Copper sulfide

The formation of sulfide and oxide films on copper has been studied in sulfide solutions containing chloride and buffered to pH = 9 with borate over the temperature range 20 °C to 80 °C. The primary goal was to investigate the susceptibility of copper to pitting corrosion over a range of temperatures expected in a deep geological repository. Films were formed electrochemically and characterized using scanning electron microscopy (SEM), energy dispersive X-ray and Raman spectroscopy and X-ray diffractometry (XRD). Chalcocite (Cu 2 S) formation was observed to occur under partially transport-controlled conditions in the potential range -0.9 V to -0.3 V vs SCE. At less negative potentials ( ≥ -0.3 V vs SCE), a transition from active dissolution to partial passivation by a copper oxide film was observed. Temperature had only a minor effect on the formation of the sulfide film, but the onset of active dissolution and oxide film formation shifted to lower potentials as the temperature increased.

Quantum dot-sensitized solar cells (QDSSCs) represent a leading-edge innovation within thirdgeneration photovoltaic systems, owing to the unique light-harvesting capabilities of quantum dots (QDs), including multiple exciton generation, tunable band gaps, and high absorption coefficients. Despite their potential for achieving power conversion efficiencies (PCE) beyond those of conventional solar technologies, challenges remain; particularly in the stability and performance of counter electrodes (CEs). Platinum (Pt), while efficient, suffers from catalytic degradation in polysulfide electrolytes, limiting its suitability for QDSSC applications. This review explores the use of transition metal sulfides (TMS), such as NiS, CoS, Cu₂S, and PbS, as alternative CE materials due to their abundance, low cost, and promising electrocatalytic properties. Emphasis is placed on their compatibility with polysulfide electrolytes, structural stability, and ability to enhance interfacial charge transfer, which directly impacts overall device performance. The paper also discusses the synthesis techniques employed, chemical bath deposition and successive ionic layer adsorption and reaction, and how they influence the morphology, adhesion, and efficiency of the CEs. Among the materials reviewed, nickel sulfide-based electrodes stand out due to their low charge transfer resistance, high Jsc values, and excellent long-term operational stability. Composite materials such as NiS/PbS and Cu₂S/graphene hybrids show synergistic effects, enhancing both catalytic performance and mechanical durability. By identifying and evaluating viable alternatives to noble metals, this study underscores the critical role of CE materials in advancing QDSSC technology toward scalable, efficient, and cost-effective solar energy solutions.

In this paper, we have reported an easy, template free and squashy solution chemistry path was applied to synthesize variegated nanostructured congregation assemblies of copper nanoparticles at room temperature using hydrazinecarbothioamide coordinated Cu(II) complex through a single route molecular precursor source. The parent compounds were heated under microwave irradiation to obtain diversified CuS nanostructures in the shapes of spheres and nanotubes were found to be assemblies of either nanoplates or nanoparticles. The formation of nanostructured CuS nano particles was detailed studied by differing the synthetic conditions such as reaction time, temperature, parent compounds ratio, and the presence of counter ions. The presence of NO3 - and SO4 2- ions as counter ions were found to be suitable for the formation of nanotubes whereas the presence of Clions initiate the formation of spherical nano assemblies of CuS nano material is obtained. The synthesized samples were character...

Co-doped ZnO nanoparticles with different Cobalt contents were prepared by direct precipitation method. The materials were characterized by XRD, SEM and TEM techniques. The XRD results indicated that the particle size of pure ZnO and Co-doped ZnO is about 30-45nm. The toxic Cr(VI) in industrial wastewaters can be removed by a reduction from Cr(VI) to Cr(III). The reduction of Cr(VI) to Cr(III) can be achieved by a photocatalytic process. The effect of Co loading on the photocatalytic activity of Co-doped ZnO in the reduction of Cr(VΙ) was studied and the results are compared with the pure ZnO. The results showed that the rate of photoreduction of Cr(VΙ) over Co-doped ZnO is much higher as compared to that of pure ZnO. The photocatalytic reaction were carried out under UV radiation towards the reduction of Cr(VI) by varying different parameters such as irradiation time, pH of the solution, catalyst amount and substrate concentration.

vol. 60 (3) 2024 K. Yang, Y. Nahmad-Molinari, L.F. Camacho-Conzález, F.M. de los Santos-García, A. Lopéz-Valdivieso Development of an efficient solar concentrator and utilization in copper extraction from copper minerals J. Min. Metall. Sect. B-Metall., 60 (3) (2024) 421-433. DOI:10.2298/JMMB240222034Y

Three approaches to economical photovoltaics: conformal Cu 2 S, organic luminescent films, and PbSe nanocrystal superlattices by Ian A. Carbone I want to thank my friends and family. Without their support and guidance, I would never have finished this degree. Thanks to Gergely Zimanyi for providing me with encouragement and direction for the modeling portion of this dissertation. Thanks to Glenn Alers for advising me on the LDS film and Cu 2 S work. Special thanks to Sue for her inspiring commitment to her students. Thanks to all of my lab-mates for all of their help and support. xi

CuS nano particles synthesized by a sonication process were deposited onto oxidized multi-wall carbon nanotubes (MWCNTs) dispersed in maleic anhydride octane 1 (MAO) copolymer matrix. MWCNTs were prepared by catalytic chemical vapor deposition from ethylene over a Co, Fe/alumina catalyst, MAO was grafted with oxidized MWCNTs under sonication at 353 K for 3 h. CuS nanoparticles were prepared from copper acetate dihydrate and thiocarbamide in this matrix while heating for 2 h. The resulting nanocomposite matrix featured uniform MWCNT dispersion and a peculiar foam-like morphology which was attributed to the effect of ultrasonic cavitation. The mean diameter of the obtained embedded hexagonal CuS nanoparticles was 3.2 nm. The optical band gap of the final product was calculated to be 2.28 eV which suggests that the CuS-MWCNT-MAO nanocomposite can be evaluated as a potential solar protection material.

