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In metallurgical practice, the material is considered of adequate quality if it meets the customer’s expectations. It is necessary to take representative samples and perform quality testing to avoid financial and intangible losses. Sample contamination and matrix and surface quality play a significant role in the accuracy of chemical analyses. The purpose of this paper is to point out the advantages of specific methods of taking samples, such as immersion and spoon sampling of molten metal, and, in the experimental part, to assess the impacts of factors affecting the quality of the sampling. The influence of time of final sampling on determining the true amount of magnesium during a single melt and the influence of duration of mixing of molten cast iron on the accuracy of chemical analysis of the control sample were investigated. It is important that the time between the modification and casting of the liquid cast iron from the casting ladle be as short as possible. This is because the magnesium burns out and thus the chemical analysis of the sample taken is not accurate. Another important factor is ensuring the melt before sampling is homogenized and has the minimum prescribed temperature (1420 °C). Increasing sample collection time will cause changes in its chemical composition.

Reconstruction of bone defects and maintaining the continuity of the mandible is still a challenge in the maxillofacial surgery. Nowadays, the biomedical research within bone defect treatment is focussed on the therapy of using innovative biomaterials with specific characteristics consisting of the body’s own substances. Hydroxyapatite ceramic scaffolds have fully acceptable phase compositions, microstructures and compressive strengths for their use in regenerative medicine. The innovative hydroxyapatite ceramics used by us were prepared using the tape-casting method, which allows variation in the shape of samples after packing hydroxyapatite paste to 3D-printed plastic form. The purpose of our qualitative study was to evaluate the regenerative potential of the innovative ceramic biomaterial prepared using this method in the therapy of the cortical bone of the lower jaw in four mature pigs. The mandible bone defects were evaluated after different periods of time (after 3, 4, 5 and 6 months) and compared with the control sample (healthy cortical bone from the opposite side of the mandible). The results of the morphological, clinical and radiological investigation and hardness examination confirmed the positive regenerative potential of ceramic implants after treatment of the mandible bone defects in the porcine mandible model.

This study was designed to investigate the effects of hydroxyapatite (HA) ceramic implants (HA cylinders, perforated HA plates, and nonperforated HA plates) on the healing of bone defects, addressing biocompatibility, biodegradability, osteoconductivity, osteoinductivity, and osteointegration with the surrounding bone tissue. The HA ceramic implants were prepared using the tape-casting method, which allows for shape variation in samples after packing HA paste into 3D-printed plastic forms. In vitro, the distribution and morphology of the MC3T3E1 cells grown on the test discs for 2 and 9 days were visualised with a fluorescent live/dead staining assay. The growth of the cell population was clearly visible on the entire ceramic surfaces and very good osteoblastic cell adhesion and proliferation was observed, with no dead cells detected. A sheep animal model was used to perform in vivo experiments with bone defects created on the metatarsal bones, where histological and immunohistochemical tissue analysis as well as X-ray and CT images were applied. After 6 months, all implants showed excellent biocompatibility with the surrounding bone tissue with no observed signs of inflammatory reaction. The histomorphological findings revealed bone growth immediately over and around the implants, indicating the excellent osteoconductivity of the HA ceramic implants. A number of islands of bone tissue were observed towards the centres of the HA cylinders. The highest degree of biodegradation, bioresorption, and new bone formation was observed in the group in which perforated HA plates were applied. The results of this study suggest that HA cylinders and HA plates may provide a promising material for the functional long-bone-defect reconstruction and further research.

Slags produced in the steelmaking industry could be a source of chromium. Slags contain, depending on different types of slags, between 2 to 5 wt.% of Cr. Roasting of slag with NaOH, followed by subsequent leaching can produce leachates which can be efficiently processed using electrocoagulation (EC). This paper provides results from the EC process optimization for Cr(VI) solutions with initial concentration 1000 mg/L of Cr(VI). Influence of pH, current intensity and NaCl concentration on the efficiency of chromium recovery, energy consumption as well as solid product composition is discussed in detail. Optimum of pH = 6 was chosen for EC processing of Cr leachates as well as current intensities of 0.1–0.5 A because of the higher Cr/Fe ratio in solid product compared to higher current intensities. Results of EC processing of four real leachates of electric arc furnace carbon steel slag (EAFC), electric arc furnace stainless steel slag (EAFS), low carbon ferrochrome slag (LC FeCr) and high carbon ferrochrome slag (HC FeCr) were evaluated. Comparison of the results of four real leachate samples is presented. Obtained final solid product was identified as (Fe0.6 Cr0.4)2O3 and with up to 20% of Cr could be used as source of chromium in the ferrochrome production.

