High Tin Content Research Articles

A Typology and Lead Isotope and Cultural Exchange Study on Bronze Knives from Shuangyuan Cemetery, Chengdu City, Southwest China

Background: Bronze knives, which have been excavated in large quantities and acquired hierarchical significance, are essential artifacts in Shu State in Southwest China. Building upon previous typological analyses of bronze knives, it is hypothesized that Shu culture may have imported foreign-style bronze knives. However, further demonstration of the provenance of metal materials, the typology of knives, and the cultural exchange necessitates a comprehensive examination through the lens of scientific analysis. The purpose of this study is to investigate the differences in the manufacturing processes and metal resources of Shu bronze knives with various cultural styles and whether bronze knives in the foreign styles were imported or locally imitated. Methods: In this study, the typology, portable X-ray fluorescence spectrometry and multi-collector inductively coupled plasma mass spectrometry were used to analyze twenty-four bronze knives unearthed from Shuangyuan cemetery, a cemetery of the Eastern Zhou Dynasty in Chengdu City, Sichuan Province, Southwest China. Results: The results of the study show that the knives of Shuangyuan Cemetery can be classified typologically into five types, encompassing both local and foreign styles. The predominant alloy composition of these knives is lead-tin bronze, characterized by a notably high tin content. Lead isotope ratios indicate that metal materials from the South China geochemical province and Yangtze geochemical province were mainly used to manufacture the bronze knives unearthed from the Shu state Conclusion: While the majority of foreign-style knives with ring-shaped heads were likely imported from neighboring regions like Chu state, distinctively styled type D and type E bronze knives appear to have been locally imitated by the Shu, showcasing a blend of external influences and indigenous innovation. The combination of typology and scientific analysis of the bronze knife may shed new light on the study of the Shu culture of the Eastern Zhou period.

Cassiterite and zircon U-Pb ages and compositions from ore-bearing and barren granites in Thailand: Constraints on the formation of tin deposits in Southeast Asia

The Southeast Asian Tin Province comprises western, central, and eastern belts and hosts significant granite-related Sn deposits. The genetic links between granites and Sn mineralization are still unclear. Most Sn deposits are in Thailand’s western and central belts, but their origin remains poorly elucidated due to the absence of direct dating of mineralization. Herein in-situ U-Pb age data of wolframite and cassiterite grains from nine representative Sn deposits in Thailand are obtained, which fall into two stages. Triassic deposits (224–210 Ma) are found in the Central belt, with Cretaceous deposits (78–67 Ma) in the Central belt being younger than those in the Western belt (84–74 Ma). However, ore-bearing granites, spanning two periods (227–205 Ma and 85–69 Ma), occur in central and western belts. Some Triassic ore-bearing granites exhibit significantly older ages than ore-forming ages. Newly identified ore-forming granites contain zircon grains with relatively low εHf(t) values (−29.5 to + 4.1; average = − 11.8), indicative of an origin from supracrustal sediments from the Sibumasu block. In contrast, barren granites have ages from 303–224 Ma and higher zircon εHf(t) values (−9.9 to + 13.2; average = +1.2), which suggests that they were derived from the juvenile mafic crust. Even after experiencing hydrothermal fluids exsolution, some low-fractionated ore-forming granites (D.I. < 90) still maintain remarkably high tin contents. Both ore-forming and barren granites crystallized under reducing conditions. Our study highlights the importance of Sn-rich sources of parental magmas in forming Sn deposits. The metasediment-rich basement of the Sibumasu block distributing along the continental margin is likely the Sn-rich source. These sources played a crucial role in forming two stages of tin deposits in distinct tectonic settings, that are syn-collisional crustal thickening in Paleo-Tethys and post-collisional extension-related settings in Neo-Tethys.

Analysis of Cooling a Printed 3D Mold Using a Casting and Solidification Simulation of a CuSn20 Bronze Bell Casting

The work done in this study is a preliminary investigation into the possibility of modelling the filling and solidification process of castings in molds made with the additive method. The work originated from an experiment to produce a bronze casting with a high tin content in an additive mold. The mold filling and solidification simulation was carried out in the MAGMASO FT program, and the lambda thermal conductivity coefficient used in the program’s material database was corrected based on the actual temperature values of the printed form. The results were compared with the modeling results for the physical properties of furan molds based on the program database. The microstructure of the castings obtained in the compared forms was assessed.