Currently, different metal sulfides (NiS, Co 9 S 8 , FeS 2 , and CuS) have been extensively studied as alternative electrodes for rechargeable batteries that can satisfy the performance requirements for more powerful energy supply and storage technologies for various applications and industries. Among them, copper sulfides have gained significant attention as a promising electrode material in rechargeable metal-ion (Li, Mg, Na, and Al) batteries. A wide range of synthesis routes and methods have been implemented in order to prepare various stoichiometry Cu x S (1 ≤ x ≤ 2) micro-/nanostructured materials with excellent electrochemical properties. Since the bulk microsized electrode materials have almost reached their performance limits for energy devices, the introduction of nanoscale Cu x S composites is now in high demand. This review focuses on the influence of the material morphology and dimensions on their performance in secondary batteries. The structures of Cu x S materials from zero-dimensional (0D) to 3D and their preparation are discussed. The primary purpose of this work is to provide an overview of the unique electrochemical and physical properties of particular structure and dimensionality which can promote these materials' application in the energy storage field. Along with this, this work summarizes the information on various synthesis strategies and how they can manage the morphologies of Cu x S micro-/nanocomposites. In the current fast technologically advancing society, the development of the most economically profitable and efficient synthesis routes is especially encouraged and required, and this aspect is also commented on in this review.

Ammonia leaching kinetics of a complex Cu-ore assaying 8.8% Cu and 36.1% Fe was examined. Mineralogical characterization indicated that the major phase of the ore was siderite with chalcopyrite as the major sulfide mineral. The effects of parameters such as agitation, temperature, NH 3 concentration, particle size and oxygen partial pressure (p O 2 ) were investigated. Under the standard leaching conditions of 125-212 µm particle size, 120 °C, 1.29 mol/L NH 3 and 202 kPa of p O 2 , about 83% Cu could be selectively extracted in 2.5 h. However, when using higher NH 3 concentration and lower particle size, more than 95% extraction was achieved. The leaching process was found to be surface reaction controlling. The estimated activation energy was (37.6±1.9) kJ/mol and empirical orders of reaction with respect to p O 2 and [NH 3 ] were about 0.2 and 1, respectively.

The current research is a spectroscopic study of Coumarin 334 dissolved in methanol. The range of concentrations of the prepared stock solution was (3.39x10-9 to 2.03x10-8) M. Some optical characteristics of this dye were investigated such as absorbance and transmission spectra, absorption coefficient, refractive and extinction coefficients, oscillation and dispersion energies, and energy band gap. The absorbance spectra were recorded at 452 nm using Broad Band Cavity Enhanced Absorption Spectroscopy (BBCEAS) which depends on increasing the path length of the traveling light from the source to the detector. The minimum absorbance amount was 0.07 with a low concentration of 3.39x10-9 M. As a result, the other optical properties were calculated on the basis of the lowest values of absorbance. The energy band gap, which is important to detect the electronic band structure of the material,  was determined; it was found to be equal to ~2.55 eV. The low values of the concentration made le...

The current research is a spectroscopic study of Coumarin 334 dissolved in methanol. The range of concentrations of the prepared stock solution was (3.39x10 -9 to 2.03x10 -8 ) M. Some optical characteristics of this dye were investigated such as absorbance and transmission spectra, absorption coefficient, refractive and extinction coefficients, oscillation and dispersion energies, and energy band gap. The absorbance spectra were recorded at 452 nm using Broad Band Cavity Enhanced Absorption Spectroscopy (BBCEAS) which depends on increasing the path length of the traveling light from the source to the detector. The minimum absorbance amount was 0.07 with a low concentration of 3.39x10 -9 M. As a result, the other optical properties were calculated on the basis of the lowest values of absorbance. The energy band gap, which is important to detect the electronic band structure of the material, was determined; it was found to be equal to ~2.55 eV. The low values of the concentration made less collision between the molecules in the materials and the incident light. This led to a reduction in the background noise and in the percentages of losses. Furthermore, the dispersion and single oscillator energies, which help to calculate the average strength of the inter-band optical transitions and to prepare the quantifiable information about the band structure of the material, were calculated to reduce with the increasing concentrations. The refractive and extinction coefficients were determined because they are considered important factors for the optical materials and found to increase with the increasing concentrations. As a result, the study of the optical behavior of Coumarin 334 highlighted the promising materials for photonics applications at very low concentrations. All these properties are considered the main factors to determine the usefulness of the materials in advanced applications and to develop the performance of the devices which depend on the optical characteristics.

