Tungsten (W), a rare metal, is categorized as a Critical and Strategic Raw Material (CRM) by the European Union (EU), with the highest economic importance of all selected CRMs since 2014. Tungsten and its derivatives are extracted from their commercial raw materials, mainly wolframite [(Fe,Mn)WO4] and scheelite (CaWO4) ores. Subsequently to mining and mineral processing, the W ore is submitted to thermal treatment and hydrometallurgy under aggressive conditions (high pressure and temperature), which are usually applied for the extraction of tungsten compounds. This paper aims to investigate a thermal route for scheelite processing using various selected chemical agents, resulting in a W-bearing material that is capable of being leached under softer conditions. In this context, a thermodynamic study of the interaction between FeWO4, MnWO4 and CaWO4 and various chemical reagents is described. The thermochemical calculations and data modeling show that, among other considerations, the reaction of CaWO4 with magnesium chloride (MgCl2) can lead to the formation of magnesium tungsten oxide (MgWO4), which appears to be more easily leachable than CaWO4. Experimental tests of the reaction of scheelite with MgCl2 appear to validate the thermodynamic predictions with satisfactory process kinetics at temperatures from 725 to 775 °C.

This review details both the conventional and emerging methods of extracting tin from cassiterite. The emerging methods reviewed include sulphuric acid leaching of SnO, cooling crystallization of SnO, sulphide leaching, alkaline leaching, and dry chlorination. From these methods, the conventional approach (direct reduction smelting) stands out as the sole method that is suitable for industrial application, with none of the emerging ones being promising enough to be a contender. The thermodynamics involved in the hydrometallurgical extraction of tin from the mineral are also discussed. ΔGo values calculated at 25 °C for the reduction–dissolution of SnO2 using reducing gases revealed feasibility only when carbon monoxide was used. An indication of the possible species produced during the hydrolysis of the oxide of the metal (SnO2 and SnO) as a function of pH (ranging from −2 to 14 and 0 to 14 for SnO2 and SnO, respectively) was noted and highlighted to link a Pourbaix diagram generated from literature data. This diagram suggests that the solubility of SnO2 in both strongly acidic and alkaline media is possible, but with a small dissolution window in each. The purification and recovery routes of the various processing techniques were then envisaged.

The chlorination of oxides of major concern in cassiterite concentrate with various chlorinating agents is investigated in light of their thermodynamic feasibilities to extract and recover their valuable metal components. Mechanisms responsible for the processes and their Gibbs free energy changes as a function of temperature to selectively separate and/or recover the metal(s) of interest and unwanted ones as their metallic chlorides are identified. Attention is given to gaseous (Cl2 and Cl2 + CO mixture) and solid (CaCl2 and MgCl2) chlorine sources, from which Cl2 + CO shows no reaction selectivity for any of the oxides but a feasible metal chloride formation for all. Chlorine gas (Cl2), on the other hand, could selectively form chlorides with metals of +2 oxidation state in their oxides, leaving those of high oxidation state unreacted. MgCl2, unlike CaCl2, is found capable of producing calcium, ferrous, and stannic chloride from their metallic oxides with enhanced reaction tendencies in the presence of silicon dioxide (SiO2). An overall study of the thermodynamic feasibility of all chlorine sources looked at alongside operational and environmental viabilities suitably suggests MgCl2 for a selective extraction of the valuable metal components in a cassiterite concentrate, in which case, moderate temperatures seem promising.

This study investigates the selective high voltage pulse (HVP) fragmentation and its role in enhancing the metallurgical performance in phosphate ore processing. We have adapted the use of HVP fragmentation to enable the complete comminution of the considered ore, without the need for additional grinding steps. The efficiency of the HVP process strongly depends upon two parameters - the discharge ratio and the electric field, which, combined, allow for an improved liberation. Furthermore, for the same feed, the high voltage pulse fragmentation provides a coarser product with fewer fines. This study also emphasizes an improved liberation of the target mineral, carbonate fluorapatite, in the 100-315 mu m fraction, while concentrating gangue minerals in the <100 mu m size fraction. These findings are supported by X-ray tomography, validating the principle of pre-weakening induced by high voltage pulses on phosphate ore and further confirming the significance of our research.

