Southwestern Sardinia, Italy, hosts several skarn, W–Sn–Mo greisen and hydrothermal deposits related to a 289±1 Ma Late Variscan granite suite. Among them, the most representative scheelite-bearing skarns belong to the San Pietro and Sinibidraxiu localities, in the Monte Tamara area, Sulcis region. The San Pietro deposit is a typical calc-silicate skarn whereas Sinibidraxiu is a sharply bounded orebody hosted in a marble unit. Optical petrographic observations and compositional data of major and trace elements were obtained for samples from both localities. San Pietro data suggests evolution from an oxidising prograde skarn stage (andradite–diopside, hematite and scheelite), to progressively more reducing conditions from the early retrograde (magnetite–cassiterite) to the late sulfide stage (arsenopyrite, stannite, molybdenite, Bi sulfosalts and Zn–Cu–Pb–Fe sulfides); Sinibidraxiu has diffuse carbonate–quartz intergrowths pseudomorphic over an early mineral assemblage with fibrous habit, followed by abundant ore mineral precipitation under reducing conditions (scheelite, arsenopyrite and Pb–Zn–Cu–Fe sulfides). Geothermometers indicate a comprehensive temperature range of 460–270°C for the sulfide stages of both deposits. The differences between the two deposits might be controlled by the distance from the source intrusion coupled with the different reactivity of the host rocks. The San Pietro mineralogy represents a more proximal skarn, contrasting with more distal mineralogical and chemical features characterising the Sinibidraxiu orebody (lack of Mo–Sn–Bi phases; LREE–MREE–HREE signature of scheelite). This investigation contributes for the first time to the identification of a W–Sn skarn system in SW Sardinia, thereby suggesting the Monte Tamara area and its surroundings as favourable for further exploration.

Electron probe microanalysis (EPMA) is based on physical relations between measured X-ray intensities of characteristic lines and their X-ray production efficiency, which depends on the specimen composition. The quality of the analysis results relies on how realistically the physical relations describe the generation and emission of X-rays. Special experiments are necessary to measure X-ray production efficiencies. A challenge in these experiments is the determination of the detection efficiency of the spectrometer as a function of the photon energy. An energy-dispersive spectrometer was used in this work, for which the efficiency was determined at metrological synchrotron beamlines with an accuracy of ±2%. X-ray production efficiencies for the L series and the Kα series of copper and zirconium and for the M and L series of tungsten were determined at energies up to 30 keV in a scanning electron microscope. These experimental values were compared with calculated X-ray production efficiencies using physical relations and material constants applied in EPMA. The objective of the comparison is the further improvement of EPMA algorithms as well as extending the available database for X-ray production efficiencies. Experimental data for the X-ray production efficiency are also useful for the assessment of spectrum simulation software.

Hydroplumboelsmoreite (IMA21-C), (Pb,□)2(W,Fe3+)2O6(H2O), is a redefined elsmoreite-group mineral in the pyrochlore supergroup. It was found in a ‘jixianite’ cotype specimen provided by Mr. Liu Jianchang, who first found ‘jixianite’ in 1979 in the Jizhou District, Tianjin City, China. The mineral occurs as yellow to reddish brown aggregates, together with raspite and another elsmoreite-group mineral under study. Hydroplumboelsmoreite occurs in cryptocrystalline form and occasionally in octahedral microcrystalline form (under 20 μm in size). The crystals are colourless and translucent with a white streak, and the lustre is adamantine to greasy. Hydroplumboelsmoreite is isotropic, with a calculated refractive index of 2.29, a Mohs hardness of ~4½–5, and a calculated density of 7.47 g⋅cm−3. The strongest five powder X-ray diffraction lines [d in Å(I)(hkl)] are 6.070(28)(111), 3.012(100)(222), 2.603(32)(004), 1.836(35)(044) and 1.568(30)(226). The crystal structure was refined to R1 = 0.0459 using 80 unique reflections collected with MoKα radiation, and the results show that the mineral is cubic, space group Fd$\bar{3}$m, with a = 10.3377(5) Å, V = 1104.77(16) Å3 and Z = 8. Electron microprobe analyses and crystal structure refinement were used to determine the empirical formula: (Pb1.05Sr0.05Ce3+0.07Na0.01□0.82)Σ2.00(W1.32Fe3+0.67Zr0.01)Σ2.00O6[(H2O)0.43O0.19□0.38]Σ1.00. The mineral was named hydroplumboelsmoreite based on the predominance of Pb, W, and molecular H2O in the A, B and Y sites, respectively.

