Uncommon corrosion phenomena of archaeological bronze alloys

In the framework of the EFESTUS project (funded by the European Commission, contract No. ICA3-CT-2002-10030) the corrosion products of a large number of archaeological bronze artefacts are investigated by means of the combined use of scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), X-ray diffraction (XRD) and optical microscopy (OM) and tentative correlation of their nature with the chemical composition of the artefacts and the burial context is proposed.The results provide good insight into the corrosion layers and evidence in some bronze Roman coins and artefacts; the occurrence of uncommon corrosion phenomena that give rise to the formation of a yellowish-green complex chlorine-phosphate of lead (pyromorphite, (PbCl)Pb₄(PO₄)₃) and of a gold-like thick layer of an iron and copper sulphide (chalcopyrite, CuFeS₂). The micro-chemical and micro-structural results show that the coins were buried in a soil enriched in phosphorus for the accidental presence of a large amount of decomposing fragments of bones or in an anaerobic and humus rich soil where the chalcopyrite layer has been produced via the interaction between the iron of the soil, the copper of the coin and the sulphur produced by the decomposition of organic matter in an almost oxygen free environment. Finally, some unusual periodic corrosion phenomena occurring in high tin bronze mirrors found at Zama (Tunisia) are described. PACS 68.55Jk; 68.35 Dv; 68.37Hk; 68.55 Nq; 81.05 Bx     

Study of tin amalgam mirrors by 119Sn Mössbauer spectroscopy and other analytical methods

From the beginning of the 16 ^th until the end of the 19 ^th century the most widely used mirrors consisted of a pane of glass backed with a reflecting layer of tin-mercury amalgam. They were made by sliding the glass pane over a tin foil covered with liquid mercury. After removal of the superfluous mercury, tin amalgam formed slowly at ambient temperature and yielded a reflecting layer adhering to the surface of the glass. Such mirrors often deteriorate in the course of time by oxidation of the tin in the amalgam to stannous or stannic oxide. ¹¹⁹Sn Mössbauer spectroscopy, scanning electron microscopy, micro-XRF and X-ray diffraction have been used to study this deterioration process. The studied specimens were a modern mirror made for the reconstruction of the Green Vault in Dresden in the early 2000s, two rather well preserved German mirrors from the 17 ^th and 19 ^th centuries and several strongly deteriorated specimens of Baroque mirrors from the south of Spain. The modern mirror consists mainly of a Sn_0.9Hg_0.1 amalgam with only 2 % of SnO₂. The older German mirrors showed more pronounced oxidation, containing 12 and 15 % of SnO₂, which did not noticeably impair their reflectivity. In the samples from the Spanish mirrors at best a few percent of metallic phase was left. The majority of the tin had oxidised to SnO₂, but between 8 and 20 % of the tin was present as SnO. X-ray diffraction yielded similar results and micro-XRF mapping using synchrotron radiation for excitation gave information on the distribution of Sn and Hg in the reflecting layer of the mirrors.     

Complementary use of X‐ray methods to study ancient production remains and metals from Northern Portugal

Archaeological artefacts recovered at Castanheiro do Vento (Northern Portugal) were characterised by integrating macro and micro‐energy dispersive X‐ray fluorescence spectrometry (EDXRF) and scanning electron microscopy with X‐ray microanalysis. The collection includes metallurgical remains (ceramic crucibles, a metallic nodule and a vitrified fragment) and metals (tools and ornaments) whose chronology spans from the Chalcolithic to the Roman Age. The study of production remains was able to identify distinct copper‐based metallurgical operations including the smelting of copper ores, the melting of copper and tin and/or the melting of bronze scrap. Micro‐EDXRF identified copper and arsenical copper tools as well as bronze and leaded bronze ornaments. The composition of tools (Cu with varying As contents: 0.46–3.6%) reveals an incipient technology, typical of the Chalcolithic till the Middle Bronze Age. On the contrary, ornaments are composed by different alloys – low tin bronze (4.8% Sn), high tin bronze (14.9% Sn) and high tin‐leaded bronze (16.5% Sn and 2.4% Pb) ? evidencing technological and economic choices that clearly indicate a late period such as the Roman Age. In conclusion, this multiproxy approach was able to study those ancient artefacts with a minimum impact on their archaeological and museological significance while providing important answers to the interpretation of the archaeological settlement and to better understand the metallurgical evolution in the Portuguese territory. Copyright © 2014 John Wiley & Sons, Ltd.     

