Archaeo-metallurgical studies of tuyeres and smelting slags found at Tharros (north-western Sardinia, Italy)

A large number of pyrometallurgical materials such as tuyeres, slags and refractory tools likely associated with metal extraction processes have been found at Tharros (north-western Sardinia, Italy) during archaeological excavations stratigraphically related to the Phoenician–Punic period (VI–III centuries BC). Micro-chemical, micro-structural and mineralogical studies have been carried out by means of the combined use of X-ray diffraction (XRD), selected-area X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) combined with energy-dispersive X-ray analysis (EDS) in order to identify pyrometallurgical processes and main relevant technological parameters. The results reveal that tuyeres, slags and refractory tools can be associated with an iron ore smelting process to extract the metal by slagging the unwanted by-products. Moreover, temperature and duration of the smelting process have been estimated through mineralogical studies and by a comparative analysis between the micro-chemical and structural features of thermally treated refractory materials and tuyeres. The results disclose the high level of technological competence of the ancient metallurgists able to carry out complex high-temperature processes to extract iron from ores by separating the metal from unwanted siliceous species.     

Phase analytical studies of industrial copper smelting slags. Part I: Silicate slags

The pyrometallurgical extraction of copper from sulfide ore concentrates is determined by the behaviour of the associated iron during smelting. Hence, ⁵⁷Fe Mössbauer spectroscopy is an attractive tool for studying the phases in silicate slags from German and Chilean smelting plants. Other methods used were ore microscopy, electron microprobe analysis, and X-ray powder diffraction.     

铜陵、南陵地区古铜矿冶遗址炉渣的科技研究

安徽铜陵、南陵地区铜矿资源丰富，古代矿冶遗址数量众多，最早可追溯至二里头文化时期。各遗址遍地分布的炉渣、炉壁等矿冶遗物，为研究中国早期的铜矿冶炼技术提供了大量的实物资料。本工作采用X射线衍射分析（XRD）、X射线荧光分析（XRF）和扫描电镜能谱分析（SEM-EDS）等多种技术手段，对安徽铜陵、南陵地区古铜矿冶遗址的炉渣样品进行检测分析，以了解该地区早期的铜矿冶炼技术。XRD分析结果显示，所检测炉渣样品的物相以铁橄榄石、辉石、钙铁辉石为主，伴有石英、方石英、磁铁矿等矿物，符合炼铜渣的物相特征。根据炉渣的SiO₂，CaO和Fe₂O₃的含量，可将51个炉渣样品分为三大类：Ⅰ类炉渣、Ⅱ类炉渣和Ⅲ类炉渣。其中，Ⅰ类炉渣钙、硅、铁含量较高，其CaO含量远高于Ⅱ类和Ⅲ类炉渣，为铁硅钙系。相较而言，Ⅱ类炉渣为高铁系，其Fe₂O₃含量明显高于Ⅰ类和Ⅲ类炉渣；Ⅲ类炉渣为高硅系，其SiO₂含量较高，钙、铁含量较低。所有炉渣样品的铁含量均高于普通熔炼渣，结合其物相分析结果，可推测全部炉渣为冶炼渣。Ⅰ类、Ⅱ类炉渣的Ca和Fe含量呈现很强的负相关性，且波动范围很大，显示二者的含量并非人工调控，更可能是来自矿石中的天然成分。据此可以推测，本地区的早期工匠可能尚未认识到含钙和含铁助熔剂的作用，没有掌握不同类型铜矿石的配矿技术。SEM-EDS的分析结果表明，炉渣中的金属颗粒夹杂以冰铜、红铜和砷铜为主，表明该地区同时存在红铜和砷铜的冶炼活动。不同品位的冰铜颗粒大多来自不同遗址，尚没有在同一遗址发现较多品位依次升高的冰铜颗粒，因而难以确认冰铜熔炼环节的存在，不能证明上述遗址是否已采用了“硫化铜矿-冰铜-铜”的冶炼技术。所发现的冰铜颗粒，可能是采用硫化铜矿死焙烧工艺或混合矿原料冶炼的结果。铜陵夏家墩遗址炉渣中砷铜颗粒的存在，表明该地区早至西周时期，很可能已掌握了采用共熔还原法冶炼砷铜的技术。相关研究结果，对探讨砷铜技术的起源和传播，以及中国早期冶金技术的发展和生产组织状况均具有重要意义。     