Native tungsten (IMA2011-004), W, is officially described as a new mineral from gold placers in the Bol'shaya Pol'ya river valley, Prepolar Urals, Russia, associated with yttriaite-(Y) and from quartz veins in the Mt Neroyka rock-crystal field, Ust–Puiva, Tyumenskaya Oblast', Russia. Tungsten forms polycrystalline grains and masses, and rarely cubo-octahedra. It is silver white to steel grey in colour, with metallic lustre and grey streak. The calculated density is 19.226 g/cm3. The Vickers hardness (VHN25) is 571.45 kg/mm2. In plane polarised light, tungsten is white with a pale-yellow tint and optically isotropic. Electron microprobe analyses of Bol'shaya Pol'ya river valley material provided W 99.27, Mo 0.06, Mn 0.04, Fe 0.01, total 99.38 wt.%. The five strongest powder X-ray diffraction lines are [dobs Å(I)(hkl)]: 2.2422(100)(110), 1.5835(25)(200), 1.2929(48)(211), 1.0010(23)(310) and 0.8457(24)(321). Tungsten is cubic, Im$\bar{3}$m, a = 3.1648(4) Å, V = 31.69(4) Å3 and Z = 2. Some additional occurrences of native tungsten and technogenic tungsten found in Nature are also described.

The difference in the defect structures produced by different ion masses in a tungsten lattice is investigated using 80 MeV Au7+ ions and 10 MeV B3+ ions. The details of the defects produced by ions in recrystallized tungsten foil samples are studied using transmission electron microscopy. Dislocations of type b = 1/2[111] and [001] were observed in the analysis. While highly energetic gold ion produced small clusters of defects with very few dislocation lines, boron has produced large and sparse clusters with numerous dislocation lines. The difference in the defect structures could be due to the difference in separation between primary knock-on atoms produced by gold and boron ions.

Hydrogen exposure has been found to result in metal embrittlement. In this work, we use nanoindentation to study the mechanical properties of polycrystalline tungsten subjected to deuterium plasma exposure. For the purpose of comparison, nanoindentation tests on exposed and unexposed reference tungsten were carried out. The results exhibit a decrease in the pop-in load and an increase in hardness on the exposed tungsten sample after deuterium exposure. No significant influence of grain orientation on the pop-in load was observed. After a desorption time of td ≥ 168 h, both the pop-in load and hardness exhibit a recovering trend toward the reference state without deuterium exposure. The decrease of pop-in load is explained using the defactant theory, which suggests that the presence of deuterium facilitates the dislocation nucleation. The increase of hardness is discussed based on two possible mechanisms of the defactant theory and hydrogen pinning of dislocations.

The Vale das Gatas tungsten mine is situated at the contact between Hercynian granite and Cambrian-Precambrian crystalline schists a few kilometers north of the village of Sabrosa, near Vila Real, in northern Portugal. Wolframite has been the principal product of the mine although several other metals of economic interest are known to occur there. The silver content of the ores was attributed by earlier workers to the presence of tetrahedrite and schapbachite, whilst this work shows matildite, pavonite, acanthite, and argyrodite to be present, together with Ag-bearing galena. The textures and compositions of these phases are described with preliminary results of fluid inclusion studies.

W-bearing rutile formed during alteration of jarosite by resurgent hydrothermal fluids in the oxide zone of the Kori Kollo gold deposit. The rutile shows sector zoning in basal sections and well developed multiple growth zones, both defined in backscatter electron images by variations in the W content. The maximum WO3 content is 5.3 wt.% and W substitutes for Ti with double substitution of Fe to maintain charge balance. The causes of multiple growth bands are considered to be changes in externally controlled variables occurring in a shallow hydrothermal system. Whereas Ti is probably leached from biotite in dacitic rocks, the W is introduced by hydrothermal fluids.

The Hatapang granite was discovered during geological mapping and mineral exploration in northern Sumatra by the British Geological Survey in conjunction with the Indonesian Directorate of Mineral Resources. The pluton comprises a two-mica granite which shows significant greisenization and veining around its margins associated with Sn and W mineralization. An Rb-Sr isochron derived for the pluton indicates an age of 80 Ma and an initial 87Sr/86Sr ratio of 0.7151. This together with major and trace element data show the Hatapang to be of clear S-type affinity.