New insight into the nature and properties of pale green surfaces of outdoor bronze monuments

The present study concerns the chemical–physical and electrochemical characterisations of the pale green surfaces formed on outdoor bronzes exposed in urban conditions. In the first part, results from investigations performed on the equestrian statue of the French king Louis XIV exposed in the Palace of Versailles (France) are given. Analyses by energy-dispersive spectrometry and Raman spectroscopy, coupled with scanning electron microscopy, show that the external layer is characterised by a marked selective dissolution of copper and zinc of the alloy leading to an important relative enrichment in tin compounds. The same phenomenon with the same magnitude, determined from dissolution factors f_Cu and f_Zn, has also been evidenced on other bronze monuments used for comparison. Proportionality between the amount of dissolved copper and zinc cations to their respective initial content in the alloy is evidenced independently of the tin content. The pale green patina appears to be a complex mixture of copper and tin compounds whose structure still needs to be more precisely characterised. In the second part, the electrochemical reactivity of tin compound enriched patina was investigated by cyclic voltammetry from a Cu10Sn electrode in sulfate solution at pH=2 and 5.6. This patina is stable at pH 5.6 but reactive at pH 2 in relation to the modification of properties of tin species in the patina. Mott–Schottky application in pH 5.6 solution revealed that the bronze patina exhibits two types of semiconducting properties according to the potential domains, similar to what has been observed for pure tin in aqueous solutions. The destabilisation of bronze patinas in outdoor conditions and consequently the cyclic erosion due to rainfall have been attributed to the modification of tin species properties rather than to the transformation of copper compounds. PACS  07.78.+s; 81.05.-t; 81.15.-z; 81.65.Kn     

Synthesis and characterization of superhydrophobic functionalized Cu(OH)2 nanotube arrays on copper foil

Superhydrophobic functionalized cupric hydroxide (Cu(OH)₂) nanotube arrays were prepared on copper foils via a facile alkali assistant surface oxidation technique. Thus nanotube arrays of Cu(OH)₂ were directly fabricated on the surface of copper foil by immersing in an aqueous solution of NaOH and (NH₄)₂S₂O₈. The wettability of the surface was changed from surperhydrophilicity to superhydrophobicity by chemical modification with 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FAS). The morphologies, microstructures, crystal structure, chemical compositions and states, and hydrophobicity of the films on the copper foil substrates were analyzed by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and water contact angle measurement. It was found that the rough structure of the surface helped to magnify the wettability. The static contact angle (CA) for water is larger than 160° and the contact angle hysteresis (CAH) is lower than 5° on the modified surface. The high roughness of the nanotube arrays along with the generated C-F chains by chemical modification contributed to the improved superhydrophobicity. The present research is expected to be significant in providing a new strategy for the preparation of novel multifunctional materials with potential industrial applications on copper substrates.     

Nano-scale copper oxidation on leadframe surface

Copper oxidation studies were carried out by means of field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and electron energy loss spectroscopy (EELS) techniques. The growth of copper oxide occurs as a copper surface comes in an oxygen containing environment. The reaction sequence leading to oxidation of the copper surface is generally accepted to be oxygen chemisorption, nucleation and growth of the surface oxide and bulk oxide growth. HRTEM examination of the cross section of the oxidized copper sample revealed the interface region in between the copper and copper oxide. At high oxidation temperature, formation of micro-voids and separations were observed along this interface region. Poor adhesion at this interface region due to micro-voids and separation were found to be the root cause of delamination issue. EELS analysis determined that for regions with intact interface the oxidation system is Cu/CuO/Cu₂O/CuO, however, in regions containing micro-voids or separation it is found to be Cu/Cu₂O/CuO.     

Investigation in the interface roughness of DC-sputtered Mo/B4C multilayer mirrors with variable layer pairs for 7-nm soft X-ray polarizers

The surface and interface roughness of Mo/B₄C multilayer mirrors for 7-nm soft X-ray polarizer with variable layer pairs (N = 50, 70, 90 and 110), fabricated by DC sputtering technique is investigated by atomic force microscopy and X-ray scattering and reflecting. The experimental results present that the surface and interface roughness of Mo/B₄C multilayer mirrors increase layer by layer from its substrate as its Mo layer thickness greater than 2 nm, and the roughness grown tendency could be characterized by a quadratic function.     