Near infrared (NIR) activable photopolymers suitable for versatile fabrication of micro-optical elements were developed. The first main objective of this article is to show that these new photopolymers can be used for microfabrication and investigate the parameters governing the microfabrication process. The impact of photonic, physico-chemical, and chemical parameters is discussed. High quality microstructures with a good control over their size and shape are demonstrated. The second main objective is to show practical examples of microlenses and waveguides implemented on single core and multiple core optical fibers, VCSELs, and glass slides are then presented. The NIR photosensitivity of this negative tone photoresists allows using the device source itself as to start the crosslinking process, which constitutes a convenient approach for micro-optics self-positioning on NIR sources and justifies the interest of such NIR photopolymer for the fabrication micro-optical elements and optical interconnects.

AbstractNear infrared (NIR) activable photopolymers suitable for versatile fabrication of micro‐optical elements were developed. The first main objective of this article is to show that these new photopolymers can be used for microfabrication and investigate the parameters governing the microfabrication process. The impact of photonic, physico‐chemical, and chemical parameters is discussed. High quality microstructures with a good control over their size and shape are demonstrated. The second main objective is to show practical examples of microlenses and waveguides implemented on single core and multiple core optical fibers, VCSELs, and glass slides are then presented. The NIR photosensitivity of this negative tone photoresists allows using the device source itself as to start the crosslinking process, which constitutes a convenient approach for micro‐optics self‐positioning on NIR sources and justifies the interest of such NIR photopolymer for the fabrication micro‐optical elements and optical interconnects.

NIR photopolymer for micro-optics applications Ihab Dika, Frédéric Diot, Véronique Bardinal, Jean-Pierre Malval, Carole Ecoffet, Aurélien Bruyant, David Barat, Benjamin Reig, Jean-Baptiste Doucet, Thierry Camps and Olivier Soppera* Ihab Dika, Frédéric Diot, Jean-Pierre Malval, Carole Ecoffet, Olivier Soppera Université de Haute-Alsace, CNRS, IS2M UMR 7361, F-68100 Mulhouse, France Université de Strasbourg, France * corresponding author : olivier.soppera@uha.fr David Barat, Benjamin Reig, Jean-Baptiste Doucet, Thierry Camps,Véronique Bardinal, LAAS CNRS,7 avenue du colonel Roche, F-31077 Toulouse, France Université de Toulouse ; UPS, INSA, INP, ISAE ; LAAS ; F-31077 Toulouse, France Aurélien Bruyant, Institut Charles Delaunay, UMR CNRS 6281, LNIO, Université de Technologie de Troyes, 12 rue Marie Curie BP 2060 10010 Troyes Cedex, France

Development of our modern society requests a number of critical and strategic elements (platinum group metals, In, Ga, Ge…) and high value added elements (Au, Ag, Se, Te, Ni…) which are often concentrated in by-products during the extraction of base metals (Cu, Pb, Zn…). Further, recycling of end-of-life materials employed in high technology, renewable energy and transport by conventional extractive processes also leads to the concentration of such chemical elements and their compounds in metallurgical by-products and/or co-products. One of these materials, copper anode slime (CAS), derived from a copper electrolytic refining factory, was used for this study. The sample was subjected to isothermal treatment from 225 to 770 °C under air atmosphere and the reaction products were systematically analyzed by scanning electron microscopy through energy dispersive spectroscopy (SEM-EDS) and X-ray diffraction (XRD) to investigate the thermal behavior of the treated sample. The main components of the anode slime (CuAgSe, Cu2-xSeyS1-y, Ag3AuSe2) react with oxygen, producing mostly copper and selenium oxides as well as Ag-Au alloys as final products at temperatures higher than 500 °C. Selenium dioxide (SeO2) is volatilized and recovered in pure state by cooling the gaseous phase, whilst copper(II) oxide, silver, gold and tellurium remain in the treatment residue.