Mössbauer spectroscopy of metals from birth to death

In today's metallurgy, precision techniques, such as X-ray and electron diffraction, electron microscopy, infrared spectroscopy and electron probe micro-analyzer, are being indispensably used, and, comparing to them, Mössbauer spectroscopy is not inferior at all in usefulness, convenience and cost benefit. Actually, however, it is not yet popular among the metallurgists probably because people believe that the Mössbauer effect is a difficult physics, radioactive sources are difficult to handle, and spectral analyses are complicated. These beliefs are in fact groundless and must be dissolved for further diffusion of this useful Mössbauer technique in metals and other industries. The present introductory talk intends to help people's better understanding and no anxiety for using the Mössbauer spectroscopy by showing how it can be applied to various problems of metals and alloys from their birth to the end, that is, from the study of minerals and ores before smelting to that of corrosion and other failures. Firstly, the principle of Mössbauer spectroscopy will be explained with simplest illustrations together with simple pictures of apparatuses including the high temperature furnace and the high pressure cell. In the second will be shown typical examples of Mössbauer patterns of magnetite, carbon steel and other alloys, with indications of how to analyze the seemingly complicated spectra. Some other examples will be shown with special apparatuses easy to measure. The usefulness and convenience of Mössbauer spectroscopy will be understood again from these examples. More examples will be on amorphous alloys and other advanced materials.     

Colorando Auro: contribution to the understanding of a medieval recipe to colour gilded silver plates

The colour of gildings can be modified by many artistic techniques. This article refers to the possibility of a specific chemical treatment to change the colour of gildings. The model samples—gilded silver plate, the mixture and the application of a medieval recipe based on ancient writings from Theophilius and Cellini have been described. We propose a strategy to identify the chemical processes involved in the change of colour of the metallic surface through the advanced study of these model samples. Synchrotron X-ray photoelectron spectroscopy and X-ray absorption spectroscopy were carried out both on the gilding with and without the application of the treatment with the aim to understand the chemical reactions occurring during the treatment.     

马家塬M21出土一件料珠的成分和风化层的研究

为研究古代人造料珠的成分和风化状况,对马家塬M21墓地内出土的一件料珠进行超景深显微观察,扫描电镜能谱分析（SEM-EDS）与拉曼光谱分析（Raman）,观察了样品表面形态、获得了样品元素组成和物相组成。结果揭示料珠主要组成成分为混合BaSO₄,PbCO₃,Pb₅Si₄O₈(OH)₁₀和Cu₂Pb₅(SO₄)₃(CO₃)(OH)₆等杂质的中国蓝,呈现为浅蓝色颗粒,由固相烧结法制作,外部黄色结壳成分为Pb₈O₅(OH)₂Cl₄。研究阐述了中国蓝工艺的发展及风化生成碱性铅化合物的原因,该料珠的元素分析显示Si含量最高,Cu和Ba的含量大略相等,而Pb的含量较低,可能代表当时硅酸铜钡料珠烧制已经开始有意控制原料的比例;碱性铅化合物应是在埋藏过程中形成的,高温烧结制备料珠时产生的氧化物未反应完全,随后被埋入地下,与碱性土壤水水合形成碱性铅化合物。该研究为古代费昂斯制品和硅酸铜钡类制品的研究提供参考,对中国古代科技史研究具有重要意义。     

Biomimetic Synthesis of Silver Nanoparticle Using Leaf Extract of Mangifera Indica and Their Antibacterial Efficacy

The aim of this study to focused on bioinspired synthesis of silver nanoparticles (AgNPs) as a viable alternative to eradicate the existing physicochemical processes. In this context, the bioinspired AgNPs were synthesized using leaf extract of M. indica. Optimization of the experimental conditions for the rapid and high yield of AgNPs in minimum investment of time and expense have been carried out along with their antibacterial efficacy evaluated. For this reason, the variation of parameters like the concentration of the silver precursors, reducing agent, time, pH, and temperature of synthesis were realized. Synthesized AgNPs were characterized by UV-Visible spectroscopy, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM) techniques. UV-Visible spectra gave surface plasmon resonance (SPR) at 440 nm for AgNPs. Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) techniques were further confirmed the synthesis and crystalline nature of AgNPs respectively. Transmission electron microscopy (TEM) observed spherical shapes of synthesized AgNPs within range 5～20 nm. The results of the current study indicate that optimization process play a pivotal role in the AgNPs synthesis and biogenic synthesized AgNPs might be used against bacterial pathogens.     