Substrate dependent properties of electrodeposited EuTe thin films

In electrodeposition, substrate besides providing mechanical support to the electrodeposit, affects significantly the structural and morphological properties of a film. Electrodeposition and characterization of EuTe thin films onto different substrates such as stainless steel (SS), titanium (Ti), copper (Cu), fluorine-doped tin oxide (F:SnO₂) covered glasses have been described. The deposition potentials have been estimated from the polarization curves. The reaction mechanism is proposed for the formation of EuTe electrodeposits. Preparative parameters such as deposition potential, current density, and deposition time are studied. The films have been characterized by X-ray diffraction, scanning electron microscopy (SEM), atomic force microscopy (AFM) and energy dispersive analysis by X-rays (EDAX) techniques. The electrodeposited EuTe films are polycrystalline on all the substrates with same cubic crystal structure. The SEM studies reveal that the surface morphology is different for the substrates studied. However, no cracks have been observed in the SEM micrographs. The AFM images show large spherical grains supporting the polycrystalline nature of the samples. The EDAX analysis shows that the EuTe films are nearly stoichiometric, slightly rich in tellurium.     

Formation of copper islands on a native SiO2 surface at elevated temperatures

A combination of in situ X-ray photoelectron spectroscopy analysis and ex situ scanning electron- and atomic force microscopy has been used to study the formation of copper islands upon Cu deposition at elevated temperatures as a basis for the guided growth of copper islands. Two different temperature regions have been found: (I) up to 250 °C only close packed islands are formed due to low diffusion length of copper atoms on the surface. The SiO₂ film acts as a barrier protecting the silicon substrate from diffusion of Cu atoms from oxide surface. (II) The deposition at temperatures above 300 °C leads to the formation of separate islands which are (primarily at higher temperatures) crystalline. At these temperatures, copper atoms diffuse through the SiO₂ layer. However, they are not entirely dissolved in the bulk but a fraction of them forms a Cu rich layer in the vicinity of SiO₂/Si interface. The high copper concentration in this layer lowers the concentration gradient between the surface and the substrate and, consequently, inhibits the diffusion of Cu atoms into the substrate. Hence, the Cu islands remain on the surface even at temperatures as high as 450 °C.     

Characterisation of baroque tin amalgam mirrors of the historical Green Vault in Dresden

The historical Green Vault, one of Europe’s most sumptuous treasure chambers, has reopened in September 2006 in the Dresden Royal Palace. For the baroque presentation of the artworks the special properties of tin amalgam mirrors are of great importance. A comprehensive analytic characterisation was necessary for restoration and reconstruction. The different original casting glasses were analysed in respect of chemical composition, roughness, waviness and optical properties like chromaticity coordinates and transmittance. The microstructure of the tin amalgam layers were investigated on metallographic cross-sections and by X-ray diffraction. The investigations reveal that the tin amalgam layers are composed of γ-HgSn_6-10 phase with a grain size between 5 and 50 μm surrounded by a thin mercury phase with about 2 wt. % tin. However the most important property of the baroque tin amalgam mirrors is a relative low reflectivity of about 59% which is drastically lower than for silver mirrors with a reflectivity of about 96%. According to the characterisation results a suitable glass for reconstruction was selected. The mirror layers were produced by historical tin amalgam technology for the rooms not destroyed by bombarding of Dresden in February 1945. For the completely destroyed Jewel Room pure tin layers were deposited by magnetron sputtering. The results show that this new technology enables an adequate substitute for the original tin amalgam layers. PACS  61.66.-f; 74.25.Gz; 61.10.Nz; 68.37.Hk     

Combined use of surface and micro-analytical techniques for the study of ancient coins