The most economically important iron-chromium bearing minerals is chromite. In natural deposits, iron(II) is frequently substituted by magnesium(II) while chromium(III) is replaced by aluminum(III) and/or iron(III) forming a complex chromium bearing material. The majority of mined chromite is intended for the production of ferrochrome which requires a chromite concentrate with high chromium-to-iron ratio. Found mostly in the spinel chromite structure, iron cannot be removed by physical mineral processing methods. In this frame, the present work deals with the reaction of chlorine and chlorine+oxygen with selected samples of chromite concentrates for assessing the reactivity of their components towards chlorinating atmosphere, allowing the preferential removal of iron, hence meeting the chromite metallurgical grade requirements. Isothermal thermogravimetric analysis was used as a reliable approach for the kinetic reactivity investigation. Results indicated a wide difference in the thermal behavior of chromite constituents in a chlorinating atmosphere when considering their respective values of apparent activation energy oscillating from about 60 to 300 kJ/mol as a function of the sample reacted fraction. During the chromite treatment by chlorine in presence of oxygen, chromium was recovered as liquid chromyl chloride by condensation of the reaction gas phase.

The geochemistry and mineralogy of REE deposits is diverse, from carbonatite-related deposits, alkaline rocks, mineral sands and ion adsorption clays to potential by-products of phosphate and bauxite, and reuse of waste materials. Despite the large number of prospects that have been explored recently, very little additional REE production has started. A major challenge is to design effective, cost-efficient and environmentally-friendly processing and extraction. Processing flow sheets have to be constructed carefully for each deposit. Translating geochemistry and mineralogy studies, including quantitative mineralogy results, into processing characteristics can be illustrated using results from the Songwe Hill carbonatite, Malawi. Combining results with other published data then allows us to make some general conclusions about the common REE ore minerals and their geological environment, including the REE fluorcarbonate series, monazite and xenotime. The use of chemicals for REE extraction is often the largest environmental burden to mitigate. A new issue is that certain REE, such as Ce, are in oversupply, and are not being recovered in some proposed processing flowsheets. It will be important to understand the environmental and commercial implications of this development.

The investigation presented here features the design of a cleaner and greener chemical process for the conversion of industrial wastes into super-oxidizing materials. The waste of interest is the iron sulfate heptahydrate (FeSO4·7H2O) mainly generated through the sulfate route used for titanium dioxide industrial production. The products of this transformation process are alkali ferrates (A2FeO4, A = Na, K) containing iron in its hexavalent state and considered as powerful oxidants characterized by properties useful for cleaning waters, wastewaters, and industrial effluents. The proposed process includes two steps: (i) The first step consisting of the pre-mixing of two solids (AOH with FeSO4·xH2O) in a rotary reactor allowing the coating of iron sulfate in the alkali hydroxides through solid–solid reactions; and (ii) the second step involves the synthesis of alkali ferrates in a fluidized bed by oxidation of the single solid obtained in the first step in diluted chlorine. The chemical synthesis of alkali ferrates can be carried out within a timeframe of a few minutes. The usage of a fluidized bed enhanced the energy and mass transfer allowing a quasi-complete control of the ferrate synthesis process. The alkali ferrate synthesis process described here possesses many characteristics aligned with the principles of the “green chemistry”.

The geochemistry and mineralogy of REE deposits is diverse, from carbonatite-related deposits, alkaline rocks, mineral sands and ion adsorption clays to potential by-products of phosphate and bauxite, and reuse of waste materials. Despite the large number of prospects that have been explored recently, very little additional REE production has started. A major challenge is to design effective, cost-efficient and environmentally-friendly processing and extraction. Processing flow sheets have to be constructed carefully for each deposit. Translating geochemistry and mineralogy studies, including quantitative mineralogy results, into processing characteristics can be illustrated using results from the Songwe Hill carbonatite, Malawi. Combining results with other published data then allows us to make some general conclusions about the common REE ore minerals and their geological environment, including the REE fluorcarbonate series, monazite and xenotime. The use of chemicals for REE extraction is often the largest environmental burden to mitigate. A new issue is that certain REE, such as Ce, are in oversupply, and are not being recovered in some proposed processing flowsheets. It will be important to understand the environmental and commercial implications of this development.