Synthesis and characterization of silver nanoparticles from (bis)alkylamine silver carboxylate precursors

A comparative study of amine and silver carboxylate adducts [R₁COOAg-2(R₂NH₂)] (R₁ = 1, 7, 11; R₂ = 8, 12) as a key intermediate in NPs synthesis is carried out via differential scanning calorimetry, solid-state FT-infrared spectroscopy, ¹³C CP MAS NMR, powder X-ray diffraction and X-ray photoelectron spectroscopy, and various solution NMR spectroscopies (¹H and ¹³C NMR, pulsed field gradient spin-echo NMR, and ROESY). It is proposed that carboxyl moieties in the presence of amine ligands are bound to silver ions via chelating bidentate type of coordination as opposed to bridging bidentate coordination of pure silver carboxylates resulting from the formation of dimeric units. All complexes are packed as lamellar bilayer structures. Silver carboxylate/amine complexes show one first-order melting transition. The evidence presented in this study shows that phase behavior of monovalent metal carboxylates are controlled, mainly, by head group bonding. In solution, insoluble silver salt is stabilized by amine molecules which exist in dynamic equilibrium. Using (bis)amine-silver carboxylate complex as precursor, silver nanoparticles were fabricated. During high-temperature thermolysis, the (bis)amine-carboxylate adduct decomposes to produce silver nanoparticles of small size. NPs are stabilized by strongly interacting carboxylate and trace amounts of amine derived from the silver precursor interacting with carboxylic acid. A corresponding aliphatic amide obtained from silver precursor at high-temperature reaction conditions is not taking part in the stabilization. Combining NMR techniques with FTIR, it was possible to follow an original stabilization mechanism.

Open image in new window

Graphical abstract The synthesis of a series (bis)alkylamine silver(I) carboxylate complexes in nonpolar solvents were carried out and fully characterized both in the solid and solution. Carboxyl moieties in the presence of amine ligands are bound to silver ions via chelating bidentate type of coordination. The complexes form layered structures which thermally decompose forming nanoparticles stabilized only by aliphatic carboxylates.

     

Micro-analytical study of interactions between oil and lead compounds in paintings

Oil paintings are complex hybrid materials, made of organic binders associated with inorganic minerals, susceptible to evolving over centuries. In particular, interactions of oil with lead compounds may give rise to the formation of lead soap aggregates, so-called protrusions. This phenomenon is studied here via X-ray and FTIR micro-analysis of an ancient painting dated from 1610. In complement, the synthesis of modern preparations, reconstructed from ancient recipes was assessed. Molecular and atomic images are obtained by combining synchrotron-based FTIR and X-ray fluorescence microscopies. Protrusions are identified in both ancient and modern samples, more particularly, in the ground layer of the paintings, below the colored layer. These observations imply that lead oxide, introduced as a siccative and not as a pigment, may be the element mainly responsible for the protrusions formation, and that this degradation may appear very rapidly on paintings. PACS 87.64.Je; 82.80.Gk; 82.40.Bj     

Anatase nanotubes as support for platinum nanocrystals

Anatase nanotubes were successfully produced via the sol–gel process involving organic titanium precursors and multi-walled carbon nanotubes as template. Controlled heat treatments were carried out in order to remove any solvents and to crystallise the initial amorphous titania coating into anatase. In order to use these structures for catalyst support, platinum particles were formed by the impregnation with hexachloroplatinic acid and subsequent calcination and reduction to obtain a final loading of 4 wt% platinum. This impregnation step was carried out either with the carbon nanotube former still present with subsequent heat treatment to remove the carbonaceous template (sample A) or with the carbon nanotube former already removed (sample B). The materials were characterised by X-ray diffraction, scanning electron microscopy and transmission electron microscopy.     