АPPLICATION OF ELECTROCHEMICALLY PREPARED Sn-Co ALLOY POWDERS AS ANODE MATERIAL FOR LITHIUM-ION BATTERIES

The electrochemical behavior of active electrode (anode) materials (AEMs) for lithium-ion battery (LIB), prepared with Sn-Co powders electrodeposited in three different current modes, was investigated. It is shown that AEM with Sn-Co powder, obtained in constant-potential mode, has the highest tin content (82.1 wt. %) and the best performance and stability in operation. The anode material, made with this Sn-Co powder, shows a first-cycle charge capacity of 450 mAh g-1, which decreases to 295 mAh g-1 for 10 battery cycles at a current load of 0.8 mA (0.1C). The data also showed that the AEM with Sn-Co powder, deposited in pulse-potential mode, which has the lowest tin content (24.5 wt. % Sn) but the highest dispersity compared to the other powders tested, shows better performance than that of a powder with a tin content of 68.6 wt. %, obtained in constant-current mode. It can be concluded that for the high electrochemical activity of the anode materials, prepared with Sn-Co powders, both the high tin content and the high dispersity and morphological uniformity of the powders are of great importance.

Modeling and design of GeSn avalanche photodiodes with high tin content for applications at 3.3 μm

Modeling and design of GeSn avalanche photodiodes with high tin content for applications at 3.3 μm

Manufacturing Techniques of Ancient Forged High-tin Bronze Wares from Archaeological Sites in Bagan, Myanmar

Bronze wares made with forged high-tin bronze technology were first produced in the Persian region of the Orient, gradually brought to India and then to China and the Korean Peninsula. By scientifically analyzing bronze artifacts of Myanmar, which is located halfway between Persia and Korea, it is possible to confirm the trade and the propagation route of technology at the time. This study scientifically analyzed bronze artifacts excavated from the Bagan ruins in Myanmar to identify the manufacturing technology. Forged high-tin bronze wares in Bagan Dynasty are with alloy compositions Cu-Sn. Composed of Cu-Sn only were manufactured by alloying Cu with Sn in a ratio of 76 wt% and 24 wt%, which is a relatively high tin content. High-tin bronze wares composed of Cu-Sn were manufactured with the bronze material of an alloy of Cu and a large amount of Sn by hot working (forging) and finished by quenching. The microstructure indicates temperatures at which the quenching was performed and various microstructures that occur in different temperature ranges are observed such as β (M), γ phase, δ phase as well as primary crystals, α phase. The presence of different microstrucures suggests multiple high-tin bronze wares were quenched at a wide range of temperatures. The non-metallic inclusions of the bronze wares contain sulfur, which indicates with high possibility that the copper provided as the raw material was extracted from copper ores containing sulfur.

Tin isotopes reveal changing patterns of tin trade, connectivity and consumption from Anatolia and Central Asia at Kültepe

Until recently, what was known about the trade of tin in the ancient Near East was based in large part on information derived from the extensive commercial archives found at the archaeological site of Kültepe (ancient Kaneš) in Turkey dating to the Middle Bronze Age (MBA) c. 1900-1750 BC. These archives were produced by an expatriate community of traders native to the city of Assur in modern-day Iraq and document an extensive shipping of tin ingots from unnamed sources east of their hometown. Tin was carried by donkeys through northern Syria and across the Taurus Mountains to Anatolia where it was sold for silver.This paper presents the first set of tin isotope analyses of bronze objects from Kültepe to test the image provided by these ancient archives, finding that all artifacts dated to the main period of Assyrian trade excavated in the residential areas of the site indeed have high tin content and high values of δ124Sn (0.77–1.74‰) relative to the NIST 3161a standard. Such high values currently compare best with ores from Central Asia. The isotopic analysis of artifacts from the Assyrian Trading Colony Period of Kültepe is therefore consistent with the textual evidence.However, Early Bronze Age samples recovered at the site are instead characterized by lower ranges that extend to neutral δ124Sn values (0.02–1.31‰). Likewise, one artifact coming from Mound Level 7 (c. 1830-1700) at the center of the site where public buildings were concentrated, and one object dated to the Hellenistic Period (Mound Level 2), when the site saw a resurgence in political importance, likewise have lower δ124Sn compositions of 0.11 and 0.31‰, respectively. Both samples also have low to moderate tin content.The Early Bronze Age artifacts form a linear array between artifacts from low δ124Sn-low Sn wt% to high δ124Sn-high Sn wt% that suggests a mixing of two compositional groups – not simply the mixing of two isotopically distinct reservoirs of tin, but also distinct in the amount of tin present in the alloy. This would be consistent with the recycling of low tin bronze objects with local tin, together with high tin bronzes containing tin from Central Asia. The two samples from Mound Levels 7 and 2 suggest that although Central Asian tin was predominant in the MBA, Anatolian tin may have continued to be used in a separate bronze production system that remained active at shifting varying of intensity throughout antiquity.