The electric discharge assisted mechanochemical milling technique has been applied to the reduction of copper sulphide using either elemental magnesium or elemental iron as the reducing agent. X-ray diffraction was employed for phase identification of starting materials and reaction products. After only 5 min processing using the Electric discharge assisted mechanical milling (EDAMM) method, Cu 2 S + Mg can be fully reduced to Cu + MgS with small amount of CuO, and Cu 2 S + Fe can be partially reduced to Cu + Cu5FeS4 (bornite). Secondary electron imaging combined with X-ray mapping was used to investigate the distribution of elements within the processed powder particles. In the case of the Mg reduced sample the product comprised large Cu grains of purity >98%, surrounded by regions of agglomerated, small particles of Cu and MgS. In the case of the Fe partially reduced sample the product comprised a mixture of Cu plus Fe phases, frequently surrounded by regions containing the bornite phase. The morphological evidence of the existence of deformed and some re-melted particles was consistent with arguments that high local temperatures can be achieved during EDAMM processing. However the SEM results also indicated that the primary reduction reaction mechanism involved the formation of agglomerates of small particles that did not exhibit melting. Further experiments under impulse plasma mode, both with and without conventional milling applied, demonstrated that a critical condition for the reduction reactions to occur is not based on temperature alone, but on how long the particles are processed within the in the gap between the milling rod and the base, under what may be described as Dusty Plasma conditions.

We report here the influence of thickness on the photosensing properties of copper sulfide (CuS) thin films. The CuS films were deposited onto glass substrate by using a simple and cost effective chemical bath deposition method. The changes in film thickness as a function of time were monitored. The films were characterized using X-ray diffraction technique (XRD), field emission scanning electron microscopy (FE-SEM), optical measurement techniques and electrical measurement. X-ray diffraction results indicate that all the CuS thin films have an orthorhombic (covellite) structure with preferential orientation along (113) direction. The intensity of the diffraction peaks increases as thickness of the film increases. Uniform deposition having nanocrystalline granular morphology distributed over the entire glass substrate was observed through FE-SEM studies. The crystalline and surface properties of the CuS thin films improved with increase in the film thickness. Transmittance (except for 210 nm thick CuS film) together with band gap values was found to decrease with increase in thickness. I-V measurements under dark and illumination condition show that the CuS thin films give a good photoresponse.

We report here the influence of thickness on the photosensing properties of copper sulfide (CuS) thin films. The CuS films were deposited onto glass substrate by using a simple and cost effective chemical bath deposition method. The changes in film thickness as a function of time were monitored. The films were characterized using X-ray diffraction technique (XRD), field emission scanning electron microscopy (FE-SEM), optical measurement techniques and electrical measurement. X-ray diffraction results indicate that all the CuS thin films have an orthorhombic (covellite) structure with preferential orientation along (113) direction. The intensity of the diffraction peaks increases as thickness of the film increases. Uniform deposition having nanocrystalline granular morphology distributed over the entire glass substrate was observed through FE-SEM studies. The crystalline and surface properties of the CuS thin films improved with increase in the film thickness. Transmittance (except for 210 nm thick CuS film) together with band gap values was found to decrease with increase in thickness. I-V measurements under dark and illumination condition show that the CuS thin films give a good photoresponse.

We demonstrate dual interface formation in nanocrystals (NCs) through cation exchange, creating epitaxial heterostructures within spherical NCs. The thickness of the inner-disk layer can be tuned to form two-dimensional (2D), single atomic layers (<1 nm). During the cation exchange reaction from copper sulfide to zinc sulfide (ZnS), we observe a solid-solid phase transformation of the copper sulfide phase in heterostructured NCs. As the cation exchange reaction is initiated, Cu ions replaced by Zn ions at the interfaces are accommodated in intrinsic Cu vacancy sites present in the initial roxbyite (Cu 1.81 S) phase of copper sulfide, inducing a full phase transition to djurleite (Cu 1.94 S)/low chalcocite (Cu 2 S), a more thermodynamically stable phase than roxbyite. As the reaction proceeds and reduces the size of the copper sulfide layer, the epitaxial strain at the interfaces between copper sulfide and ZnS increases and is maximized for a copper sulfide disk ∼5 nm thick. To minimize this strain energy, a second phase transformation occurs back to the roxbyite phase, which shares a similar sulfur sublattice to wurtzite ZnS. The observation of a solid-solid phase transformation in our unique heterostructured NCs provides a new pathway to control desired phases and an insight into the influence of cation exchange on nanoscale phase transitions in heterostructured materials.

We demonstrate dual interface formation in nanocrystals (NCs) through cation exchange, creating epitaxial heterostructures within spherical NCs. The thickness of the inner-disk layer can be tuned to form two-dimensional (2D), single atomic layers (<1 nm). During the cation exchange reaction from copper sulfide to zinc sulfide (ZnS), we observe a solid-solid phase transformation of the copper sulfide phase in heterostructured NCs. As the cation exchange reaction is initiated, Cu ions replaced by Zn ions at the interfaces are accommodated in intrinsic Cu vacancy sites present in the initial roxbyite (Cu 1.81 S) phase of copper sulfide, inducing a full phase transition to djurleite (Cu 1.94 S)/low chalcocite (Cu 2 S), a more thermodynamically stable phase than roxbyite. As the reaction proceeds and reduces the size of the copper sulfide layer, the epitaxial strain at the interfaces between copper sulfide and ZnS increases and is maximized for a copper sulfide disk ∼5 nm thick. To minimize this strain energy, a second phase transformation occurs back to the roxbyite phase, which shares a similar sulfur sublattice to wurtzite ZnS. The observation of a solid-solid phase transformation in our unique heterostructured NCs provides a new pathway to control desired phases and an insight into the influence of cation exchange on nanoscale phase transitions in heterostructured materials.