Recently, the utilization of renewable natural cellulosic materials, such as wood, plants, and waste paper in the preparation of building materials has attracted significant interest. This is due to their advantageous properties, low environmental impact and low cost. The objective of this paper is to investigate the influence of recycled cellulosic fibers (in the amount 0.5 wt % of the filler and binder weight) and superplasticizer (in the amount 0.5 wt % of the cement weight) on the resulting properties of cement composites (consistency of fresh mixture, density, thermal conductivity, and compressive and flexural strength) for hardening times of 1, 3, 7, 28, and 90 days. Plasticizer use improved the workability of fresh cement mixture. In comparison to the reference sample, the results revealed a decrease in density of 6.8% and in the thermal conductivity of composites with cellulosic fibers of 34%. The highest values of compressive (48.4 MPa) and flexural (up to 7 MPa) strength were achieved for hardened fiber cement specimens with plasticizer due to their significantly better dispersion of cement particles and improved bond strength between fibers and matrix.

Abstract This work studied the thermal stability, electrical, and thermoelectrical properties of copper(I) selenide, Cu2Se synthesized by high-energy milling in a planetary ball mill. The phase composition was investigated by X-ray powder diffraction analysis and scanning electron microscopy. The conversion of the precursors during mechanochemical synthesis and the stability of the product was monitored by thermal analysis. The dependence of electrical properties on the product porosity was observed. For the densification of Cu2Se, the method of spark plasma sintering was applied to prepare suitable samples for thermoelectric characterization. High-temperature thermoelectric properties of synthetic Cu2Se were compared to its natural analogue-mineral berzelianite in terms of its potential application in energy conversion. Based on the results a relatively high figure-of-merit, ZT parameter (~ 1.15, T = 770 K) was obtained for undoped Cu2Se, prepared by rapid mechanochemical reaction (5 min). Cyclic voltammetry measurements of Na/NaClO4/Cu2Se cell implied that mechanochemically synthesized Cu2Se could be used as a promising intercalation electrode for sodium-ion batteries.

In this work, a nanocomposite consisting of ternary chalcogenide CuInS2 and TiO2 was prepared and its optical and optoelectrical properties were investigated. The CuInS2/TiO2 nanocomposite was produced via one-step mechanochemical synthesis and characterized from the crystal structure, microstructural, morphology, surface, optical, and optoelectrical properties viewpoints. X-ray diffraction confirmed the presence of both components, CuInS2 and TiO2, in the nanocomposite and revealed a partial transformation of anatase to rutile. The presence of both components in the samples was also proven by Raman spectroscopy. HRTEM confirmed the nanocrystalline character of the samples as crystallites ranging from around 10 nm and up to a few tens of nanometers were found. The presence of the agglomerated nanoparticles into larger grains was proven by SEM. The measured optical properties of CuInS2, TiO2, and CuInS2/TiO2 nanocomposites demonstrate optical bandgaps of ~1.62 eV for CuInS2 and 3.26 eV for TiO2. The measurement of the optoelectrical properties showed that the presence of TiO2 in the CuInS2/TiO2 nanocomposite increased its conductivity and modified the photosensitivity depending on the ratio of the components. This study has demonstrated the possibility of preparing a CuInS2/TiO2 nanocomposite material with promising applications in optoelectronics in the visible region in an eco-friendly manner.