Explosive crystallization of amorphous germanium-tin films by irradiation with a 3-keV electron beam

Much effort has been expended to obtain thin films of metastable solid solutions of germanium (Ge) that contain as high tin (Sn) content as possible because of their excellent electronic and optoelectronic properties. On the basis of our previous study on amorphous Ge, we demonstrated in this study that irradiation of substrate-free films of amorphous Ge100−xSnx (x = 8, 11, and 19 at. %) with a low-energy electron beam of 3 keV at ambient temperature can induce instantaneous wide-area crystallization (explosive crystallization). Characteristic spiral crystal growth associated with explosive crystallization occurred with areas exceeding 50 μm in diameter around a scanned area of the electron beam of 8 × 8 μm2. As a result, solid solutions of GeSn with Sn concentration up to 19 at. % were obtained with the suppression of precipitation of β-Sn. The region of explosive crystallization reduced in size with increasing Sn content. In addition, thermal analyses revealed that the heat released during crystallization of amorphous GeSn films decreased with increasing Sn content. This relationship indicates that the heat release at the growth front plays a key role in the propagation of explosive crystallization of a-GeSn.

О бисере из «белого металла» андроновского населения: к вопросу об истоках традиции

Beads made of "white metal" are found in Altai on the one hand, in the Andronovo (Fedorovo) burial site Chekanovsky Log X, on the other hand. They are discovered at the steppe-type sites of the north of Middle Asia, where this category of adornments is quite often. Moreover, in some burials the number of beads is extremely large (300–1200 pieces). The focus in this article is given to the description of Middle Asian complexes with finds of "white metal" beads. The article mainly considers the issue of their chemical composition. According to the spectral analysis, the Middle-Asian beads consisted of copper with a high content of tin or a complex tin-based alloy. Such a composition gave the items a silvery color. It is suggested that such beads were used by the Middle Asia people to substitute silver, more expensive and rare metal. It is assumed that not the beads themselves were valued, but the clothes skillfully embroidered with them. The author concludes that the tradition to use clothes embroidered with beads emerged in the steppe-type sites of Central Asia (Dashti-Kozi, Muminabad burial sites, etc.) due to contacts with the local farmers. But farmers preferred to make beads from stone instead. The tradition to use clothes embroidered with beads of semi-precious gems arises among them probably as a result of contacts with civilizations of the Near East. Such clothes appeared among steppe herders of Middle Asia not to simple copy farmers’ images. They mastered metallurgy and metalworking early enough and preferred metal in making jewelry, including beads. The finds of “white metal” beads in the Chekanovsky Log X burial site is another confirmation of the previously expressed point of view that the Andronovo population of Altai formed under the influence of migration impulses from the southern regions, including Middle Asia.

Pd/CeO2-SnO2 catalysts with varying tin content: Promotion of catalytic properties and structure modification

1%Pd/CeO2-SnO2 catalysts with varying Ce/Sn ratio were synthesized by counter-precipitation followed by calcination in a wide temperature range. The catalysts with Ce/Sn < 3/1 possess high thermal stability after calcination up to 1000 °C while maintaining low-temperature activity in CO oxidation. The PdOx clusters serving as active centers in CO oxidation are modified by Sn upon calcination. High tin content (Ce/Sn = 1/3) provides the activity of the catalysts in CH4 oxidation due to stabilization of PdO nanoparticles in the form of core@shell PdO@(CeO2 + SnO2) structures. Formation of the nanoheterophase structure upon calcination plays a key role in the stabilization of Pd-active centers of different types.