The extraction of tin through smelting of cassiterite (SnO2) has generated considerable amounts of slag in the main production areas of South-East Asia, Africa, and South America. Tantalum and niobium naturally occur in cassiterite deposits and are concentrated in the slag during the smelting process. Tin slags have often been disposed as industrial waste despite contents of tantalum and niobium ranging from 2 to 25%. Conventional hydrometallurgical processes for the concentration of tantalum and niobium oxides utilizing high concentration of strong acids such as HF or H2SO4 are environmentally and economically challenging. This paper describes an original and greener approach for the selective dissolution of the slag amorphous matrix, and the concentration of tantalum and niobium oxides in a solid residue. Starting from a slag containing about 15% (Ta,Nb)2O5, sequential alkaline and acid leaching stages resulted in the production of a 63% (Ta + Nb) oxides concentrate, which is comparable to commercial grade of mineral concentrates.

Deep-UV (DUV) laser patterning has been widely used in recent years for micro-and nanopatterning, taking advantage of the specific properties of irradiation with high-energy photons. In this paper, we show the usefulness of DUV laser patterning for preparing surfaces with controlled chemical properties at the micro-and nanoscale. Our motivation was to develop a simple and versatile method for chemical patterning at multiscales (from mm to nm) over relatively wide areas (mm(2) to cm(2)). The chemical properties were provided by self-assembled monolayers (SAMs), prepared on glass or silicon wafers. We first investigated their modification under our irradiation conditions (ArF laser) using AFM, XPS and contact angle measurements. Photopatterning was then demonstrated with minimum feature sizes as small as 75 nm, and we showed the possibility to regraft a second SAM on the irradiated regions. Finally, we used these chemically patterned surfaces for directed self-assembly of several types of objects, such as block copolymers, sol-gel materials and liquids by vapor condensation.

The kinetics of chlorination of hematite by Cl2+O2 have been investigated in the temperature range from 600 to 1025 °C by using thermogravimetric analysis (TGA). The effects of Cl2/O2 ratio, gas velocity, temperature and partial pressure of reactive gases on the reaction rate were determined. The reaction rate of Fe2O3 chlorination increased steadily with Cl2/O2 ratio reaching the maximum for the chlorination in absence of oxygen. The hematite chlorination process by Cl2+O2 was characterized by an apparent activation energy of about 148 kJ/mol in the whole temperature range studied. The apparent reaction orders with respect to Cl2+O2, Cl2 and O2 at 750 °C were about 0.71, 1.44, and -0.61, respectively. Almost the same values of reaction orders were obtained at 950 °C.

Iron sulfate, in particular FeSO4·7H2O, is derived from titanium dioxide production and the steel pickling process. Regarding TiO2 manufacturing, the amount of the resultant FeSO4·7H2O can be as high as 6 tons per ton of produced TiO2, leading to a huge amount of ferrous sulfate heptahydrate, which is considered an environmental and economic concern for the titanium dioxide industry in European countries. The present paper focuses on the thermal treatment of ferrous sulfate (heptahydrate and monohydrate) samples under different conditions. Nonisothermal thermogravimetric (TG) analysis was used to study the behavior of iron sulfate samples at temperatures of up to 1000 °C in Cl2 + O2, O2, and N2 atmospheres. Results showed that the dehydration of iron sulfate heptahydrate in nitrogen started at room temperature and resulted in iron sulfate tetrahydrate (FeSO4·4H2O). The ferrous sulfate monohydrate (FeSO4·H2O) was formed at temperatures close to 150 °C, while the anhydrous ferrous sulfate (FeSO4) was obtained when the samples were heated in nitrogen at over 225 °C. The kinetic features of FeSO4 decomposition into Fe2O3 were revealed under isothermal conditions at temperatures ranging from 500 to 575 °C. The decomposition of iron sulfate was characterized by an apparent activation energy of around 250 kJ/mol, indicating a significant temperature effect on the decomposition process. The obtained powder iron oxide could be directed to the agglomeration unit of iron and the steelmaking process.