Search

Binary AsxSe100−x alloys from the border of a glass-forming region (65 < x < 70) subjected to nanomilling in dry and dry–wet modes are characterized by the XRPD, micro-Raman scattering (micro-RS) and revised positron annihilation lifetime (PAL) methods complemented by a disproportionality analysis using the quantum–chemical cluster modeling approach. These alloys are examined with respect to tetra-arsenic biselenide As4Se2 stoichiometry, realized in glassy g-As65Se35, glassy–crystalline g/c-As67Se33 and glassy–crystalline g/c-As70Se30. From the XRPD results, the number of rhombohedral As and cubic arsenolite As2O3 phases in As-Se alloys increases after nanomilling, especially in the wet mode realized in a PVP water solution. Nanomilling-driven amorphization and reamorphization transformations in these alloys are identified by an analysis of diffuse peak halos in their XRPD patterning, showing the interplay between the levels of a medium-range structure (disruption of the intermediate-range ordering at the cost of an extended-range one). From the micro-RS spectroscopy results, these alloys are stabilized by molecular thioarsenides As4Sen (n = 3, 4), regardless of their phase composition, remnants of thioarsenide molecules destructed under nanomilling being reincorporated into a glass network undergoing a polyamorphic transition. From the PAL spectroscopy results, volumetric changes in the wet-milled alloys with respect to the dry-milled ones are identified as resulting from a direct conversion of the bound positron–electron (Ps, positronium) states in the positron traps. Ps-hosting holes in the PVP medium appear instead of positron traps, with ~0.36–0.38 ns lifetimes ascribed to multivacancies in the As-Se matrix. The superposition of PAL spectrum peaks and tails for pelletized PVP, unmilled, dry-milled, and dry–wet-milled As-Se samples shows a spectacular smoothly decaying trend. The microstructure scenarios of the spontaneous (under quenching) and activated (under nanomilling) decomposition of principal network clusters in As4Se2-bearing arsenoselenides are recognized. Over-constrained As6·(2/3) ring-like network clusters acting as pre-cursors of the rhombohedral As phase are the main products of this decomposition. Two spontaneous processes for creating thioarsenides with crystalline counterparts explain the location of the glass-forming border in an As-Se system near the As4Se2 composition, while an activated decomposition process for creating layered As2Se3 structures is responsible for the nanomilling-driven molecular-to-network transition. [ABSTRACT FROM AUTHOR]

Polyamorphic transformations driven by high-energy mechanical ball milling (nanomilling) are recognized in a melt-quenched glassy alloy of tetra-arsenic triselenide (As4Se3). We employed XRPD analysis complemented by thermophysical heat-transfer and micro-Raman spectroscopy studies. A straightforward interpretation of the medium-range structural response to milling-driven reamorphization is developed within a modified microcrystalline model by treating diffuse peak-halos in the XRPD patterns of this alloy as a superposition of the Bragg-diffraction contribution from inter-planar correlations, which are supplemented by the Ehrenfest-diffraction contribution from inter-atomic and/or inter-molecular correlations related to derivatives of thioarsenide As4Sen molecules, mainly dimorphite-type As4Se3 ones. These cage molecules are merely destroyed under milling, facilitating the formation of a polymerized network with enhanced calorimetric heat-transfer responses. Disruption of intermediate-range ordering, due to weakening of the FSDP (the first sharp diffraction peak), accompanied by an enhancement of extended-range ordering, due to fragmentation of structural entities responsible for the SSDP (the second sharp diffraction peak), occurs as an interplay between medium-range structural levels in the reamorphized As4Se3 glass alloy. Nanomilling-driven destruction of thioarsenide As4Sen molecules followed by incorporation of their remnants into a glassy network is proved by micro-Raman spectroscopy. Microstructure scenarios of the molecular-to-network polyamorphic transformations caused by the decomposition of the As4Se3 molecules and their direct destruction under grinding are recognized by an ab initio quantum-chemical cluster-modeling algorithm. [ABSTRACT FROM AUTHOR]