We demonstrate dual interface formation in nanocrystals (NCs) through cation exchange, creating epitaxial heterostructures within spherical NCs. The thickness of the inner-disk layer can be tuned to form two-dimensional (2D), single atomic layers (&lt;1 nm). During the cation exchange reaction from copper sulfide to zinc sulfide (ZnS), we observe a solid-solid phase transformation of the copper sulfide phase in heterostructured NCs. As the cation exchange reaction is initiated, Cu ions replaced by Zn ions at the interfaces are accommodated in intrinsic Cu vacancy sites present in the initial roxbyite (Cu1.81S) phase of copper sulfide, inducing a full phase transition to djurleite (Cu1.94S)/low chalcocite (Cu2S), a more thermodynamically stable phase than roxbyite. As the reaction proceeds and reduces the size of the copper sulfide layer, the epitaxial strain at the interfaces between copper sulfide and ZnS increases and is maximized for a copper sulfide disk ∼ 5 nm thick. To minimiz...

Patterned copper sulfide (Cu x S) microstructures on Si (1 1 1) wafers were successfully fabricated by a relatively simple solution growth method using copper sulfate, ethylenediaminetetraacetate and sodium thiosulfate aqueous solutions as precursors. The Cu x S particles were selectively deposited on a patterned self-assembled monolayer of 3-aminopropyltriethoxysilane regions created by photolithography. To obtain high quality Cu x S films, preparative conditions such as concentration, proportion, pH and temperature of the precursor solutions were optimized. Various techniques such as optical microscopy, atomic force microscopy (AFM), X-ray diffraction, optical absorption and scanning electrochemical microscopy (SECM) were employed to examine the topography and properties of the micro-patterned Cu x S films. Optical microscopy and AFM results indicated that the Cu x S micro-pattern possessed high selectivity and clear edge resolution. From combined X-ray diffraction analysis and optical band gap calculations we conclude that Cu 9 S 5 (digenite) was the main phase within the resultant Cu x S film. Both SECM image and cyclic voltammograms confirmed that the Cu x S film had good electrical conductivity. Moreover, from SECM approach curve analysis, the apparent electron-transfer rate constant (k) in the micro-pattern of Cu x S dominated surface was estimated as 0.04 cm/s. The SECM current map showed high edge acuity of the micro-patterned Cu x S.

The insertion of polyethyleneoxide in a lamellar copper iron sulfide of formula CuFeS2 by an exchange reaction of potassium from KCuFeS2 with an aqueous solution of the polymer was performed. The characterization of the new compound by X-ray diffraction and IR absorption spectroscopy shows that the layer structure of the precursor has been retained and that the polymer adopts a zigzag configuration between the layers.

In this paper a model of conventional and electrochemical bioleaching of high grade complex copper sulfide ores or flotation concentrates in isothermal stirred tank reactors is presented and compared to experimental data. Experiments were conducted in an electrobioreactor using a mixed culture of moderate thermophile microorganisms at pulp density 20% (w/v), leaching time 10 days, stirring rate 600 rpm and temperature 50 °C. The behavior of conventional and electrochemical bioleaching processes was described with a combined reaction-based kinetic model. The model considers the effects of mineralogical composition of the feed, the properties of the initial solution, the presence of iron-and sulfur oxidizing microorganisms and both the passivation and electroreduction of chalcopyrite on the values of copper recovery, pH and redox potential during the processes. Comparing the values obtained from the integrated semi-empirical model with the experimental data showed that the model results are in good agreement with the real leaching data of copper recovery, ORP (oxidation reduction potential) and pH for the mentioned processes under different experimental conditions.

The present study aimed to enhance the electrical conductivity of carbon nanotube (CNT) fibers by introducing copper sulfide (CuS) into them. CuS forms a very stable compound with an electrical conductivity as high as 10 6 S/m, and it was introduced into CNT fibers by treating them with polyethyleneimine (PEI) to introduce amine groups on the CNTs. The CNT fibers were then treated with a solution of copper sulfate/sodium thiosulfate, which increased their electrical conductivity by ≥100 % (4×10 5 S/m) relative to that of untreated CNT fibers. This study also examined how the CuS plating changed the structure, morphology, and mechanical properties of CNT fibers. The results indicate that the modulus of elasticity of CuS-plated CNTs increased by 2.86 times (11.34 N/tex) and the elongation-at-break decreased by half.

In this study, uniform gold (Au) nanoparticles (NPs) were prepared using seed-mediated growth method. The particle size was controlled by tuning the dosage of seed solution. Au@PS core-shell NPs were then synthesized by introducing a polystyrene (PS) shell (2-3 nm thick) around the core of Au NPs (115 nm). Evaluation of the surface plasmon (SP) optical properties indicated that wavelength of SP resonance of Au NPs increased gradually with increase in the particle size. This red shift was about 0.92 nm per 1 nm increase in particle size. The results also indicated that the zeta potential and optical properties of Au NPs could be adjusted by coating PS on the outside. Therefore, surface modifications and surface coating were effective ways to control the optical properties of Au NPs.