By means of the combined use of surface and micro-analytical techniques the surface chemical composition of ancient coins and some aspects of their manufacturing techniques and of degradation mechanisms have been elucidated. Two case histories are described concerning silver Roman Republican coins and some coins plated with thin films of silver and gold. In particular, the coinage methods, the silvering and gilding techniques and the origin of the embrittlement of these selected Roman coins have been studied by means of the combined use of selected-area X-ray photoelectron spectroscopy (SA-XPS) and scanning electron microscopy and energy-dispersive spectrometry (SEM+EDS). This innovative approach has been utilised in order to gain further insight into the microchemical structure of the external regions of the coins as well as of the bulk features. The results show the use of mercury to coat a copper or silver core with a thin film of precious metals that could be considered the most important advance in the technology of gilding to be made in antiquity. Furthermore, the microchemical investigation of brittle Roman silver coins has allowed us to identify the origin of this troublesome problem. The microchemical results indicate that brittleness is induced by the presence of a low amount of lead that is retained in supersaturated solution when the cast blank was produced. This latter element segregates at the grain boundaries during the coin production and the subsequent long-term ageing at room temperature, thus inducing the alloy fracturing along the weakened grain boundaries. PACS 68.55.Jk; 68.35.Dv; 68.37.Hk; 68.55.Nq; 81.05.Bx     

Electrochemical performance of Sn-Sb-Cu film anodes prepared by layer-by-layer electrodeposition

A novel layer-by-layer electrodeposition and heat-treatment approach was attempted to obtain Sn-Sb-Cu film anode for lithium ion batteries. The preparation of Sn-Sb-Cu anodes started with galvanostatic electrochemically depositing antimony and tin sequentially on the substrate of copper foil collector. Sn-Sb and Cu-Sb alloys were formed when heated. The SEM analysis showed that the crystalline grains become bigger and the surface of the Sn-Sb-Cu anode becomes more denser after annealing. The energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) analysis showed the antimony, tin and copper were alloyed to form SnSb and Cu₂Sb after heat treatment. The X-ray photoelectron spectroscopy (XPS) analysis showed the surface of the Sn-Sb-Cu electrode was covered by a thin oxide layer. Electrochemical measurements showed that the annealed Sn-Sb-Cu anode has high reversible capacity and good capacity retention. It exhibited a reversible capacity of about 962 mAh/g in the initial cycle, which still remained 715 mAh/g after 30 cycles.     

On-line Surface Area Measurement of Concentrated Slurries using low field spin-lattice relaxation NMR

A method for the rapid on-line determination of surface area and solids content in flowing concentrated slurries using low field NMR spin-lattice relaxation measurements has been developed and demonstrated. The relationship between flow and spin-lattice relaxation time (T₁) of protons in water at 20 MHz was examined using aqueous copper sulfate solutions. The ability to measure surface area and solids concentration in both stagnant (stopped flow) and flowing systems via NMR was demonstrated using several different concentrated aqueous titania and glass slurries (20 to 80 weight percent) for which the dried powder surface area was previously determined via nitrogen adsorption/BET analysis and the solids content determined gravimetrically. Surface areas were also calculated from particle size analysis and found to vary by up to an order of magnitude from the adsorption and NMR results.     

Structure and photocatalytic properties of copper-doped rutile TiO2 prepared by a low-temperature process

Copper-doped titania with variable Cu/Ti ratios have been prepared via a simple aqueous-phase method at 85 °C. The obtained products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and UV-vis absorption spectra analysis. The photocatalytic properties of the products were tested by photocatalytic degradation of aqueous brilliant red X-3B solution. The results showed that the sample with 2% copper doping has the best photocatalytic activity, which is 3 times that of undoped rutile titania. The effect of the doped copper on the structure and property of TiO₂ has also been discussed.     

BaSnF4 fast ion conductor: Variations versus the method of preparation and anomalous temperature variation of the quadrupole splitting

A new method of preparation of high performance fluoride ion conductor, BaSnF₄, by water leaching of newly discovered barium tin(II) chloride fluorides, has been designed, and the materials have been studied and compared to the solid prepared by the usual dry method. The unit-cell parameters and crystallite dimensions were found to vary with the method of preparation. In addition, the crystallite dimensions were found to be highly anisotropic for the samples obtained by the wet method. The Mössbauer spectrum is made of a large tin(II) quadrupole doublet, and a broad tin(IV) oxide peak due to surface oxidation. The tin(II) spectrum is in agreement with covalently bonded tin(II) having a strongly stereoactive lone pair. An unusually high dependence of the quadrupole splitting at low temperatures was observed (5.8 times larger than for α-SnF₂).     