Multifunctional nanocomposites from an equimolar As4S4/Fe3O4 cut section have been successfully fabricated from coarse-grained bulky counterparts, employing two-step mechanochemical processing in a high-energy mill operational in dry- and wet-milling modes (in an aqueous solution of Poloxamer 407 acting as a surfactant). As was inferred from the X-ray diffraction analysis, these surfactant-free and surfactant-capped nanocomposites are β-As4S4-bearing nanocrystalline–amorphous substances supplemented by an iso-compositional amorphous phase (a-AsS), both principal constituents (monoclinic β-As4S4 and cubic Fe3O4) being core–shell structured and enriched after wet milling by contamination products (such as nanocrystalline–amorphous zirconia), suppressing their nanocrystalline behavior. The fluorescence and magnetic properties of these nanocomposites are intricate, being tuned by the sizes of the nanoparticles and their interfaces, dependent on storage after nanocomposite fabrication. A specific core–shell arrangement consisted of inner and outer shell interfaces around quantum-confined nm-sized β-As4S4 crystallites hosting a-AsS, and the capping agent is responsible for the blue-cyan fluorescence in as-fabricated Poloxamer capped nanocomposites peaking at ~417 nm and ~442 nm, while fluorescence quenching in one-year-aged nanocomposites is explained in terms of their destroyed core–shell architectures. The magnetic co-functionalization of these nanocomposites is defined by size-extended heterogeneous shells around homogeneous nanocrystalline Fe3O4 cores, composed by an admixture of amorphous phase (a-AsS), nanocrystalline–amorphous zirconia as products of contamination in the wet-milling mode, and surfactant. [ABSTRACT FROM AUTHOR]

The Interoceanmetal Joint Organization's (IOM) exploration license is granted in the area located within the Clarion–Clipperton Zone of the Eastern Central Pacific. All activities related to exploration of minerals in this area are beyond the limits of national jurisdiction and come under the provision of the United Nations Convention on the Law of the Sea and related regulations. The geological survey, which was the subject of the exploration, focused on the polymetallic nodule deposits. Other activities covered the tests of nodule processing, including alternative methods of metal extraction. This article describes the methodology of the bioleaching process and provides a summary of the initial results of the bioleaching test, applied to the samples of polymetallic nodules taken from the H22 exploration block of the IOM exploration area. The bioleaching efficiency under different pulp density conditions was studied. The enrichment of heterotrophic Mn-reducing microorganisms was prepared as the leaching medium. Bioleaching of the samples took place with different sample weights in order to determine the maximum possible extraction yield and the highest concentration of elements obtained in the leachate. During the bioleaching, the media were also exchanged to achieve maximum polymetallic nodule decomposition with regular addition of nutrients for heterotrophic Mn-reducing bacteria. The bioleaching efficiency of the polymetallic nodules increased to 100% (without Cu) when the pulp density was reduced to 0.1% (w/v). The discontinuous bioleaching and washing process recovered 55% Mn, 36% Ni, 15% Co, 27% Zn, and 38% Cu when the pulp density was increased to 10% (w/v). To achieve total Mn, Cu, Zn, Co, and Ni recovery from the polymetallic nodules, an intermittent bioleaching with about 25 changes of 60% of the medium was required when the pulp density was increased to 10% (w/v). Bioleaching has the potential to be used as an environmentally friendly alternative to other commonly used options for leaching and processing. [ABSTRACT FROM AUTHOR]

CuFeS2/TiO2 nanocomposite has been prepared by a simple, low-cost mechanochemical route to assess its visible-light-driven photocatalytic efficiency in Methyl Orange azo dye decolorization. The structural and microstructural characterization was studied using X-ray diffraction and high-resolution transmission electron microscopy. The presence of both components in the composite and a partial anatase-to-rutile phase transformation was proven by X-ray diffraction. Both components exhibit crystallite size below 10 nm. The crystallite size of both phases in the range of 10–20 nm was found and confirmed by TEM. Surface and morphological properties were characterized by scanning electron microscopy and nitrogen adsorption measurement. Scanning electron microscopy has shown that the nanoparticles are agglomerated into larger grains. The specific surface area of the nanocomposite was determined to be 21.2 m2·g−1. Optical properties using UV-Vis and photoluminescence spectroscopy were also investigated. CuFeS2/TiO2 nanocomposite exhibits strong absorption with the determined optical band gap 2.75 eV. Electron paramagnetic resonance analysis has found two types of paramagnetic ions in the nanocomposite. Mössbauer spectra showed the existence of antiferromagnetic and paramagnetic spin structure in the nanocomposite. The CuFeS2/TiO2 nanocomposite showed the highest discoloration activity with a MO conversion of ~ 74% after 120 min irradiation. This study has shown the possibility to prepare nanocomposite material with enhanced photocatalytic activity of decoloration of MO in the visible range by an environmentally friendly manner [ABSTRACT FROM AUTHOR]