The greisens are quartz-mica-topaz rocks and are almost totally deficient in Na. Trioctahedral mica compositions progress from biotite through siderophyllite to zinnwaldite during final differentiation and greisenization of the granite. Accompanying dioctahedral micas are phengitic. Associated with late-stage differentiation of the granite is the precipitation of tourmaline and various Nb-Ta oxides. Sn and W mineralization is manifested as cassiterite in the greisens, while wolframite tends to be related to quartz veining. A later and lower temperature sulphide event produced a suite of base metal sulphides and Ag-Bi-Pb sulphosalts. The identification of a Sn-W granite of Cretaceous age in northern Sumatra provides a link with occurrences of economically important Late Cretaceous Sn-W granites in Thailand and Burma and increases the potential of an area which until recently was thought to lie outside the SE Asian tin belt.

Thermal reduction in wolframite (composition: Fe1-xMnxWO4 (0.08<x<0.87)) from different deposits in Argentina, was analysed using a temperature-programmed reduction (TPR) technique. X-ray powder diffraction analysis (XRPD), vibrational spectroscopy (IR and Raman), scanning electron microscopy (SEM) and electron microprobe analysis (EDAX) were used to assess the relationship between reactivity degree in a reducing atmosphere (H2 10% – N2 90%) and chemical composition of wolframite.Similar studies were carried out with other related minerals, especially the ones found in natural deposits as alteration or association products. Stability of the solid solution serial members is correlated with redox properties of divalent cations.

Microstructure and phase evolution in magnetron sputtered nanocrystalline tungsten and tungsten alloy thin films are explored through in situ TEM annealing experiments at temperatures up to 1000 °C. Grain growth in unalloyed nanocrystalline tungsten transpires through a discontinuous process at temperatures up to 550 °C, which is coupled to an allotropic phase transformation of metastable β-tungsten with the A-15 cubic structure to stable body centered cubic (BCC) α-tungsten. Complete transformation to the BCC α-phase is accompanied by the convergence to a unimodal nanocrystalline structure at 650 °C, signaling a transition to continuous grain growth. Alloy films synthesized with compositions of W–20 at.% Ti and W–15 at.% Cr exhibit only the BCC α-phase in the as-deposited state, which indicate the addition of solute stabilizes the films against the formation of metastable β-tungsten. Thermal stability of the alloy films is significantly improved over their unalloyed counterpart up to 1000 °C, and grain coarsening occurs solely through a continuous growth process. The contrasting thermal stability between W–Ti and W–Cr is attributed to different grain boundary segregation states, thus demonstrating the critical role of grain boundary chemistry in the design of solute-stabilized nanocrystalline alloys.

The propagation of a pre-existing center crack in single crystal tungsten under cyclic loading was examined by molecular dynamics (MD) simulations at various temperatures. The results indicated that the deformation mechanism and fracture behavior at crack tip were differences for variously oriented cracks. The [001](010) crack propagated as the form of the formation of slip, while the deformation mechanisms of [10−1](101) crack were blunting voids at 300 K. At higher temperature, many more slip systems were activated resulting in the change of mode of crack propagation. Simulated results showed that the effect of temperature on deformation mechanism and fracture behavior of [001](010) crack was more sensitive than that of [10−1](101) crack. Meanwhile, the influence of a 5〈310〉{110} model grain boundary (GB) on crack propagation was also discussed. Detailed analysis showed that the grain boundary resisted the crack growth by changing the deformation mechanisms and the path of crack propagation at crack tip before the crack reached the grain boundary, and had an important influence on the crack growth rate.

Density functional theory calculations and molecular dynamics with a recently developed potential for W–He were used to evaluate the thermal stability of helium-vacancy clusters (nHe.mv) as well as pure interstitial helium clusters in tungsten. The stability of such objects results from a competitive process between thermal emission of vacancies, self interstitial atoms (SIAs), and helium, depending on the helium-to-vacancy ratio in mixed clusters or helium number in pure interstitial helium clusters. We investigated in particular the ground state configurations as well as the activation barriers of self trapping and trap mutation, i.e., the emission of one SIA along with the creation of one vacancy from a vacancy-helium or pure helium object.

Plasma was generated by focusing 10 ns Nd:YAG (λ = 1064 nm) laser pulse on the thick tungsten target. The laser fluence at the target was varied in the range of 3.57–10.97 J/cm2. The ion emission from the expanding tungsten plasma was analyzed with the help of an ion collector and time-of-flight electrostatic ion energy analyzer. About 44 times rise in the ion charge per laser shot was observed in the investigated laser fluence range. The measured threshold fluence for onset of the tungsten plasma was 3.27 J/cm2. The estimated plume expansion coefficient Zinf/Xinf = 2.5 ± 0.2 was in agreement with the previous experimental studies and the predictions of self-similar plume expansion model. The electrostatic ion energy analyzer study showed that charge state of the W ions increases with the laser fluence and maximum ion charge state was 5+. It was observed that threshold fluence for appearance of a specific charge state can be measured. A clear correlation between the relative abundances of W(n−1)+, Wn+, and W(n+1)+ indicates that higher order charge states are most probably produced by stepwise ionization process.

