďže ten sa vytvára iba v prímorských oblastiach [4].Rozpúšťanie medi má nasledujúci mechanizmus: [2, 6]. Príprava umelej patiny na medi a jej zliatinách bola študovaná veľmi dlho, v súčasnosti existujú postupy pre jej prípravu [7][8][9]. V dnešnej dobe väčšina chemických analýz takýchto artefaktov, analýza koróznych procesov a kolorimetrické analýzy sa robia kvôli určeniu pravosti a pôvodu bronzovej zliatiny [9][10][11][12][13][14][15]. Medzi techniky používané na charakterizáciu patín patria skenovacia elektrónová mikroskopia (SEM) s energiovo disperznou spektroskopiou (EDS), elektrochemická impedančná spektroskopia (EIS) a infračervená spektroskopia s Fourierovou transformáciou (FTIR) [16, 17]

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Micro Raman spectroscopy used for the study of corrosion products on copper alloys: study of the chemical composition of artificial patinas used for restoration purposes

Cited by 64 publications

References 14 publications

Study of copper nitrate‐based patinas

Study of copper nitrate‐based patinas

Evidence for the degradation of an alloy pigment on an ancient Italian manuscript

Copper and copper patina

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