Effect of Copper Selenide Modification on the Conductivity of PA6, PA66, PAN,and PES Fibers

Textile production has been steadily increasing for a few decades and, as a result, the amount of industrial textile waste is also increasing. This waste can be reused as raw material to produce new functional composites. Such materials can be used for special purposes with varying combinations of physical and chemical properties by using polymers modified with thin semiconductive or electrically conductive layers of binary inorganic compounds. In this paper, a study of the possibilities of altering the properties of synthetic fiber conductivity by modification with copper selenide is presented. A two-step adsorption/diffusion method was used for the copper selenide layer forming on the surface of the fibers. The treatment process was repeated cyclically. To evaluate the morphological properties of Cu_xSe treated fibers, scanning electron microscopy (SEM) and energy dispersion X-ray (EDX) were performed. The study showed that the chosen modification method is more suitable for PA and PAN fibers. Dense layers of copper selenides were successfully formed on their surface, which significantly reduced their electrical resistance.     

Effect of In-Incorporation and Annealing on CuxSe Thin Films

A study of indium-incorporated copper selenide thin-film deposition on a glass substrate using the successive ionic adsorption and reaction method (SILAR) and the resulting properties is presented. The films were formed using these steps: selenization in the solution of diseleniumtetrathionate acid, treatment with copper(II/I) ions, incorporation of indium(III), and annealing in an inert nitrogen atmosphere. The elemental and phasal composition, as well as the morphological and optical properties of obtained films were determined. X-ray diffraction data showed a mixture of various compounds: Se, Cu_0.87Se, In₂Se₃, and CuInSe₂. The obtained films had a dendritic structure, agglomerated and not well-defined grains, and a film thickness of ~90 μm. The band gap values of copper selenide were 1.28–1.30 eV and increased after indium-incorporation and annealing. The optical properties of the formed films correspond to the optical properties of copper selenide and indium selenide semiconductors.     

Thermoelectric Properties of Cu2Se Synthesized by Hydrothermal Method and Densified by SPS Technique

The aim of the work was to obtain copper (I) selenide Cu₂Se material with excellent thermoelectric properties, synthesized using the hydrothermal method and densified by the spark plasma sintering (SPS) method. Chemical and phase composition studies were carried out by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) methods. Measurements of thermoelectric transport properties, i.e., electrical conductivity, the Seebeck coefficient, and thermal conductivity in the temperature range from 300 to 965 K were carried out. Based on these results, the temperature dependence of the thermoelectric figure of merit ZT as a function of temperature was determined. The obtained, very high ZT parameter (ZT~1.75, T = 965 K) is one of the highest obtained so far for undoped Cu₂Se.     

Copper Chalcogenide–Copper Tetrahedrite Composites—A New Concept for Stable Thermoelectric Materials Based on the Chalcogenide System

For the first time, an alternative way of improving the stability of Cu-based thermoelectric materials is proposed, with the investigation of two different copper chalcogenide–copper tetrahedrite composites, rich in sulfur and selenium anions, respectively. Based on the preliminary DFT results, which indicate the instability of Sb-doped copper chalcogenide, the Cu_1.97S–Cu₁₂Sb₄S₁₃ and Cu_2−xSe–Cu₃SbSe₃ composites are obtained using melt-solidification techniques, with the tetrahedrite phase concentration varying from 1 to 10 wt.%. Room temperature structural analysis (XRD, SEM) indicates the two-phase structure of the materials, with ternary phase precipitates embed within the copper chalcogenide matrix. The proposed solution allows for successful blocking of excessive Cu migration, with stable electrical conductivity and Seebeck coefficient values over subsequent thermal cycles. The materials exhibit a p-type, semimetallic character with high stability, represented by a near-constant power factor (PF)—temperature dependences between individual cycles. Finally, the thermoelectric figure-of-merit ZT parameter reaches about 0.26 (623 K) for the Cu_1.97S–Cu₁₂Sb₄S₁₃ system, in which case increasing content of tetrahedrite is a beneficial effect, and about 0.44 (623 K) for the Cu_2−xSe–Cu₃SbSe₃ system, where increasing the content of Cu₃SbSe₃ negatively influences the thermoelectric performance.     

