Micro‐Raman innovative methodology to identify Ag–Cu mixed sulphides as tarnishing corrosion products

Mixed Cu–Ag alloys with different compositions have been produced and subjected to an accelerated sulphidation process which causes the development of a mixed sulphide‐rich corroded film on their surface. It was called tarnishing, that is, the formation of a blue‐brownish patina when Cu–Ag alloys are exposed in a sulfur‐containing atmosphere. The structures of the pristine alloys have been determined by the combined analytical techniques as scanning electron microscopy energy dispersive X‐ray microanalysis and X‐ray diffraction. The experimental conclusions confirmed the occurrence of micro phase separation with the formation of different dendritic domains of about 10 µm in width. The sulphidized samples were firstly investigated by optical microscopy and X‐ray diffraction in order to verify the homogeneity of the patina and to identify the different AgCuS phases appearing on the alloy surfaces. It was observed that, despite the inherent micro‐heterogeneity of the alloys, the sulphide layer was throughout uniform in composition at the micro‐scale. The complex scenario of the relative stability of all the various mixed sulphides involved was then explored by micro‐Raman spectroscopy (μ‐RS), pointing out that the Cu‐for‐Ag substitution in the crystal lattice of the mixed Ag–Cu sulphides caused a monotonous blue shift of the vibrational wavenumbers in Raman spectra. This study has unveiled microscopic details of the tarnishing process, furnishing an innovative, cheap and non‐destructive methodology based on μ‐Raman spectroscopy for the evaluation of the silver‐copper artefacts via the compositions of their corroded products. Copyright © 2016 John Wiley & Sons, Ltd.     

Interaction of a piezoelectric ceramic based on lead-zirconium-titanium solid solution with different solders

Thermodynamic estimation of the interaction of a piezoelectric ceramic based on the lead-zirconium-titanium (PZT) solid solution with lead, tin, copper, silver, palladium, and their alloys has been performed. The results of thermodynamic calculations have been experimentally verified by estimating the adhesion and capillary properties of solders on a PZT piezoelectric ceramic.     

High‐Strength Pressure‐Free Bonding Using Cu and Ni‐Sn Nanoparticles

High‐strength pressure‐free bonding is investigated using Cu nanoparticles as an alternative to conventional solders. Focus is placed on the morphology of Ni‐Sn intermetallic nanoparticles, an additive to a paste of Cu nanoparticles, for improvement of sinterability. The shear strength increases from 23.2 (Cu nanoparticles only) to 31.8 MPa, when 10 wt% of the newly synthesized 15‐nm Ni₃Sn₂ nanocubes is mixed with the Cu nanoparticle paste. This is the first example of the use of base metal nanoparticles under pressure‐free conditions to achieve the bonding strength of an ordinary Pb‐free solder (Sn‐Ag‐Cu). The addition of smaller Ni₃Sn₂ nanocubes 8 nm in size or irregularly shaped Ni₃Sn₂ nanoparticles (25.0 MPa) results in a limited increase in shear strength (26.6 MPa), while the addition of micrometer‐sized Ni₃Sn₂ particles results in a decrease in shear strength (21.5 MPa). The effects of the size and shape of the added Ni₃Sn₂ particles on the shear strength are discussed based on SEM observation of the sintered layers.     

Thickness and composition of gold and silver alloys determined by combining EDXRF‐analysis and transmission measurements

Energy‐dispersive X‐ray fluorescence (EDXRF)‐analysis is a technique which in the case of metals analyzes thin surface layers. For example, when gold and silver alloys are analyzed, it typically interests a depth of microns up to a maximum of tens of microns. Therefore, it can give wrong results or be affected by a large indetermination when the sample composition is altered because of surface processes, as often happens when silver alloys are oxidated, and sometimes in the case of gold alloys rich on copper or silver. A complementary technique was therefore developed, of bulk analysis, which uses the same equipment employed for EDXRF‐analysis; the X‐ray beam from the X‐ray tube is monochromatized by means of a tin secondary target, which K lines bracket the silver‐K discontinuity. The sample to be analyzed is positioned between the secondary target and the detector. This technique is able to determine (by measuring the attenuation of tin‐K rays) thickness and/or composition of gold and silver alloys having a thickness of less than about 120 µm for gold and about 0.7 mm for silver. The method was tested with Au–Ag–Cu alloys of known composition and thickness and then applied to gold and silver artifacts from the tomb of the Lady of Cao, which belongs to the Moche pre‐hispanic culture from the North of Peru, and dates about 300 A.D. Copyright © 2014 John Wiley & Sons, Ltd.     