The Ag-Cu-S layer formed on PE demonstrated a wide variation in thickness. The cross-section showed the average thickness of sulfide layers on PE increase from 1.9 µm to 5.6 µm with the increase in the sulfurization time and from 1.9 µm to 3.9 µm with the increase of treating time in the solution of copper salts. The electronic micrographs of the sulfide layers indicate the creation of an irregular but continuous base of small dendrites and agglomerates. With the increase in the sulfurization time and treating time in copper (II/I) salt solution observed an increase of the agglomerates size. Energy dispersive spectroscopy results indicate that modified layers are poor in copper (0.5 at. % -1.5 at. %). The atomic ratios of Ag/Cu/S, calculated from the quantification of the peaks (excluded C and O elements) give the values (%) of 8.3:1.5:4.4, 8.7:0.5:4.3 and 23:1.2:10.9, respectively. In all cases, energy dispersive spectroscopy measurements revealed the modified layers are nearly stoichiometric Ag 2 S.

Cu x S layers on polyamide obtained by a sorption-diffusion method have been studied. These layers are formed when ions of higher polythionates and sulfur sorbed into polyamide react with a solution of Cu(I-II) salt. By potentiometric studies it has been determined that x varies in the interval 1< x < 2 in electrically conductive or semiconductive copper sulfide layers. The composition of the Cu x S layer changes more significantly during the first 30 days in the direction of x decreasing. X-ray diffraction studies of the Cu x S layers revealed six phases: with x = 2 (chalcocite), x = 1.9375 (djurleite), x = 1.75 (anilite), x = 1.12 (yarrowite), x = 1.06 (talnakhite), and x = 1 (covellite). The phase composition of the Cu x S layer depends on the period of keeping in Cu(I-II) salt solution and on the sulfur concentration in the polyamide.

Semiconductive and electrically conductive copper sulfide thin layers are widely studied and used in various fields of modern technology. Polymers with thin sulfide layers belong to composites. Those composite materials are of particular interest for the fabrication of substrates for deposition of metal and semiconductor, solar selective coatings, solar cells, photoconductors, sensors etc. Practical application of copper sulfide coatings in various fields of engineering stimulates the interest in developing of new technologies. A sorption-diffusion method of obtaining copper sulfide layers is a new technology in which, after adsorption of the sulfuration agent, the polymer substance is treated with copper salt aqueous solution. In present study as polymer sulfuration agent polythionic acid (H 2 S n O 6 , n = 9-45) aqueous solutions were used. Highly sulfured polythionic acids were synthesized for the first time in the Kaunas

12 O 6 , has been investigated. The measurement of IR and UV absorption spectra has shown that sulfur is sorbed on -it is diffused in the PA films in the form of polythionate anions. The concentration of sulfur in PA increases with the increase in the sulfurization time, the sulfur content in the polythionate molecules and the temperature of the sulfur precursor solution. The concentrations of sulfur obtained in the polymer treated with a solution of dodecathionic acid (up to ~8 mmol/cm 3 ) are significantly higher than those obtained in the PA films treated with the solutions of lower potassium polythionates (up to ~0.07-0.22 mmol/cm 3 ). Copper sulfide layers are formed on the surface of the PA film if the sulfurized polymer is treated with a solution of copper(II / I) salts. The conditions of polymer initial sulfurization determine the concentration of copper in PA, the stoichiometric composition of Cu x S layers and the variation of the electrical sheet resistance of Cu x S layers. The concentration of copper in PA increases with the increase in the sulfurization time, the sulfur content in the polythionate anion and the temperature of the precursor solution, and varies from 0.0035 to ~8 mmol/cm 3 . Ten Cu x S phases -chalcocite (Cu 2 S and Cu 1.96 S), anilite (Cu 7 S 4 and Cu 7 S 5 ), djurleite (Cu 31 S 16 and Cu 19375 S), copper sulfide (CuS 2 ), digenite (Cu 9 S 5 ), yarrowite (Cu 9 S 8 ) and covelline (CuS) -were identified on copper sulfide layers on the polymer surface by X-ray diffraction analysis. The electrical sheet resistance of Cu x S layers obtained decreases with the increase in the sulfurization duration and temperature, and the number of sulfur atoms in the polythionate anion.

Cu x S layers on polyamide obtained by a sorption-diffusion method have been studied. These layers are formed when ions of higher polythionates and sulfur sorbed into polyamide react with a solution of Cu(I-II) salt. By potentiometric studies it has been determined that x varies in the interval 1< x < 2 in electrically conductive or semiconductive copper sulfide layers. The composition of the Cu x S layer changes more significantly during the first 30 days in the direction of x decreasing. X-ray diffraction studies of the Cu x S layers revealed six phases: with x = 2 (chalcocite), x = 1.9375 (djurleite), x = 1.75 (anilite), x = 1.12 (yarrowite), x = 1.06 (talnakhite), and x = 1 (covellite). The phase composition of the Cu x S layer depends on the period of keeping in Cu(I-II) salt solution and on the sulfur concentration in the polyamide.