Effect of Reducing Agent on Characteristics and Antibacterial Activity of Copper-Containing Particles in Textile Materials

Textile materials modified with copper-containing particles have antibacterial and antiviral properties that have prospects for use in healthcare. In the study, textile materials were saturated with copper-containing particles in their entire material volume by the absorption/diffusion method. The antibacterial properties of modified textile materials were confirmed by their inhibitory effect on Staphylococcus aureus, a Gram-positive bacterium that spreads predominantly through the respiratory tract. For the modification, ordinary textile materials of various origins and fiber structures were used. Technological conditions and compositions of modifying solutions were established, as well as the most suitable textile materials for modification. To assess the morphological and physical characteristics of copper-containing particles and the textile materials themselves, X-ray diffraction, a scanning electron microscope, and an energy-dispersive X-ray spectrum were used. In modified textile samples, XRD data showed the presence of crystalline phases of copper (Cu) and copper (I) oxide (Cu₂O). On the grounds of the SEM/EDS analysis, the saturation of textile materials with copper-containing particles depends on the structure of the textile materials and the origins of the fibers included in their composition, as well as the modification conditions and the copper precursor.     

Antiferromagnet–Ferromagnet Transition in Fe1−xCuxNbO4

Iron niobates, pure and substituted with copper (Fe_1−xCu_xNbO₄ with x = 0–0.15), were prepared by the solid-state method and characterized by X-ray diffraction, Raman spectroscopy, and magnetic measurements. The results of the structural characterizations revealed the high solubility of Cu ions in the structure and better structural stability compared to the pure sample. The analysis of the magnetic properties showed that the antiferromagnetic–ferromagnetic transition was caused by the insertion of Cu²⁺ ions into the FeNbO₄ structure. The pure FeNbO₄ structure presented an antiferromagnetic ordering state, with a Néel temperature of approximately 36.81K. The increase in substitution promoted a change in the magnetic ordering, with the state passing to a weak ferromagnetic order with a transition temperature (T_c) higher than the ambient temperature. The origin of the ferromagnetic ordering could be attributed to the increase in super-exchange interactions between Fe/Cu ions in the Cu²⁺-O-Fe³⁺ chains and the formation of bound magnetic polarons in the oxygen vacancies.     

Copper-Doped Biphasic Calcium Phosphate Powders: Dopant Release,Cytotoxicity and Antibacterial Properties

Cytotoxicity and antibacterial properties associated with the dopant release of Cu-doped Biphasic Calcium Phosphate (BCP) powders, mainly composed of hydroxyapatite mixed with β-tricalcium phosphate powders, were investigated. Twelve BCP ceramics were synthesized at three different sintering temperatures (600 °C, 900 °C and 1200 °C) and four copper doping rates (x = 0.0, 0.05, 0.10 and 0.20, corresponding to the stoichiometric amount of copper in Ca₁₀Cu_x(PO₄)₆(OH)_2-2xO_2x). Cytotoxicity assessments of Cu-doped BCP powders, using MTT assay with human-Mesenchymal Stem Cells (h-MSCs), indicated no cytotoxicity and the release of less than 12 ppm of copper into the biological medium. The antibacterial activity of the powders was determined against both Gram-positive (methicillin-sensitive (MS) and methicillin resistant (MR) Staphylococcus aureus) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacteria. The Cu-doped biomaterials exhibited a strong antibacterial activity against MSSA, MRSA and E. coli, releasing approximatively 2.5 ppm after 24 h, whereas 10 ppm were required to induce an antibacterial effect against P. aeruginosa. This study also demonstrated that the culture medium used during experiments can directly impact the antibacterial effect observed; only 4 ppm of Cu²⁺ were effective for killing all the bacteria in a 1:500 diluted TS medium, whereas 20 ppm were necessary to achieve the same result in a rich, non-diluted standard marrow cell culture medium.     