In this study we demonstrate the synthesis of quaternary semiconductor nanocrystals of stannite Cu2FeSnS4/rhodostannite Cu2FeSn3S8 (CFTS) via mechanochemical route using Cu, Fe, Sn and S elements as precursors in one-pot experiments. Methods of X-ray diffraction (XRD), nitrogen adsorption, high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS) were applied to characterize properties of the unique nanostructures. Mechanochemical route of synthesis induced new phenomena like explosive character of reaction, where three stages could be identified and the formation of nanostructures 5&-10 nm in size. By using XPS method, Cu(I), Fe(II), Sn(IV) and S(-II) species were identified on the surface of CFTS. The value of optical band gap 1.27 eV is optimal for semiconductors applicable as absorbers in solar cells. The significant photocatalytic activity of the CFTS nanocrystals was also evidenced. The obtained results confirm the excellent properties of the quaternary semiconductor nanocrystals synthesized from earth-abundant elements. [ABSTRACT FROM AUTHOR]

The possibilities surrounding positronics, a versatile noninvasive tool employing annihilating positrons to probe atomic-deficient sub-nanometric imperfections in a condensed matter, are analyzed in application to glassy arsenoselenides g-AsxSe100−x (0 < x < 65), subjected to dry and wet (in 0.5% PVP water solution) nanomilling. A preliminary analysis was performed within a modified two-state simple trapping model (STM), assuming slight contributions from bound positron–electron (Ps, positronium) states. Positron trapping in g-AsxSe100−x/PVP nanocomposites was modified by an enriched population of Ps-decay sites in PVP. This was proven within a three-state STM, assuming two additive inputs in an overall trapping arising from distinct positron and Ps-related states. Formalism of x3-x2-CDA (coupling decomposition algorithm), describing the conversion of Ps-decay sites into positron traps, was applied to identify volumetric nanostructurization in wet-milled g-As-Se, with respect to dry-milled ones. Under wet nanomilling, the Ps-decay sites stabilized in inter-particle triple junctions filled with PVP replaced positron traps in dry-milled substances, the latter corresponding to multi-atomic vacancies in mostly negative environments of Se atoms. With increased Se content, these traps were agglomerated due to an abundant amount of Se-Se bonds. Three-component lifetime spectra with nanostructurally- and compositionally-tuned Ps-decay inputs and average lifetimes serve as a basis to correctly understand the specific "rainbow" effects observed in the row from pelletized PVP to wet-milled, dry-milled, and unmilled samples. [ABSTRACT FROM AUTHOR]

The impact of high-energy milling on glassy arsenic monoselenide g-AsSe is studied with X-ray diffraction applied to diffuse peak-halos proper to intermediate- and extended-range ordering revealed in first and second sharp diffraction peaks (FSDP and SSDP). A straightforward interpretation of this effect is developed within the modified microcrystalline approach, treating "amorphous" halos as a superposition of the broadened Bragg diffraction reflexes from remnants of some inter-planar correlations, supplemented by the Ehrenfest diffraction reflexes from most prominent inter-molecular and inter-atomic correlations belonging to these quasi-crystalline remnants. Under nanomilling, the cage-like As4Se4 molecules are merely destroyed in g-AsSe, facilitating a more polymerized chain-like network. The effect of nanomilling-driven molecular-to-network reamorphization results in a fragmentation impact on the correlation length of FSDP-responsible entities (due to an increase in the FSDP width and position). A breakdown in intermediate-range ordering is accompanied by changes in extended-range ordering due to the high-angular shift and broadening of the SSDP. A breakdown in the intermediate-range order is revealed in the destruction of most distant inter-atomic correlations, which belong to remnants of some quasi-crystalline planes, whereas the longer correlations dominate in the extended-range order. The microstructure scenarios of milling-driven reamorphization originated from the As4Se4 molecule, and its network derivatives are identified with an ab initio quantum-chemical cluster modeling code (CINCA). [ABSTRACT FROM AUTHOR]