Characterisation and reproduction of yellow pigments used in central Italy for decorating ceramics during Renaissance

This study presents the characterisation of prototypical yellow pigments used during the Renaissance period in Italy and the successful reproduction of homologous materials in accordance with the ancient recipes. Moreover, a large number of yellow decorative layers of Sicilian ceramic artefacts dated back from 13th to the 19th century have been selected and the main chemical, structural and minero-petrografic features have been studied by X-ray diffraction, optical microscopy and scanning electron microscopy-energy dispersive spectrometry. These results have been compared with literature data of some yellow decorations of Renaissance ceramics made in central Italy. Comparison has also been made with homologous materials that have been successfully reproduced in accordance with ancient recipes described by Cipriano Piccolpasso in the textbook: “I Tre Libri dell’Arte del Vasaio” using the same ingredients proposed by this artist. Such yellow materials reproduce the typical yellow colorants used by craftsmen of relevant sites for ceramic fabrication in central Italy, namely Città di Castello, Urbino and Castel Durante, during the 16th century.Comparative arguments have shown some intriguing differences that are indicators of both technological transfer processes between central and southern Italy as well as of some local implementations likely due to specific raw materials locally available. PACS 81.05.Je; 82.80.-d; 68.37.Hk; 68.55.-a; 61.66.Fn; 61.10.Nz     

Heating of an Atomic Force Microscope tip by femtosecond laser pulses

During the 18th Egyptian dynasty (1570–1292 B.C.), opaque white, blue and turquoise glasses were opacified by calcium antimonate crystals dispersed in a vitreous matrix. The technological processes as well as the antimony sources used to manufacture these crystals remain unknown. Our results shed a new light on glassmaking history: contrary to what was thought, we demonstrate that Egyptian glassmakers did not use in situ crystallization but first synthesized calcium antimonate opacifiers, which do not exist in nature, and then added them to a glass. Furthermore, using transmission electron microscopy (TEM) for the first time in the study of Egyptian opaque glasses, we show that these opacifiers were nano-crystals. Prior to this research, such a process for glassmaking has not been suggested for any kind of ancient opaque glass production. Studying various preparation methods for calcium antimonate, we propose that Egyptian craftsmen could have produced Ca₂Sb₂O₇ by using mixtures of Sb₂O₃ or Sb₂O₅ with calcium carbonates (atomic ratio Sb/Ca=1) heat treated between 1000 and 1100°C. We developed an original strategy focused on the investigation of the crystals and the vitreous matrices using an appropriate suite of high-sensitivity and high-resolution micro- and nano-analytical techniques (scanning electron microscopy (SEM), X-ray diffraction (XRD), TEM). Synchrotron-based micro X-ray absorption near edge spectroscopy (μ-XANES) proved to be very well suited to the selective measure of the antimony oxidation state in the vitreous matrix. This work is the starting point for a complete reassessment not only of ancient Egyptian glass studies but more generally of high-temperature technologies used throughout antiquity.     

Controlled growth of large＇scale silver nanowires

Large-scale silver nanowires with controlled aspect ratio were synthesized via reducing silver nitrate with 1, 2- propanediol in the presence of poly （vinyl pyrrolidone） （PVP）. Scanning electron microscopy, transmission electron microscopy and x-ray powder diffraction were employed to characterize these silver nanowires. The diameter of the silver nanowires can be readily controlled in the range of 100 to 400 nm by varying the experimental conditions. X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy results show that there exists no chemical bond between the silver and the nitrogen atoms. The interaction between PVP and silver nanowires is mainly through the oxygen atom in the carbonyl group.     

Technological study of ancient ceramics produced in Casteldurante (central Italy) during the Renaissance

In order to recover the ancient tradition concerning the materials used for the decoration, majolica shards produced during the Renaissance period in Casteldurante, a famous centre for ceramic production in Italy (Marche), have been examined. In the present study, pigments used for the decorations have been investigated by means of inductively coupled plasma optical emission spectrometry (ICP-OES), scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM-EDX) and diffuse-reflectance UV-Vis spectroscopy. Ochre, lead antimonate yellow, copper-based pigment and smalt have been used as colourants to obtain respectively yellow-orange, yellow, green and blue decorations in accordance with what is reported by the ancient recipes. PACS 81.05.Mh; 82.80.-d; 61.66.Fn; 61.66.Hq     

Synthesis and characterization of myristic acid capped silver nanoparticles

Reduction of silver myristate (AgMy) under mild thermal reaction conditions in a dipolar aprotic solvent i.e. N, N-dimethylformamide (DMF) has been carried out. UV–visible absorption measurements of dried and re-dispersible brown flocculants showed broad features of surface plasmon resonance (SPR) due to silver nanoparticles. The freshly isolated particles showed absorption bands at 414 and 485 nm, respectively, due to inter-particle coupling or clustering of silver ions and silver atoms. X-ray diffraction (XRD) pattern of fcc zero-valent silver resulted in crystallite size of about 10 nm. Scanning electron microscopy (SEM) revealed formation of rod shaped silver with increasing reaction temperature. Thermal analysis (TGA) showed about 10% weight loss due to organic capping.     