Selenite Substituted Calcium Phosphates: Preparation,Characterization, and Cytotoxic Activity

The aim of this study was to prepare a biomimetic selenium substituted calcium phosphate system for potential application in osteosarcoma therapy. Calcium phosphate (CaP) systems substituted with selenite ions were prepared by the wet precipitation method, using biogenic CaCO₃ (derived from cuttlefish bone), CO(NH₂)₂-H₃PO₄, and Na₂SeO₃·5H₂O as reagents. Starting reaction mixtures were prepared based on the formula for selenite-substituted hydroxyapatite, Ca₁₀(PO₄)_6-x(SeO₃)_x(OH)₂, with Ca/(P + Se) molar ratio of 1.67 and Se/(P + Se) molar ratio of: 0, 0.01, 0.05, and 0.10, respectively. The prepared CaP powders were characterized by Fourier transform infrared spectrometry, elemental analysis, scanning electron microscopy, X-ray powder diffraction analysis and Rietveld refinement studies. Phase transformation and ion release were analyzed during 7 days of incubation in simulated body fluid at 37 °C. The metabolic activity of healthy and osteosarcoma cell lines was assessed by cell cytotoxicity and viability test. The as-prepared powders were composed of calcium-deficient carbonated hydroxyapatite (HAp), octacalcium phosphate (OCP), and amorphous calcium phosphate (ACP). Along with the selenite substitution, the presence of Sr²⁺, Na⁺, and Mg²⁺ was detected as a result of using cuttlefish bone as a precursor for Ca²⁺ ions. Inductively coupled plasma mass spectrometry analysis showed that the Se/(P + Se) molar ratios of selenite substituted powders are lower than the nominal ratios. Heat treated powders were composed of HAp, α-tricalcium phosphate (α-TCP) and β-tricalcium phosphate (β-TCP). Doping CaP structure with selenite ions improves the thermal stability of HAp. The powder with the Se/(P + Se) molar ratio of 0.007 showed selective toxicity to cancer cells.     

Copper Surface Treatment Method with Antibacterial Performance Using “Super-Spread Wetting” Properties

In this work, a copper coating is developed on a carbon steel substrate by exploiting the superwetting properties of liquid copper. We characterize the surface morphology, chemical composition, roughness, wettability, ability to release a copper ion from surfaces, and antibacterial efficacy (against Escherichia coli and Staphylococcus aureus). The coating shows a dense microstructure and good adhesion, with thicknesses of approximately 20–40 µm. X-ray diffraction (XRD) analysis reveals that the coated surface structure is composed of Cu, Cu₂O, and CuO. The surface roughness and contact angle measurements suggest that the copper coating is rougher and more hydrophobic than the substrate. Inductively coupled plasma atomic emission spectroscopy (ICP-AES) measurements reveal a dissolution of copper ions in chloride-containing environments. The antibacterial test shows that the copper coating achieves a 99.99% reduction of E. coli and S. aureus. This study suggests that the characteristics of the copper-coated surface, including the chemical composition, high surface roughness, good wettability, and ability for copper ion release, may result in surfaces with antibacterial properties.     

Effect of Cu Substitution and Heat Treatment on Phase Formation and Magnetic Properties of Sm12Co88−xCux Melt-Spun Ribbons