Micro‐EDXRF investigation of Chalcolithic gold ornaments from Portuguese Estremadura

Chalcolithic gold artefacts assigned to the Bell Beaker Culture in Portuguese Estremadura were analysed by micro‐energy dispersive X‐ray fluorescence spectrometry. These high‐status jewels comprise beads of tubular, spiral and double‐conical type, a spiral ring and a wire fragment. The collection is mainly composed of gold with 8.7–16.3 wt% Ag and <0.04 wt% Cu. Additionally, there is a typologically uncommon double‐conical bead showing a lower Ag content (6.7 wt%). The relative intensity of the Ag‐Kα and Ag‐Lα X‐rays from artefacts established the existence of a surface layer depleted in silver, while the reasonable effective penetration depth of the Ag‐Kα (about 25–30 μm) provided suitable results for such high fineness gold alloys. A uniform Au–Ag composition at the joint indicates that the double‐conical bead was made by joining two sheets without solder. Overall, the collection shows a composition that is similar to known Chalcolithic gold in Portuguese Estremadura but different from coeval gold in Southwestern Iberian Peninsula. The distinct compositional pattern of Chalcolithic gold in Portuguese Estremadura seems to be inconsistent with the natural variability of silver content in alluvial deposits of gold in Iberian Peninsula, thus suggesting a continuous use of particular sources and limited exchange of nuggets and jewels with the neighbouring region. Copyright © 2017 John Wiley & Sons, Ltd.     

Ag–Cu/Pmma Nanocomposites Produced By Modification of PMMA with Bimetallic EEW-Nanoparticles

Russian Physics Journal - Using the method of electrical explosion of copper and silver wires in an argon atmosphere, Cu–94Ag, Cu–65Ag, and Cu–22Ag bimetallic nanoparticles are...     

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In ITER Feeder system, the superconducting joints and the current leads should use solder to weld. In this paper, Bi-2223/Ag iswelded with different kinds of solders, and the weld procedure and the measuring device are introduced in this paper. The electrical property of the superconducting joint under liquid nitrogen was also measured and the result showed that Bi50Sn9Pb31, In99.99 and high melting point solder Sn96.5Ag3Cu0.5 have a lower resistance under liquid nitrogen, and satisfy the requirement for temperature gradient. This can make a reference for the solder measurement and choice of ITER Feeder system.     

Molecular dynamics study of interfaces in solids

The interfaces of heterostructures were studied in the framework of molecular dynamics to reveal a periodic interface stress distribution on the micro scale. The calculations were performed for copper and silver and for two different types of heterostructures: a heterostructure consisting of perfect Cu and Ag crystals and a heterostructure formed by Ag vapor deposition on a perfect Cu substrate. The calculation results allowed several conclusions about the origin of a chessboard interface structure and about certain mechanisms of its modification depending on the nanostructure size, boundary conditions, and method of heterostructure formation.     

Formation of nanoislands in the course of copper deposition on a Cu(111)-(9 × 9)-Ag surface

The process of copper deposition on a structured Cu(111)-(9 × 9)-Ag surface, which represents a (9 × 9) loop dislocation network, is studied by scanning tunneling microscopy. It is found that, when the substrate temperature is 100 K and the copper coverage is 0.1–0.4 of a monolayer, islands of a size no greater than 50 Å are formed at the Ag/Cu(111) interface. The islands remain stable as the sample is heated to room temperature. The shape and boundaries of the nanoislands follow the initial surface superstructure and are determined by the nonuniformity of the interaction of the upper silver layer with the copper substrate. The mechanism of island formation and the origin of their stability are explained in terms of the atom exchange between the adsorbate and substrate.     