安徽枞阳出土西周至战国时期青铜器的矿料来源研究

采用激光剥蚀电感耦合等离子体质谱(LA-ICP-MS),对枞阳境内出土西周至战国时期青铜器和汤家墩遗址出土炼渣中的铜颗粒进行微量元素原位无损分析,以探讨枞阳县境内出土青铜器的铜矿来源。结果表明,枞阳汤家墩遗址冶炼铜金属颗粒中的Co,As,Sb,Ag和Bi等元素含量较高,其微量元素特征不同于铜陵和铜绿山的冶炼金属铜;从西周至战国时期,枞阳青铜器所用铜矿来源比较稳定,主要来自汤家墩遗址周边的枞阳县境内,有少量器物的铜矿可能来自长江以南的铜陵地区;LA-ICP-MS可用于青铜器和古铜矿冶遗址炼渣中所夹杂铜颗粒的微量元素原位无损分析,从而为利用炼渣探讨古矿冶遗址冶炼金属产品的微量元素特征奠定了基础,对探讨三代青铜器的矿料来源研究具有重要的应用价值。     

Laser based fabrication of chitosan mediated silver nanoparticles

We report fabrication of silver nanoparticles (Ag NPs) by laser ablation technique in different concentrations of aqueous chitosan solution. The ablation process of silver plate was carried out by using a nanosecond Q-switched Nd:YAG pulsed laser and the characterization of Ag NPs was done by Transmission electron microscopy, UV-Vis spectroscopy, and X-ray diffraction. UV-visible plasmon absorption spectra revealed that the formation efficiency as well as the stability of nanoparticles was increased by addition of chitosan. On the other hand, the size decrement of nanoparticles was more remarkable in the higher chitosan concentration.     

Study of ancient mortars from the Roman Villa of Pollio Felice in Sorrento (Naples)

The study of ancient mortars is an important aspect of building conservation: the choice of the materials has varied according to historical period, regional habits, and their specific function in the structure. Ancient mortars are composites, comprising hydraulic or aerial binding materials, and aggregates, passive or active, which may react with binding material. Moreover, they were modified during setting, hardening, and aging, according to processes not yet well known. In this paper, we present a study of ancient mortars from the Villa of Pollio Felice of Sorrento (Naples). The analysis has been performed by conventional techniques (grain-size distribution, lime-percentage analysis, optical and electron microscopy, and X-ray diffraction) and by means of a laboratory X-ray microdiffractometer equipped with an image plate detector. This system, applied for the first time to archaeological studies, can reach a spatial resolution of a few tenths of microns and it allows us to obtain separate phase identification of binder and filler particles. PACS 07.85.Nc; 61.10.Nz     

Photoinduced formation and aggregation of silver nanoparticles at the surface of carboxymethylcellulose films

Formation and aggregation of photolytic silver nanoparticles at the surface of silver salt of carboxymethylcellulose films (CMCAg films) have been investigated. Detailed X-ray photoelectron spectroscopy (XPS) study and field emission type scanning electron microscopy (FE-SEM) observation have been carried out to characterize silver nanoparticles at the film surface. When the CMCAg films were irradiated with UV light in wet air at room temperature for 30–60 min, silver nanoparticles of ca. 10 nm size were formed at the irradiated surface. According to the FE-SEM observation, the growth of the particle diameter and aggregation of nanoparticles took place after prolonged irradiation, and finally, the irradiated side of the film surface was densely covered with the silver nanoparticles of ca. 35 nm size. Chemical composition analysis by the XPS measurements has confirmed the increase in the atomic concentration of silver with irradiation time. It is suggested that silver atoms and clusters can move in the film and precipitate at the irradiated surface.