The phase structure and microstructure of Sm₁₂Co_88−xCu_x (x = 0, 2, 4, 6, 8, 10; at.%) as-cast alloys and melt-spun ribbons prepared via the arc-melting method and melt-spun technology were studied experimentally by X-ray diffraction (XRD) and scanning electron microscope (SEM) with energy dispersive spectroscopy (EDS). The results reveal that the Sm₁₂Co_88−xCu_x (x = 0) as-cast alloy contains Sm₂Co₁₇ and Sm₅Co₁₉ phases, while the Sm₁₂Co_88−xCu_x (x = 2) as-cast alloy is composed of Sm₂Co₁₇, Sm₂Co₇ and Sm(Co, Cu)₅ phases. Sm₂Co₁₇ and Sm(Co, Cu)₅ phases are detected in Sm₁₂Co_88−xCu_x (x = 4, 6, 8, 10) as-cast alloys. Meanwhile, Sm₁₂Co_88−xCu_x ribbons show a single SmCo₇ phase, which is still formed in the ribbons annealed at 1023 K for one hour. After annealed at 1123 K for two hours, cooled slowly down to 673 K at 0.5 K/min and then kept for four hours, the ribbons are composed of Sm₂Co₁₇ and Sm(Co, Cu)₅ phases. The magnetic measurements of Sm₁₂Co_88−xCu_x ribbons were performed by vibrating sample magnetometer (VSM). The results exhibit that the maximum magnetic energy product ((BH)_max), the coercivity (H_cj) and the remanence (B_r) of the Sm₁₂Co_88−xCu_x ribbons increase generally with the increase in Cu substitution. In particular, the magnetic properties of the ribbons annealed at 1123 K and 673 K increase significantly with the increase in Cu substitution, resulting from the increase in the volume fraction of the formed Sm(Co, Cu)₅ phase after heat treatment.     

Real-Time Monitoring the Growth of Epitaxial CoxFe3−xO4 Ultrathin Films on Nb-Doped SrTiO3(001) via Reactive Molecular Beam Epitaxy by Means of Operando HAXPES

In this work, we present a comprehensive study on real-time monitoring the growth of epitaxial Co_xFe_3−xO₄ thin films grown on SrTiO₃(001) substrates via reactive molecular beam epitaxy. The growth process was monitored during evaporation by means of time resolved operando hard X-ray photoelectron spectroscopy (HAXPES). We prepared ultrathin ferrite films using different oxygen partial pressures, showing pure metallic, light oxidic, and cobalt ferrite-like growth. Additional X-ray diffraction measurements confirm HAXPES results.     

Study of the Layer-Type BST Thin Film with X-ray Diffraction and X-ray Photoelectron Spectroscopy

In the present paper, results of X-ray photoelectron studies of electroceramic thin films of barium strontium titanate, Ba_1−xSr_xTiO₃ (BST), composition deposited on stainless-steel substrates are presented. The thin films were prepared by the sol-gel method. A spin-coating deposition of BST layers with different chemical compositions was utilized so the layer-type structure of (0-2) connectivity was formed. After the deposition, the thin-film samples were heated in air atmosphere at temperature T = 700 °C for 1 h. The surfaces of BST thin films subjected to thermal treatment were studied by X-ray diffraction. X-ray diffraction measurements confirmed the perovskite-type phase for all grown thin-film samples. The oxidation states of the elements were examined by the X-ray photoelectron spectroscopy method. X-ray photoelectron spectroscopy survey spectra as well as high-resolution spectra (photo-peaks) of the main metallic elements, such as Ti, Ba, and Sr, were compared for the layer-type structures, differing in the deposition sequence of the barium strontium titanate layers constituting the BST thin film.     

Structural and Optical Properties of La1?xSrxTiO3+δ

La_1−xSr_xTiO_3+δ has attracted much attention as an important perovskite oxide. However, there are rare reports on its optical properties, especially reflectivity. In this paper, its structural and optical properties were studied. The X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and spectrophotometer were used to characterize the sample. The results show that with increasing Sr concentration, the number of TiO₆ octahedral layers in each “slab” increases and the crystal structure changes from layered to cubic structure. A proper Sr doping (x = 0.1) can increase the reflectivity, reaching 95% in the near infrared range, which is comparable with metal Al measured in the same condition. This indicates its potential applications as optical protective coatings or anti-radiation materials at high temperatures.     