The detailed mineralogical and microgeochemical characteristics of polymetallic nodules collected from the Interoceanmetal Joint Organization (IOM, Szczecin, Poland) claim area, Eastern Clarion-Clipperton Fracture Zone (CCFZ, Eastern Pacific) were described in this study. The obtained data were applied for the delimitation of nodule growth generations and estimation of the growth ratios (back-stripping using the Co-chronometer method). The applied methods included bulk X-ray powder diffraction (XRD) and electron probe microanalysis (EPMA), providing information about Mn-Fe minerals and clays composing nodules, as well as the geochemical zonation of the growth generations. The analyzed nodules were mostly diagenetic (Mn/Fe > 5), with less influence on the hydrogenous processes, dominated by the presence of 10-Å phyllomanganates represented by todorokite/buserite, additionally mixed with birnessite and vernadite. The specific lithotype (intranodulith), being an integral part of polymetallic nodules, developed as a result of the secondary diagenetic processes of lithification and the cementation of Fe-rich clays (potentially nontronite and Fe-rich smectite), barite, zeolites (Na-phillipsite), bioapatite, biogenic remnants, and detrital material, occurs in holes, microcaverns, and open fractures in between ore colloforms. The contents of ∑(Ni, Cu, and Co) varied from 1.54 to 3.06 wt %. Several remnants of siliceous microorganisms (radiolarians and diatoms) were found to form pseudomorphs. The applied Co-chronometer method indicated that the nodules' age is mainly Middle Pliocene to Middle Pleistocene, and the growth rates are typical of diagenetic and mixed hydrogenetic–diagenetic (HD) processes. Additionally, few nodules showed suboxic conditions of nucleation. Growth processes in the eastern part of the CCFZ deposit might have been induced with the Plio-Pleistocene changes in the paleooceanographic conditions related to the deglaciation of the Northern Hemisphere. [ABSTRACT FROM AUTHOR]

In this study, we demonstrate the feasibility of Bi-doped tetrahedrite Cu12Sb4−xBixS13 (x = 0.02–0.20) synthesis in an industrial eccentric vibratory mill using Cu, Sb, Bi and S elemental precursors. High-energy milling was followed by spark plasma sintering. In all the samples, the prevailing content of tetrahedrite Cu12Sb4S13 (71–87%) and famatinite Cu3SbS4 (13–21%), together with small amounts of skinnerite Cu3SbS3, have been detected. The occurrence of the individual Cu-Sb-S phases and oxidation states of bismuth identified as Bi0 and Bi3+ are correlated. The most prominent effect of the simultaneous milling and doping on the thermoelectric properties is a decrease in the total thermal conductivity (κ) with increasing Bi content, in relation with the increasing amount of famatinite and skinnerite contents. The lowest value of κ was achieved for x = 0.2 (1.1 W m−1 K−1 at 675 K). However, this sample also manifests the lowest electrical conductivity σ, combined with relatively unchanged values for the Seebeck coefficient (S) compared with the un-doped sample. Overall, the lowered electrical performances outweigh the benefits from the decrease in thermal conductivity and the resulting figure-of-merit values illustrate a degradation effect of Bi doping on the thermoelectric properties of tetrahedrite in these synthesis conditions. [ABSTRACT FROM AUTHOR]

This paper presents the economic structure, assumptions, and relations of deep-sea mining project assessment and the results of its evaluation, based on exploration activities and research in the field of geology, mining technology, processing technology, and environmental and legislative studies. The Interoceanmetal Joint Organization (IOM) and cooperating organizations conducted a study incorporating those elements of the project that are recognized as most important for commercial viability. On the basis of formulated financial flow of operating and capital expenses of one processing technology the possible market unit price of polymetallic nodules was estimated and the result is presented in this paper. The rapidly changing economic situation, affected inter alia by the COVID-19 pandemic, is reflected in the study and updated results are based on recent changes in metal prices. Although assumptions related to mining costs need to be confirmed during pilot mining tests, promising results have been shown in the case of the use of high-pressure acid leaching processing technology (HPAL) as well as in the case of raw ore sales. A pre-feasibility study of the project will focus on the two most promising variants of the model. [ABSTRACT FROM AUTHOR]

In this study, CuInS2/ZnS nanocrystals were synthesized by a two-step mechanochemical synthesis for the first time. In the first step, tetragonal CuInS2 was prepared from copper, indium and sulphur precursors. The obtained CuInS2 was further co-milled with zinc acetate dihydrate and sodium sulphide nonahydrate as precursors for cubic ZnS. Structural characterization of the CuInS2/ZnS nanocrystals was performed by X-ray diffraction analysis, Raman spectroscopy and transmission electron microscopy. Specific surface area of the product (86 m2/g) was measured by low-temperature nitrogen adsorption method and zeta potential of the particles dispersed in water was calculated from measurements of their electrophoretic mobility. Optical properties of the nanocrystals were determined using photoluminescence emission spectroscopy. [ABSTRACT FROM AUTHOR]