Lithuania) during long period of time deals mainly with the chemistry of chalcogens-sulfur, selenium and tellurium. During last three decades and at present an object of our applied and theoretical studies is the mechanism of chalcogen compounds’ reactions, synthesis and study of derivatives of hydrides of chalcogens (H2Sx, H2Sex,H2Tex), use of polychalcogen compounds. During last decade exceptionally interesting property of compounds rich in low oxidation state chalcogen atoms (particularly of polysulphides, polythionates and seleno- and telluropolythionates) was found – they act as chalcoganating agents towards dielectrics (polymers, plastics, glass, amorphous silicon). Further interaction of chalcogenized dielectrics with copper (I/II) salt solution leads to the formation of CuxS,CuxSe, CuxTe and mixed- CuxS-CuySe and CuxS-CuyTe thin films, which have different electric transport properties, e.g. are semiconductors or electrical conductors. The preparative conditions such as conc...

It is shown that the water solution of dodecathionic acid, H 2 S 12 O 6 , acts effectively as the sulfuration agent of polyamide 6. The study of the kinetics of sulfur sorptiondiffusion into polyamide 6 at the temperatures of 20–50 °C showed that the values of sulfur concentration obtained in polyamide 6 (up to ~7.5 mmol·cm –3 ) increase with the increase of the duration of treatment and the temperature of H 2 S 12 O 6 solution. Copper sulfide, Cu x S, layers are formed on the surface of polyamide 6 film, if the sulfured polymer is treated with a solution of Cu(II/I) salt at temperature of 78 °C: the anionic particles S 12 O 6 2– containing sulfur atoms of low oxidation state react with the copper ions. The conditions the initial sulfuration of the polymer determine the concentration of copper and the composition of sulfide layer: the concentration of copper in the polyamide 6 film increases (up to 9.5 mmol·cm –3 ) with the increase of the duration and temperature of the polymer sul...

12 O 6 , has been investigated. The measurement of IR and UV absorption spectra has shown that sulfur is sorbed on -it is diffused in the PA films in the form of polythionate anions. The concentration of sulfur in PA increases with the increase in the sulfurization time, the sulfur content in the polythionate molecules and the temperature of the sulfur precursor solution. The concentrations of sulfur obtained in the polymer treated with a solution of dodecathionic acid (up to ~8 mmol/cm 3 ) are significantly higher than those obtained in the PA films treated with the solutions of lower potassium polythionates (up to ~0.07-0.22 mmol/cm 3 ). Copper sulfide layers are formed on the surface of the PA film if the sulfurized polymer is treated with a solution of copper(II / I) salts. The conditions of polymer initial sulfurization determine the concentration of copper in PA, the stoichiometric composition of Cu x S layers and the variation of the electrical sheet resistance of Cu x S layers. The concentration of copper in PA increases with the increase in the sulfurization time, the sulfur content in the polythionate anion and the temperature of the precursor solution, and varies from 0.0035 to ~8 mmol/cm 3 . Ten Cu x S phases -chalcocite (Cu 2 S and Cu 1.96 S), anilite (Cu 7 S 4 and Cu 7 S 5 ), djurleite (Cu 31 S 16 and Cu 19375 S), copper sulfide (CuS 2 ), digenite (Cu 9 S 5 ), yarrowite (Cu 9 S 8 ) and covelline (CuS) -were identified on copper sulfide layers on the polymer surface by X-ray diffraction analysis. The electrical sheet resistance of Cu x S layers obtained decreases with the increase in the sulfurization duration and temperature, and the number of sulfur atoms in the polythionate anion.

CuxS layers on polyamide obtained by a sorption-diffusion method have been studied. These layers are formed when ions of higher polythionates and sulfur sorbed into polyamide react with a solution of Cu(I-II) salt. By potentiometric studies it has been determined that x varies in the interval 1&lt; x &lt; 2 in electrically conductive or semiconductive copper sulfide layers. The composition of the CuxS layer changes more significantly during the first 30 days in the direction of x decreasing. X-ray diffraction studies of the CuxS layers revealed six phases: with x = 2 (chalcocite), x = 1.9375 (djurleite), x = 1.75 (anilite), x = 1.12 (yarrowite), x = 1.06 (talnakhite), and x = 1 (covellite). The phase composition of the CuxS layer depends on the period of keeping in Cu(I-II) salt solution and on the sulfur concentration in the polyamide.

The Ag-Cu-S layer formed on PE demonstrated a wide variation in thickness. The cross-section showed the average thickness of sulfide layers on PE increase from 1.9 µm to 5.6 µm with the increase in the sulfurization time and from 1.9 µm to 3.9 µm with the increase of treating time in the solution of copper salts. The electronic micrographs of the sulfide layers indicate the creation of an irregular but continuous base of small dendrites and agglomerates. With the increase in the sulfurization time and treating time in copper (II/I) salt solution observed an increase of the agglomerates size. Energy dispersive spectroscopy results indicate that modified layers are poor in copper (0.5 at. % -1.5 at. %). The atomic ratios of Ag/Cu/S, calculated from the quantification of the peaks (excluded C and O elements) give the values (%) of 8.3:1.5:4.4, 8.7:0.5:4.3 and 23:1.2:10.9, respectively. In all cases, energy dispersive spectroscopy measurements revealed the modified layers are nearly stoichiometric Ag 2 S.