Accelerated Degradation Test and Predictive Failure Analysis of B10 Copper-Nickel Alloy under Marine Environmental Conditions

This paper studies the corrosion behavior of B10 copper-nickel alloy in marine environment. Accelerated degradation test under marine environmental conditions was designed and performed based on the accelerated testing principle and the corrosion degradation mechanism. With the prolongation of marine corrosion time, the thickness of Cu₂O film increased gradually. Its corrosion product was Cu₂(OH)₃Cl, which increased in quantity over time. Cl⁻ was the major factor responsible for the marine corrosion of copper and copper alloy. Through the nonlinear fitting of corrosion rate and corrosion quantity (corrosion weight loss), degradation data of different corrosion cycles, the quantitative effects of two major factors, i.e., dissolved oxygen (DO) and corrosion medium temperature, on corrosion behavior of copper alloy were analyzed. The corrosion failure prediction models under different ambient conditions were built. One-day corrosion weight loss under oxygenated stirring conditions was equivalent to 1.31-day weight loss under stationary conditions, and the corrosion rate under oxygenated conditions was 1.31 times higher than that under stationary conditions. In addition, corrosion medium temperature had a significant effect on the corrosion of B10 copper sheet.     

Thermoelectric Properties of Cu2Se Nano-Thin Film by Magnetron Sputtering

Thermoelectric technology can achieve mutual conversion between thermoelectricity and has the unique advantages of quiet operation, zero emissions and long life, all of which can help overcome the energy crisis. However, the large-scale application of thermoelectric technology is limited by its lower thermoelectric performance factor (ZT). The thermoelectric performance factor is a function of the Seebeck coefficient, electrical conductivity, thermal conductivity and absolute temperature. Since these parameters are interdependent, increasing the ZT value has always been a challenge. Here, we report the growth of Cu₂Se thin films with a thickness of around 100 nm by magnetron sputtering. XRD and TEM analysis shows that the film is low-temperature α-Cu₂Se, XPS analysis shows that about 10% of the film’s surface is oxidized, and the ratio of copper to selenium is 2.26:1. In the range of 300–400 K, the maximum conductivity of the film is 4.55 × 10⁵ S m⁻¹, which is the maximum value reached by the current Cu₂Se film. The corresponding Seebeck coefficient is between 15 and 30 µV K⁻¹, and the maximum ZT value is 0.073. This work systematically studies the characterization of thin films and the measurement of thermoelectric properties and lays the foundation for further research on nano-thin-film thermoelectrics.     

Syntheses and Characterizations of CuIn1-xZnxSe2 Chalcopyrite Nanoparticles

CuIn_1-xZn_xSe₂ powders with various atomic percentages (x = 0, 0.05, 0.11, 0.16 and 0.21) were synthesized with the solvothermal method using metal chlorides and ethylendiamine as sources of precursors and a solvent, respectively. The experiment aims to investigate the effect of atomic percentages of Zn_x compounds on the structural and optical properties of CuIn_1-xZn_xSe₂ in order to improve future technological applications based on this material. The powders’ chalcopyrite phases were identified by X-ray diffraction. Energy dispersive X-ray spectroscopy analysis revealed the presence of Cu, In, Zn and Se with the expected atomic ratio of Zn/(In + Zn). Scanning electron microscopy and transmission electron microscopy analysis showed that the powders have large-scale desert rose-like structures. The nanopowders’ optical study by UV-visible spectrophotometry showed that the CuIn_1-xZn_xSe₂ energy gap values increase with the molar fraction of Zn_x. A change from 1.15 to 1.4 eV was observed.     

A Novel Mineral-like Copper Phosphate Chloride with a Disordered Guest Structure: Crystal Chemistry and Magnetic Properties

Novel copper phosphate chloride has been obtained under middle-temperature hydrothermal conditions. Its crystal structure was established based on the low-temperature X-ray diffraction data: Na₂Li_0.75(Cs,K)_0.5[Cu₅(PO₄)₄Cl]·3.5(H₂O,OH), sp. gr. C2/m, a = 19.3951(8) Å, b = 9.7627(3) Å, c = 9.7383(4) Å, β = 99.329(4)°, T = 150 K, MoK_α (λ = 0.71073 Å), R = 0.049. The crystal structure includes tetrameric copper clusters as the main building blocks, which are built of four CuO₄Cl pyramids sharing apical Cl vertices. The clusters are combined through phosphate groups and additional copper-centered polyhedra to form two mostly ordered periodic layers. Between the layers and inside the framework channels, alkali ions, H₂O molecules, or OH groups are statistically distributed. Na₂Li_0.75(Cs,K)_0.5[Cu₅(PO₄)₄Cl]·3.5(H₂O,OH) is a synthetic modification of a sampleite-polymorph of the lavendulan mineral group and represents a new member in a mero-plesiotype series of copper phosphates and arsenates, for which the crystal structures contain two-periodic [Cu₄X(TO₄)₄]_∞ modules (T = As, P; X = Cl, O). Magnetically, this phase exhibits the phase transition at T_C = 6.5 K, below which it possesses a weak ferromagnetic moment.     