A cluster dynamics model based on rate theory has been developed to describe the accumulation and diffusion processes of helium in tungsten under helium implantation alone or synergistic irradiation with neutron, by involving different types of objects, adopting up-to-date parameters and complex reaction processes as well as considering the diffusion process along with depth. The calculated results under different conditions are in good agreement with experiments much well. The model describes the behavior of helium in tungsten within 2D space of defect type/size and depth on different ions incident conditions (energies and fluences) and material conditions (system temperature and existent sinks), by including the synergistic effect of helium-neutron irradiations and the influence of inherent sinks (dislocation lines and grain boundaries). The model, coded as IRadMat, would be universally applicable to the evolution of defects for ions/neutron irradiated on plasma-facing materials.

The lattice parameters of α-alumina have been determined for temperatures in the range 20<T<1050 °C, using the lattice parameter of tungsten as a thermometer and a simple furnace in the diffractometer on the Australian beamline at the Photon Factory, Tsukuba, Japan. It is shown that the accuracy of this technique for measurement of cell parameters at temperatures up to ∼1200 °C is limited at present by uncertainty in the cell parameters of the reference material (i.e., tungsten) at high temperatures. Some problems with the equipment are discussed.

Morphological and chemical characteristics were determined for airborne tungsten particles in Fallon, Nevada, a town that is distinguishable environmentally by elevated airborne tungsten and cobalt. From samples of airborne dust collected previously at six different places in Fallon, tungsten-rich dust particles were isolated and analyzed with automated electron microprobe and wavelength-dispersive spectrometry. Representative W particles were further analyzed using transmission electron microscopy. Morphologically, Fallon W particles are angular and small, with minimum and maximum sizes of ≤1 μm and 5.9 μm in diameter, respectively. The number and size of tungsten-rich particles decrease in Fallon with distance from a hard-metal facility located near the center of town. Chemically, Fallon airborne W particles include mixtures of tungsten with cobalt plus other metals such as chromium, iron, and copper. No W-rich particles were identifiable as CaWO4 (scheelite) or MnWO4 (huebnerite). From d-spacings, Fallon particles are most consistent with identification as tungsten carbide. Based on these multiple lines of evidence, airborne W particles in Fallon are anthropogenic in origin, not natural. The hard-metal facility in Fallon processes finely powdered W and W-Co, and further investigation using tracer particles is recommended to definitively identify the source of Fallon's airborne tungsten.

In this article, the secondary electron-emission properties of both vertically and laterally inhomogeneous samples are discussed. To study the effect of surface coverage, the total electron-emission yield of tungsten and niobium samples was measured as a function of primary electron energy and oxide thickness. A method is suggested to avoid charging difficulties during AES measurements of samples that consist of both metal and various insulator parts.

The influence of W on the temporal evolution of γ′ precipitation toward equilibrium in a model Ni-Al-Cr alloy is investigated by three-dimensional atom-probe (3DAP) microscopy and transmission electron microscopy (TEM). We report on the alloys Ni-10 Al-8.5 Cr (at.%) and Ni-10 Al-8.5 Cr-2 W (at.%), which were aged isothermally in the γ + γ′ two-phase field at 1073 K, for times ranging from 0.25 to 264 h. Spheroidal-shaped γ′ precipitates, 5–15 nm diameter, form during quenching from above the solvus temperature in both alloys at a high number density (∼1023 m−3). As γ′ precipitates grow with aging at 1073 K, a transition from spheriodal- to cuboidal-shaped precipitates is observed in both alloys. The elemental partitioning and spatially resolved concentration profiles across the γ′ precipitates are obtained as a function of aging time from three-dimensional atom-by-atom reconstructions. Proximity histogram concentration profiles (Hellman et al., 2000) of the quaternary alloy demonstrate that W concentration gradients exist in γ′ precipitates in the as-quenched and 0.25-h aging states, which disappear after 1 h of aging. The diffusion coefficient of W in γ′ is estimated to be 6.2 × 10−20 m2 s−1 at 1073 K. The W addition decreases the coarsening rate constant, and leads to stronger partitioning of Al to γ′ and Cr to γ.