Semiconductive and electrically conductive layers of copper sulfides on the polyamide 6 (PA) surface were formed using the sorption-diffusion method and a water solution of potassium pentathionate, K 2 S 5 O 6, as a precursor of polymer sulfurization. Pentathionate anions containing chains of divalent sulfur atoms of low oxidation state, -O 3 S-S-S-S-SO 3 -, are sorbed-diffused into PA films if they are treated with K 2 S 5 O 6 solution. The concentration of sorbed sulfur increases with an increase of the temperature and concentration of the precursor solution and the duration of PA treatment. Cu x S layers are formed on the surface of PA film when a sulfurized polymer is treated with the water solution of copper(II / I) salt: pentathionate anions react with copper ions. The concentration of copper increases (up to ~40 mg • g -1 ) with increasing the concentration and temperature of the precursor solution. XRD results confirmed the formation of Cu x S layers on the surface of PA. The phase composition of Cu x S layer depends on the concentration and temperature of potassium pentathionate solution and on the duration of initial treatment in the K 2 S 5 O 6 solution. The layers are composed of the low-conductive tetragonal chalcocite, Cu 1.96 S, monoclinic djurleite, Cu 1.9375 S, electrically conductive rhomhedral digenite, Cu 9 S 5 , orthorhombic anilite, Cu 7 S 4 , and cubic CuS 2 . The phase composition determines the electrical characteristics of the layers obtained: the sheet resistance varies from 0.104 to 1.52 • 10 3 KΩ / □. X-ray photoelectron spectroscopy confirmed formation of copper sulfides of various phases. The regularities established in the present work enable formation of Cu x S layers of a desirable composition and conductivity.

Cu x S layers on polyamide obtained by a sorption-diffusion method have been studied. These layers are formed when ions of higher polythionates and sulfur sorbed into polyamide react with a solution of Cu(I-II) salt. By potentiometric studies it has been determined that x varies in the interval 1< x < 2 in electrically conductive or semiconductive copper sulfide layers. The composition of the Cu x S layer changes more significantly during the first 30 days in the direction of x decreasing. X-ray diffraction studies of the Cu x S layers revealed six phases: with x = 2 (chalcocite), x = 1.9375 (djurleite), x = 1.75 (anilite), x = 1.12 (yarrowite), x = 1.06 (talnakhite), and x = 1 (covellite). The phase composition of the Cu x S layer depends on the period of keeping in Cu(I-II) salt solution and on the sulfur concentration in the polyamide.

Semiconductive and electrically conductive copper sulfide thin layers are widely studied and used in various fields of modern technology. Polymers with thin sulfide layers belong to composites. Those composite materials are of particular interest for the fabrication of substrates for deposition of metal and semiconductor, solar selective coatings, solar cells, photoconductors, sensors etc. Practical application of copper sulfide coatings in various fields of engineering stimulates the interest in developing of new technologies. A sorption-diffusion method of obtaining copper sulfide layers is a new technology in which, after adsorption of the sulfuration agent, the polymer substance is treated with copper salt aqueous solution. In present study as polymer sulfuration agent polythionic acid (H 2 S n O 6 , n = 9-45) aqueous solutions were used. Highly sulfured polythionic acids were synthesized for the first time in the Kaunas

Copper sulfide is a promising p-type inorganic semiconductor for optoelectronic devices such as solar cells, due its small band gap energy and its electrical properties. In this work nanocrystalline copper sulfide (CuxS), with two stoichiometric ratios (x = 2, 1.8) was obtained by one-pot synthesis at 220, 230, 240 and 260 °C in an organic solvent and amorphous CuxS was obtained in aqueous solution. Nanoparticle-like nucleation centers are formed at lower temperatures (220 °C), mixtures of morphologies (nanorods, nanodisks and nanoprisms) are seen at 230 and 240 °C, in which the nanodisks are predominant, while big hexagonal/prismatic crystals are obtained at 260 °C according to TEM results. A mixture of chalcocite and digenite phases was found at 230 and 240 °C, while a clear transition to a pure digenite phase was seen at 260 °C. The evolution of morphology and transition of phases is consistent to the electrical, optical, and morphological properties of the copper sulfide. In fac...

In this research, the spectral detection of copper oxide is reported from different combustion tests of chalcopyrite particles and copper concentrates. Combustion experiments were performed in a bench reactor. In all the tests, the radiation emitted from the sulfide particle reactions was captured in the VIS–NIR range. The obtained spectral data were processed by using the airPLS (adaptive iteratively reweighted penalized least squares) algorithm to remove their baseline, and principal component analysis (PCA) and the multivariate curve resolution method alternate least squares (MCR-ALS) methods were applied to identify the emission lines or spectral bands of copper oxides. The extracted spectral pattern is directly correlated with the emission profile reported in the literature, evidencing the potential of using spectral analysis techniques on copper sulfide combustion spectra.