Roles of different components of complex inclusion in pitting of 321 stainless steel: Induction effect of CaS and inhibition effect of TiN

Pitting behavior of 321 stainless steel (SS) in sodium chloride solution was studied by potentiostatic pulse technique triggering pits. Pure TiN inclusion and complex inclusion with core-shell structure are found in 321 SS. The former has no effect on pitting performance, while CaS in the latter is the exact inducer of pitting. Mechanism of pitting initiation and propagation induced by complex inclusions was proposed. When CaS content differs little, inhibition effect of TiN shell on pitting propagation is the main reason why a complex inclusion with higher TiN content is more resistant to pitting.

Microstructural evolution and performance of high-tin-content Cu40Sn60 (wt. %) core/shell powder TLPS bonding joints

This paper investigated the microstructure evolution and performance of high tin content Cu@Sn core/shell (60 wt% Sn) powder transient liquid phase sintering bonding. The formation and evolution mechanism of voids were analyzed. Results showed that, after consuming Sn, the joint was mainly composed of Cu6Sn5, Cu3Sn, and Cu, raising the remelting temperature of the joint to 400 °C. The porosity in the joint was decreased firstly, then increased, and finally decreased with bonding time. The maximum porosity was 0.876% and 1.052% at 300 °C for 150 min and 340 °C for 120 min. With the bonding time increased, the room temperature (RT) shear strength was increased first, then decreased, and finally remained stable. In contrast, the high-temperature (350 °C) shear strength was increased first, then remained stable with bonding time. The joint was possessed excellent RT (20.79 MPa) and high-temperature (18.46 MPa) shear strength. The electrical resistivity of joints was increased first, then remained stable with bonding time. The electrical resistivity was reached its maximum value of 1.83 × 10−5 Ω·cm at 300 °C for 150 min. The thermal conductivity of the joint was 28.72 W/(m·K), 26.83 W/(m·K), and 25.99 W/(m·K) at 30 °C, 250 °C, and 350 °C, respectively.

Micro-structural and micro-chemical investigation of Samnite high-tin bronze cuirass discs: ancient metallurgy in central Italy

In the present study, micro-structural and micro-chemical investigation of archaeological bronze artefacts provided new insight about the metallurgical manufacture of defensive weapons by the Samnite’s metalsmiths in central Italy from the archaic necropolis of Barrea (AQ) and Torrebruna (CH). In particular, the metallurgical features, the chemical composition and the manufacturing process of Cu-based high-tin alloys used to produce cuirass discs were investigated. These artifacts were used to protect the warrior’s heart (i.e. the kardiophylaches) but were also and more importantly a distinctive sign of rank and role of warriors of the archaic age (VI BC). The Samnite cuirass discs are multi-material artifacts made of a decorated bronze central part with a complex metallurgical structure, due to the presence of different Cu-Sn phases, and a surrounding iron cladding to support the disk. These discs were studied by different surface and bulk techniques, namely Optical Microscopy (OM), Field Emission Scanning Electron Microscopy coupled with energy dispersive X-ray microanalysis (FE-SEM-EDS), X-ray Diffraction (XRD) and Infrared Spectroscopy (FTIR). The combined use of these techniques proved the high technological level of the Samnite metallurgists. In fact, their particular composition, having an uncommon high content of tin, made their manufacturing process difficult because of the intrinsic brittleness of the alloy. This work disclose the ability of Samnites people to successfully manipulate fragile high tin bronze alloys by inducing temporary phase changes and, thus, facilitating the mechanical shaping of the artifact.

Tribotechnical Properties of Sintered Antifriction Aluminum-Based Composite under Dry Friction against Steel.

The disadvantage of antifriction Al–Sn alloys with high tin content is their low bearing capacity. To improve this property, the aluminum matrix of the alloys was alloyed with zinc. The powder of Al–10Zn alloy was blended with the powder of pure tin in the proportion of 40/60 (wt.%). The resulting mixture of the powders was compacted in briquettes and sintered in a vacuum furnace. The sintered briquettes were subjected to subsequent pressing in the closed press mold at an elevated temperature. After this processing, the yield strength of the sintered (Al–10Zn)–40Sn composite was 1.6 times higher than that of the two-phase Al–40Sn one. The tribological tests of the composites were carried out according to the pin-on-disk scheme without lubrication at pressures of 1–5 MPa. It was established that the (Al–10Zn)–40Sn composite has higher wear resistance compared with the Al–40Sn one. However, this advantage becomes insignificant with an increase in the pressure. It was found that the main wear mechanism of the investigated composites under the dry friction process is a delamination of their highly deformed matrix grains.

