Raman investigation of the patina layers on Hungarian copper ingots from a fifteenth century shipwreck

Abstract

We report results of the patina study of underwater archeological finding of medieval copper objects performed by means of the Raman and complementary spectroscopic techniques. The objects were found submerged in the sea as cargo part of the ship which sunk in the Gulf of Gdańsk in 1408. The excavated collection consists of 230 oval ingots of the size and mass up to about 60 cm and 18 kg (total of 2 tons), respectively. In the Raman spectra of the strongly porous ingot encrustation, the bands corresponding to the main patina representatives such as cuprite (Cu2O), atacamite (Cu2(OH)3Cl) and chalcopyrite (CuFeS2), and also chalcocite (Cu2S) and covellite (CuS) are observed and confirmed by the elemental analysis. Raman bands located at 1473 cm−1 and also at 909 and 511 cm−1 are ascribed to the organic Ca‐oxalate (whewellite, CaC2O4 · H2O) in agreement with the infrared spectra and surface morphology observed in microscope images. The presence of S, C, Ca, and Fe revealed by the energy dispersive X‐ray spectroscopy indicate on patina components resulting from reactions in the microbial environment in seawater and on contributions coming from iron bars, tar, and burnt remains which were also found in the excavated cargo. The results are consistent with literature data on copper ingots from Hungary traded along the south–north route in medieval Europe. Copyright © 2016 John Wiley & Sons, Ltd.

Raman spectroscopy characterization of 10‐cash productions from the late Chinese emperors to the Republic

“…Figure compares the Raman spectra of cuprite and tenorite with that of coin Peiyang #01. The spectrum of cuprite shows two main bands at 114 and 220 cm −1 , accompanied by shoulders at 145 and 186 cm −1 , which are in agreement with literature data . Weak, broad bands also appear at 420, 525, and 625 cm −1 .…”

“…Due to its sensitivity and noninvasive character, Raman spectroscopy is being increasingly used in the study of artistic and archaeological objects . In particular, Raman spectroscopy has been used for identifying corrosion products in copper/bronze and other metals and characterizing artistic patinas produced in copper‐base alloys …”

“…[7][8][9][10][11] Due to its sensitivity and noninvasive character, Raman spectroscopy is being increasingly used in the study of artistic and archaeological objects. [12] In particular, Raman spectroscopy has been used for identifying corrosion products in copper/bronze and other metals [13][14][15][16][17][18][19] and characterizing artistic patinas produced in copper-base alloys. [20][21][22][23][24][25] In this report, we describe the use of Raman spectroscopy for discriminating different monetary emissions.…”

Recent advances in linear and non‐linear Raman spectroscopy. Part XI

“…Zmuda‐Trzebiatowska carried out a Raman investigation of the patina layers on Hungarian copper ingots from a 15th century shipwreck. Their results are consistent with literature data on copper ingots from Hungary traded along the south–north route in medieval Europe …”

“…Their results are consistent with literature data on copper ingots from Hungary traded along the south-north route in medieval Europe. [116] 14.2 | Frescos, mortars, paintings including wall and rock paintings, plates, plasters, and textiles Badillo-Sanchez and Baumann compared palette characterization of oil-on-canvas paintings of two well-known 19th-century Colombian artists by confocal Raman spectroscopy. Common pigments, such as vermillion, carbon black, Prussian blue, lead white, as well noncommon pigment as siderite (used as yellow by Espinosa), were clearly identified.…”