In this study, two copper(II) complexes, [Cu(C6H8N3S2)2]Cl2 (1) and [Cu(C7H10N3S2)2]Cl2·H2O (2), were synthesized from 2-(thiophen-2-ylmethylene)hydrazine-1-carbothioamide (L1H) and 2-(1-(thiophen-2-yl)ethylidene)hydrazine-1-carbothioamide (L2H) respectively and characterized using various spectroscopic techniques and elemental analyses. The as-prepared complexes were used as single-source precursors for the synthesis of oleylamine-capped (OLA@CuxSy), hexadecylamine-capped (HDA@CuxSy), and dodecylamine-capped (DDA@CuxSy) copper sulphide nanoparticles (NPs) via the thermolysis method at 190 °C and 230 °C and then characterized using powder X-ray diffraction (p-XRD), UV-visible spectroscopy, transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The p-XRD diffraction patterns confirmed the formation of crystalline rhombohedral digenite Cu9S5 with the space group R-3m. The TEM images showed the formation of nanoparticles of various shapes including hexagonal, r...

Cu o Cu 2+ S 2- Cu 2+ CuO CuS Cu 2+ Sulfidation Cu o CuS Agar Agar/CuS NP nanocomposite films Glycerol 90 o C Improved UV-shielding, water vapor barrier property, and mechanical strength Potent antibacterial activity against food-borne pathogens Agar Agar/Cus 0.25 Agar/Cus 0.5 Agar/Cus 1.5 Agar/Cus 2.0

vol. 60 (3) 2024
K. Yang, Y. Nahmad-Molinari, L.F. Camacho-Conzález, F.M. de los Santos-García, A. Lopéz-Valdivieso
Development of an efficient solar concentrator and utilization in copper extraction from copper minerals
J. Min. Metall. Sect. B-Metall., 60 (3) (2024) 421-433. DOI:10.2298/JMMB240222034Y

The discoloring interaction between the artist's pigments cadmium yellow and the copper-containing malachite, an interaction that is conjectured to cause black spotting in oil paintings of the 19th and early 20th centuries, was examined using X-ray mapping and scatter diagram analysis. The application of these coupled techniques confirmed that copper sulfide phases were produced during discoloration reaction. Scatter diagram analysis indicated that two copper sulfide stoichiometries ~CuS and Cu 3 S 2 ! were present as reaction products where previously only crystalline CuS ~covellite! had been identified by X-ray diffraction. The results demonstrate the potential of X-ray mapping coupled with scatter diagram analysis for the identification of both crystalline and X-ray amorphous phases produced by such complex heterogeneous interactions and their applicability to the investigation of interactions of artists' pigments.

The discoloring interaction between the artist&#39;s pigments cadmium yellow and the copper-containing malachite, an interaction that is conjectured to cause black spotting in oil paintings of the 19th and early 20th centuries, was examined using X-ray mapping and scatter diagram analysis. The application of these coupled techniques confirmed that copper sulfide phases were produced during discoloration reaction. Scatter diagram analysis indicated that two copper sulfide stoichiometries (CuS and Cu3S2) were present as reaction products where previously only crystalline CuS (covellite) had been identified by X-ray diffraction. The results demonstrate the potential of X-ray mapping coupled with scatter diagram analysis for the identification of both crystalline and X-ray amorphous phases produced by such complex heterogeneous interactions and their applicability to the investigation of interactions of artists&#39; pigments.

The structural changes in Cu" S films have been monitored by x-ray diffraction and correlated to the chemical changes taking place on the Cu" S surface, the latter monitored by XPS. The results show: evaporated Cu" S films contained chalcocite, free copper phases, and probably a third phase (of sulfur); resistivity is related to the amounts of free Cu and S in the film; air heat treatments converted chalcocite to Cu deficient phases and resulted in the disappearance of the sulfide and predominance of CuS0 4 'nH 2 0 and CuO; argon heat treatment tended to react Cu and S to form Cu. S; Cd is detected on the surface of Cu" S deposited onto CdS and is significantly increased in amount by heat treatments. These results can be related to chemical processes occurring on Cu" S/CdS and Cu" S/(Zn,Cd)S solar cells. For the CdS cell, oxides and sulfates of Cu and Cd are found on the Cu" S surface and the sulfates are enhanced by the heat treatment in moist air. CuO and CuS0 4 are formed in the absence of Cd, and dominate the Cu" S surface.

The structural changes in CuxS films have been monitored by x-ray diffraction and correlated to the chemical changes taking place on the CuxS surface, the latter monitored by XPS. The results show: evaporated CuxS films contained chalcocite, free copper phases, and probably a third phase (of sulfur); resistivity is related to the amounts of free Cu and S in the film; air heat treatments converted chalcocite to Cu deficient phases and resulted in the disappearance of the sulfide and predominance of CuSO4⋅nH2O and CuO; argon heat treatment tended to react Cu and S to form CuxS; Cd is detected on the surface of CuxS deposited onto CdS and is significantly increased in amount by heat treatments. These results can be related to chemical processes occurring on CuxS/CdS and CuxS/(Zn,Cd)S solar cells. For the CdS cell, oxides and sulfates of Cu and Cd are found on the CuxS surface and the sulfates are enhanced by the heat treatment in moist air. CuO and CuSO4 are formed in the absence of Cd...

Hyperspectral-enhanced dark field microscopy to correlate Au/CuS NPs’ changes in their physicochemical properties induced by cellular environments with their functionality as photothermal probes by tracking their scattering profile evolution in real time.