Металлические изделия из памятников саргатской культуры Притоболья

The article is devoted to the presentation of the results of an analytical study of metal products from the Sargatka culture sites of the Tobol river region by X-ray fluorescence analysis to clarify the directions of contacts of the local population. As a result of the analysis, we have received evidence of the wide distribution of products made of pure copper (Сu), tin bronze (Cu+Sn) and brass (Cu+Zn) among the population of the Sargatka culture, and we also noted the use of rare alloys not previously identified on the materials of the Sargatka culture: leaded brass (Cu+Zn+Pb) and leadtin bronze (Cu+Pb+Sn). Such a variety of alloys indicates the presence of broad trade and exchange relations among the population of the Sargatka culture at different stages of its existence. The new data do not contradict the idea widespread in the literature about the receipt of ingots and products made of pure copper from Itkul metallurgists, as well as things made of bronze with a high tin content from Central Asia, the Volga region, the Cisurals, the eastern regions of Siberia, Altai and Transbaikal. The new material allowed us to draw a conclusion about the origin of lead-tin bronze products from the Xiongnu of Transbaikal, and jewelry made of double and three-component leaded brass from the population of the Kushan period of Northern Bactria.

Band structure critical point energy in germanium–tin alloys with high tin contents

The dielectric functions of germanium–tin alloy thin-films, deposited by molecular beam epitaxy on bulk Ge substrates, with relatively high Sn contents from 15 to 27 at. %, were measured by variable angle spectroscopic ellipsometry over the wavelength range from 0.190 to 6 μm, using a combination of ultraviolet-visible and infrared ellipsometers. The band structure critical point energies, specifically the E1 and E1 + Δ1 optical transitions, were extracted from the measurements by a method of parametric oscillator modeling and second derivative analysis. With increasing Sn content, the transitions shifted to lower energies, and for alloys with less than 20% Sn, the numerical values agreed reasonably with predictions based on deformation potential theory that accounted for film strain. For the higher Sn alloys, the critical point energies from measurements agreed less well with deformation potential theory. These results provide information on the band structure of GeSn alloys with high Sn contents, which are increasingly important for long-wave infrared devices and applications.

Increasing the Piezoactivity of Manufactured Composite Piezoceramic Transformers by Combining the Processes of Soldering and Polarization

Abstract The article is devoted to solving the problem of ensuring high piezoactivity of composite piezoceramic transformers, in which the component parts are connected by soldering. The existing connection features have been analysed for the elements of composite piezoceramic transformers and the results have shown that during soldering the piezoceramic elements are exposed to thermal shock leading to depolarization of piezoceramics and deterioration of its piezoelectric properties. Diminution of temperature depolarizing effect is possible using low-temperature solders with a high tin content. However, in this case, the diffusion process of the electrode material of the piezoelectric element into the solder increases and the mechanical connection strength decreases. To eliminate these negative phenomena and solve the problem, a new method has been developed for connecting elements of composite piezoceramic transformers by soldering, where a polarizing voltage is applied to the composite piezoceramic transformer when heating and cooling, which prevents depolarization of the domain structure of piezoceramic elements. At the same time, high temperature ensures that polarization is carried out at lower values of the electric tension, and a more mobile domain structure after polarization has a lower level of coercive forces and, accordingly, a greater stability of parameters ov er time. Experimental verification has shown that the relative resonance gap increases by 6 % with a decrease in the dispersion of this value by 12 %, which indicates an increase in piezoactivity and stability of the characteristics of composite piezoceramic transformers manufactured using the solution above.