Blue copper proteins: Synthesis, spectra, and structures of CuN(3)(SR) and CuN(3)(SR) active site analogues

The reaction of Cu(SR) or [Cu(SR)][ClO₄] derivatives (SR = p-nitrobenzenethiolate or O-ethylcysteinate) with potassium hydrotris(3,5-dimethyl-1-pyrazolyl)borate produces redox pairs of the stoichiometry Cu^IN₃(SR) and Cu^IIN₃(SR). These complexes are well-defined synthetic approximations to the proposed N₃S binding sites of blue (type 1) copper electron transfer proteins. The compounds were investigated by a variety of chemical and spectral (optical, resonance Raman, and electron paramagnetic resonance) techniques; the complex K[Cu(hydrotris(3,5-dimethyl-1-pyrazolyl)borate)(p- NO₂C₆H₄S]-2 acetone was also studied by single-crystal x-ray diffraction methods. The spectrochemical characteristics of the Cu^IIN₃(SR) species are in large part similar to the native system and thus provide some perspective regarding the origin of the unique type 1 spectral parameters and electron transfer properties.     

CuA and CuZ are variants of the electron transfer center in nitrous oxide reductase

Nitrous oxide reductase (N₂OR) is a dimeric copper-dependent bacterial enzyme that catalyzes the reduction of N₂O to N₂ as part of the denitrification pathway. In the absence of an x-ray crystal structure, the current model of the nature of the copper sites within the enzyme is based on four copper atoms per monomer and assigns two copper atoms to an electron transfer center, Cu_A, a bis-thiolate-bridged dinuclear copper center found to date only in N₂OR and cytochrome c oxidase, and two copper atoms to a second dinuclear center, Cu_Z, presumed to be the site of catalysis. Based on detailed analysis of the low temperature magnetic CD spectra of N₂OR, this paper revises the current model and proposes that both Cu_A and Cu_Z are variants of an electron transfer center and hence that all of the observed optical features are due to this electron transfer center. It is proposed further that the presence of these different forms provides a mechanism for the delivery of two electrons to an active site comprising copper ions lacking thiolate coordination.     

Enhanced rate of intramolecular electron transfer in an engineered purple CuA azurin

The recent expression of an azurin mutant where the blue type 1 copper site is replaced by the purple Cu_A site of Paracoccus denitrificans cytochrome c oxidase has yielded an optimal system for examining the unique electron mediation properties of the binuclear Cu_A center, because both type 1 and Cu_A centers are placed in the same location in the protein while all other structural elements remain the same. Long-range electron transfer is induced between the disulfide radical anion, produced pulse radiolytically, and the oxidized binuclear Cu_A center in the purple azurin mutant. The rate constant of this intramolecular process, k_ET = 650 ± 60 s⁻¹ at 298 K and pH 5.1, is almost 3-fold faster than for the same process in the wild-type single blue copper azurin from Pseudomonas aeruginosa (250 ± 20 s⁻¹), in spite of a smaller driving force (0.69 eV for purple Cu_A azurin vs. 0.76 eV for blue copper azurin). The reorganization energy of the Cu_A center is calculated to be 0.4 eV, which is only 50% of that found for the wild-type azurin. These results represent a direct comparison of electron transfer properties of the blue and purple Cu_A sites in the same protein framework and provide support for the notion that the binuclear purple Cu_A center is a more efficient electron transfer agent than the blue single copper center because reactivity of the former involves a lower reorganization energy.