Synthesis of tin oxides SnO2–x in the entire composition range (x = 0 to 1) by ion‐beam sputter‐deposition

Ion‐beam sputter‐deposition (IBSD) was used to reactively deposit tin oxide crystalline films at oxygen fluxes of 3–15 sccm and at substrate temperatures of 100–600 °C. Analysing the samples by X‐ray diffraction and Raman spectro‐ scopy yields a map of the crystalline structures in dependence on the growth parameters. In addition to SnO₂, pure SnO films of high quality and an intermediate phase such as Sn₂O₃ or Sn₃O₄ can be reproducibly obtained. Thus, IBSD is, to our knowledge, the only thin‐film deposition technique verified yet to reliably produce samples in the entire composition range of tin oxides. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

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.     

Sono and electrochemical synthesis and characterization of copper core–silver shell nanoparticles

Cu–Ag core–shell nanopowders have been prepared by ultrasound-assisted electrochemistry followed by a displacement reaction. The composition of the particles has been determined by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX). The XRD patterns versus time displacement show that higher are the silver peaks intensities, weaker are the copper ones. That exhibits the progressive recovering of copper by silver. EDX results and quartz crystal microbalance results indicate that various reaction mechanisms are implied in this process. Transmission electron microscopy (TEM) points out variable nanometric diameter grain and some small agglomerates. Elemental mapping obtained by electron energy-loss spectroscopy (EELS) underlines the core–shell structure.     

Sn3.0Ag0.5Cu倒装焊点中的电迁移

采用10⁴ A/cm²数量级的电流密度对Sn30Ag05Cu倒装焊点中的电迁移机理作了研究.电迁移引起的原子（或空位）的迁移以及在此过程中形成的焦耳热,使Sn30Ag05Cu倒装焊点的显微形貌发生变化.电迁移作用下,由于空位的定向迁移和局部的电流聚集效应使阴极芯片端焊料与金属间化合物界面形成薄层状空洞.处于阴极的Cu焊盘的Ni（P）镀层与焊料间也产生了连续性空洞,但空洞面积明显小于处于阴极的芯片端焊料与金属间化合物界面.焊盘中的Cu原子在电迁移作用下形成与电子流方向一致的通量,最终导致焊点高电流密度区域出现连续性的金属间化合物且金属间化合物量由阴极向阳极逐渐增多. 关键词： Sn30Ag05Cu 倒装 焊点 电迁移     

Raman investigations of TiO2 nanotube substrates covered with thin Ag or Cu deposits

A tubular array of TiO₂ nanotubes on Ti matrix was used as a support for Ag or Cu sputter‐deposited layers intended for surface‐enhanced Raman scattering (SERS) investigations. The composite samples of Ag/TiO₂–nanotube/Ti and Cu/TiO₂–nanotube/Ti were studied with the aid of scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) [and scanning Auger microscopy (SAM)] to reveal their characteristic morphological and chemical features. Raman spectra of pyridine (as a probe molecule) were measured after it had been adsorbed on the TiO₂–nanotube/Ti substrates covered with thin Ag or Cu deposit as well as on the bulk electrochemically roughened Ag or Cu reference substrates. It was found that the SERS spectra measured for pyridine adsorbed on the bulk silver substrate were significantly different than the spectra measured on the TiO₂–nanotube/Ti substrates covered the Ag layer. The spectra measured for pyridine adsorbed on the Ag/TiO₂–nanotube/Ti suggest that on the surface of such a composite substrate there are many Lewis acidic sites. Spectra typical for pyridine adsorbed on acidic sites were observed even after deposition of a relatively thick silver layer (e.g. an Ag layer with an average thickness of 80 nm) on the TiO₂–nanotube/Ti support. Our findings suggest that TiO₂–nanotube/Ti support is a promising substrate for the preparation of metallic nano‐clusters on a support containing acidic active sites. Copyright © 2009 John Wiley & Sons, Ltd.     

A study of the microstructure,thermal properties and wetting kinetics of Sn–3Ag–<Emphasis Type="Italic">x</Emphasis>Zn lead-free solders