Selective laser processing of ink-jet printed nano-scaled tin-clad copper particles

The deposition of tin-clad nano-size copper particles was carried out by means of ink-jet printing. Curing the particles on Polyimide (PI) turned them into soldered structures using an Nd-YAG laser. Area coverage of 55% was achieved for a single-layer print. Subsequent laser sintering increased this value to 95%. A Butanol-based copper ink and an aqueous tin (Sn)-clad Copper (Cu) ink were produced and were ink-jetted in this work. These nano-metallic inks showed excellent suspension stability with particle weight concentrations as high as 5%. The ink components were examined by measuring the particle size distribution in a dispersed condition, and the melting temperature. A piezo ink-jet print head was used to deposit the inks onto a moveable substrate. The thermal effect of the laser irradiation allowed approaching and connecting adjacent particles by melting the particle’s tin coating. The results were examined with regard to structure and soldering properties using EDX, SEM and optical microscopy.     

Microchemical investigation of Greek and Roman silver and gold plated coins: coating techniques and corrosion mechanisms

Within the framework of a project financially supported by the European Commission (contract Nr. 509126, acronym PROMET) the metallurgical techniques used by Romans and Greeks for coating the copper core of coins with a thin or thick layer of gold or silver are studied by means of the combined use of scanning electron microscopy combined with energy dispersive spectrometry (SEM-EDS) and optical microscopy (OM) techniques.This approach is utilised to gain further insight into the micro-chemical structure of the external regions of the coins as well as into the bulk metallurgical features. The results indicate that several methods were used by the Greek and Roman craftsmen including the mechanical application of a thin malleable gold or silver foils to be welded via thermal treatment. The analytical approach is also used for investigating the corrosion products grown on the coins during the long-term burial and for identifying degradation mechanisms.PACS 68.55Jk; 68.35 Dv; 68.37Hk; 68.55 Nq; 81.05 Bx     

Sensing low concentrations of CO using flame-spray-made Pt/SnO2 nanoparticles

Tin dioxide nanoparticles of different sizes and platinum doping contents were synthesized in one step using the flame spray pyrolysis (FSP) technique. The particles were used to fabricate semiconducting gas sensors for low level CO detection, i.e. with a CO gas concentration as low as 5 ppm in the absence and presence of water. Post treatment of the SnO₂ nanoparticles was not needed enabling the investigation of the metal oxide particle size effect. Gas sensors based on tin dioxide with a primary particle size of 10 nm showed signals one order of magnitude higher than the ones corresponding to the primary particle size of 330 nm. In situ platinum functionalization of the SnO₂ during FSP synthesis resulted in higher sensor responses for the 0.2 wt% Pt-content than for the 2.0 wt% Pt. The effect is mainly attributed to catalytic consumption of CO and to the associated reduced sensor response. Pure and functionalized tin dioxide nanoparticles have been characterized by Brunauer, Emmett and Teller (BET) surface area determination, X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM) and scanning transmission electron microscopy (STEM) while the platinum oxidation state and dispersion have been investigated by X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS). The sensors showed high stability (up to 20 days) and are suitable for low level CO detection: <10 ppm according to European and 50 ppm according to US legislation, respectively.     

Large-scale synthesis of rutile SnO2 nanorods

A high yield of tin oxide (SnO₂) nanorods was obtained via annealing a nanoscale precursor in the molten salt flux and surfactant. X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, selected area electron diffraction and infrared spectroscopy showed that the nanorods are composed of SnO₂ with rutile structure. The surfactant and temperature have a profound influence on the production of SnO₂ nanorods.     

Production of amorphous tin oxide thin films and microstructural transformation induced by heat treatment

X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and high resolution transmission electron microscopy were used to study tin oxide thin films deposited on Si(100) substrates at room temperature using pulsed laser deposition techniques with a sintered cassiterite SnO₂ target and subsequently heat-treated. X-ray diffraction and scanning electron microscopy results demonstrated that the as-prepared thin films consisted of an amorphous matrix as well as plume-like features, which are shown many micropores. The thin films that were heat treated for 2 h at 150 °C had tetragonal rutile nanocrystalline SnO₂ structures. The microstructural evolution of the tin oxide thin films during the heat treatment is discussed in the paper. PACS 81.15.Fg; 73.61Jc; 81.05.Gc; 81.40.Ef