Mechanical properties and electrical discharge machinability of SPS sintered Y-TZP- and YGd-TZP-titanium nitride composites

Electrical discharge machining (EDM) of ceramics provides an opportunity to manufacture complex shape components from sintered blanks provided the material has a sufficiently high electrical conductivity. In this study yttria and yttria-gadolinia co-stabilized zirconia powders (Y-TZP, YGd-TZP) were produced by intensive co-milling. Fully dense composite ceramics with TZP matrix and 28–32 ​vol% titanium nitride dispersion were manufactured by spark plasma sintering and subsequently ED-machined by die sinking in oil based dielectric.The materials offer high strength of 1200–1450 ​MPa coupled with an attractive fracture resistance of 7–7.8 ​MPa√m. The ceramics exhibit a high electric conductivity of 21–74 ​kS/m with the highest values observed for the co-stabilized matrix and the higher TiN content. ED machining can be carried out at high machining rates of >1 ​mm³/min. The dominant material removal mechanism is melting. ED-machining leaves only a very thin glass-like process zone at the surface, the bulk material stays widely unaffected.

Ceramic Glazed Painted Eggs Production Technology Based on Kyiv Archaeological Materials

Glazed painted eggs were one of the most vivid manifestations of Ancient Rus’ ceramic art. Nevertheless, today there are still unsolved problems in study of this category of archaeological material. It concerns technological aspects. These articles were made of ordinary pottery loam in a band way. They were formed hollow and contained a small ceramic ball in the inner part. After the molding they were fired, then covered with transparent glaze, which served as a background. In most cases green and fulvous glaze was used. Then, by using a special tubular instrument the painting was made with glaze of another colour, usually yellow and green, and the item was heated up again in the kiln in order to smooth the surface. Paintings were not multifarious. There were three main types of designs: ordinary stripes, which surrounded the item several times; unsystematic stripes that were put lengthwise and athwart; and also braces, which were the most common ornament. The question of the Ancient Rus’ glaze, which covered the glazed painted eggs, was raised in the 1960-ies by T. Makarova. However, today, on the basis of our collection and in the context of significant changes in the field of science, we have succeeded in clarifying and extending the known facts. The Nanomedtech Electron Microscopy Laboratory with the help of a Tescan Mira 3 LMU scanning microscope and the Gatan Pecs 682 precision etching and coating system was kindly performed with spectral analysis. Spectral analysis confirmed that Ancient Rus’ glaze had a lead-silica composition with a high content of tin. Brown colour was obtained by iron oxide, yellow by lead, green by copper. A general glaze formula was developed, which should consist essentially of Pb and Si oxide. On the example of two samples that have the same yellow colour, the difference in the quantitative composition of the components and their percentage can be seen that, by-turn, confirms the view of the relative dimensions of component measurement. The analysis of a small amount of material allowed describing the technology of painted eggs manufacturing.

Nitrogen plasma immersion ion implantation treatment of Ti6Al7Nb alloy for bone-implant applications: Enhanced in vitro biological responses and in vivo initial bone-implant contact

Ti6Al4V alloy has been widely applied to orthopedic and dental implants; however, V ions release may have detrimental side effects. Ti6Al7Nb alloy provides mechanical characteristics similar to those of Ti6Al4V while with fewer potentially biological side effects. In the present investigation, nitrogen plasma immersion ion implantation (N-PIII) treatment was applied to Ti6Al7Nb alloy surfaces. N-PIII surface treatment formed a thin (< 100 nm) TiN-containing film on Ti6Al7Nb surface. A higher applied N-PIII voltage resulted in a higher TiN content on Ti6Al7Nb surface. Compared to the untreated Ti6Al7Nb surface, the N-PIII treated Ti6Al7Nb surface had higher surface roughness, hydrophilicity, hardness, corrosion resistance in simulated body fluid, protein (fibronectin) adsorption, and growth of human bone marrow mesenchymal stem cells, particularly Ti6Al7Nb surface with a higher TiN content. Initial bone-implant contact was investigated in vivo by implanting Ti6Al7Nb screw-type implants (with and without N-PIII treatment) in the femur of mini-pigs for two weeks. At two weeks of post-implantation, the N-PIII treated implant surface with a higher TiN content showed a higher initial bone-implant contact than other implants. Overall, the proposed N-PIII treatment of Ti6Al7Nb alloy surface (particularly with a higher TiN content) enhanced in vitro corrosion resistance, protein adsorption, and cell response as well as in vivo initial bone-implant contact.