Microstructure, thermal properties and wetting kinetics of Sn–3Ag–xZn solders (x = 0.4, 0.6, 0.8, 1, 2 and 4 wt%) were systematically investigated. The results indicate that a small amount of Zn (Zn wt% ≤ 1 wt%) has a rather moderate effect on the microstructure morphology of the Sn–3Ag–xZn solders. The microstructures are composed of a β-Sn phase and the mixture of Ag₃Sn and ζ-AgZn particles. However, the β-Sn phase reduces its volume fraction in the entire microstructure and the intermetallic compounds population increases with the increasing of Zn content. The microstructure is dramatically changed with a further increase in the Zn content. The γ-AgZn phase is formed in a Sn–3Ag–2Zn solder. The ε-AgZn phase is formed in a Sn–3Ag–4Zn solder. The melting temperature and the undercooling of the Sn–3Ag–xZn solder alloys decrease with the increase in Zn content, reach to a minimum value when the content of Zn is 1 wt%, and then increase with further increase in Zn content. The Sn–3Ag–1Zn demonstrates the minimum value of 228.13 °C in the melting temperature and 13.87 °C in undercooling. The wetting kinetics of the main spreading stage features the power law of R ⁿ  ~ t (n = 1), which is controlled by chemical reactions at the triple line.     

Interaction of silver atoms with iridium and with a two-dimensional graphite film on iridium: Adsorption,desorption, and dissolution

The initial stages in the interaction of silver with the (111)Ir surface and with a two-dimensional graphite film (2D GF) on (111)Ir were studied by high-resolution electron Auger spectroscopy in ultrahigh vacuum. The growth mechanisms of silver films and the desorption fluxes of Ag atoms were determined, and their desorption energies estimated. It was found that the Ag desorption fluxes from a 2D GF on Ir and from a thick silver film on the pure metal are similar and considerably (an order of magnitude) smaller than the sublimation fluxes from bulk silver at the same temperatures. The activation energy for desorption from a submonolayer film varies from 3.2 eV for coverage θ=1 to 3.7 eV at θ ～ 0. It was shown that silver atoms do not penetrate into the substrate bulk throughout the temperature range covered (300–1800 K).     

Inclusions and metal composition of ancient copper‐based artefacts: a diachronic view by micro‐EDXRF and SEM‐EDS

A diachronic view of the metallurgy in the Portuguese territory during the first three millennia after its appearance in the Iberian Peninsula is presented based on the current state of the art. Results of micro‐energy dispersive X‐ray fluorescence (micro‐EDXRF) analyses made on metal artefacts to determine their composition and scanning electron microscopy with energy dispersive analysis (SEM‐EDS) analyses to study microstructural features as inclusions are shown to illustrate trends and specificities of each chronological period. Generally, in early periods, namely during the Copper Age and first stages of the Bronze Age, unalloyed copper and arsenical copper were at use, and only by the Late Bronze Age (LBA) did tin bronze substitute almost completely the previous role of copper. In the Early Iron Age, during the Orientalising period, a general decrease in the average tin content in bronzes seems to happen. Regarding the inclusions observed in the metal matrix, these seem to suffer a diversification with the appearance of tin bronzes. By the Copper Age, only Cu? O and Cu? As? O inclusions are observed, while by the LBA Cu? S inclusions become regular, besides others less frequent, as Sn? O, Cu? S? Fe and Pb globules. Overall, with the present analytical study, the complementary character of micro‐EDXRF and SEM‐EDS in the study of ancient metals is demonstrated, providing a first general overview of the ancient metallurgy at the Portuguese territory which is of key importance to specific investigations of the future. Copyright © 2011 John Wiley & Sons, Ltd.     

Cerium oxide nanoparticles protect primary mouse bone marrow stromal cells from apoptosis induced by oxidative stress

The sintering of a silver (Ag) nanoparticle film by laser beam irradiation was studied using a CW DPSS laser. The laser sintering of the Ag nanoparticle thin film gave a transparent conductive film with a thickness of ca. 10 nm, whereas a thin film sintered by conventional heat treatment using an electronic furnace was an insulator because of the formation of isolated silver grains during the slow heating process. The laser sintering of the Ag nanoparticle thin film gave a unique conductive network structure due to the rapid heating and quenching process caused by laser beam scanning. The influences of the laser sintering conditions such as laser scan speed on the conductivity and the transparency were studied. With the increase of scan speed from 0.50 to 5.00 mm/s, the surface resistivity remarkably decreased from 4.45 × 10⁸ to 6.30 Ω/sq. The addition of copper (Cu) nanoparticles to silver thin film was also studied to improve the homogeneity of the film and the conductivity due to the interaction between the oxidized surface of Cu nanoparticle and a glass substrate. By adding 5 wt% Cu nanoparticles to the Ag thin film, the surface resistivity improved to 2.40 Ω/sq.