The Fe3O4@SiO2@ZnO composite was synthesized via the simultaneous deposition of SiO2 and ZnO onto pre-prepared Fe3O4 nanoparticles. Physicochemical methods (TEM, EDXS, XRD, SEM, FTIR, PL, zeta potential measurements, and low-temperature nitrogen adsorption/desorption) revealed that the simultaneous deposition onto magnetite surfaces, up to 18 nm in size, results in the formation of an amorphous shell composed of a mixture of zinc and silicon oxides. This composite underwent modification to form Fe3O4@SiO2@ZnO*, achieved by activation with H2O2. The modified composite retained its structural integrity, but its surface groups underwent significant changes, exhibiting pronounced catalytic activity in the photodegradation of methyl orange under UV irradiation. It was capable of degrading 96% of this azo dye in 240 min, compared to the initial Fe3O4@SiO2@ZnO composite, which could remove only 11% under identical conditions. Fe3O4@SiO2@ZnO* demonstrated robust stability after three cycles of use in dye photodegradation. Furthermore, Fe3O4@SiO2@ZnO* exhibited decreased PL intensity, indicating an enhanced efficiency in electron-hole pair separation and a reduced recombination rate in the modified composite. The activation process diminishes the electron-hole (e−)/(h+) recombination and generates the potent oxidizing species, hydroxyl radicals (OH˙), on the photocatalyst surface, thereby playing a crucial role in the enhanced photodegradation efficiency of methyl orange with Fe3O4@SiO2@ZnO*.

In the presented article, an electrocoagulation method using a steel cathode and a steel anode was used to obtain chromium from laboratory-prepared model solutions with known compositions. The study aimed to analyze the effect of solution conductivity, pH, and 100% efficiency of chromium removal from the solution, as well as the highest possible Cr/Fe ratio in the final solid product throughout the process of electrocoagulation. Different concentrations of chromium (VI) (100, 1000, and 2500 mg/L) and different pH values (4.5, 6, and 8) were investigated. Various solution conductivities were provided by the addition of 1000, 2000, and 3000 mg/L of NaCl to the studied solutions. Chromium removal efficiency equal to 100% was achieved for all studied model solutions for different experiment times, depending on the selected current intensity. The final solid product contained up to 15% chromium in the form of mixed FeCr hydroxides obtained under optimal experimental conditions: pH = 6, I = 0.1 A, and c (NaCl) = 3000 mg/L. The experiment indicated the advisability of using a pulsed change of electrode polarity, which led to a reduction in the time of the electrocoagulation process. The results may help in the rapid adjustment of the conditions for further electrocoagulation experiments, and they can be used as the optimization experimental matrix.

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

Nickel mono- (NiSe) and diselenide (NiSe2) were produced from stoichiometric mixtures of powdered Ni and Se precursors by the one-step, undemanding mechanochemical reactions. The process was carried out by high-energy milling for 30 and 120 min in a planetary ball mill. The kinetics of the reactions were documented, and the products were studied in terms of their crystal structure, morphology, electrical, and optical properties. X-ray powder diffraction confirmed that NiSe has hexagonal and NiSe2 cubic crystal structure with an average crystallite size of 10.5 nm for NiSe and 13.3 nm for NiSe2. Their physical properties were characterized by the specific surface area measurements and particle size distribution analysis. Transmission electron microscopy showed that the prepared materials contain nanoparticles of irregular shape, which are agglomerated into clusters of about 1–2 μm in diameter. The first original values of electrical conductivity, resistivity, and sheet resistance of nickel selenides synthesized by milling were measured. The obtained bandgap energy values determined using UV–Vis spectroscopy confirmed their potential use in photovoltaics. Photoluminescence spectroscopy revealed weak luminescence activity of the materials. Such synthesis of nickel selenides can easily be carried out on a large scale by milling in an industrial mill, as was verified earlier for copper selenide synthesis.

The subject of interest in this study was lead cementation with zinc from solution after conventional agitate acidic leaching of converter dust from secondary copper production. The kinetics of lead cementation from an acid solution of lead acetate using zinc powder was studied. The optimal cementation conditions for removing lead from the solution were determined to have a stirring intensity of 300 rpm, a zinc particle size distribution mm and an ambient temperature. Under these conditions, an almost 90% efficiency in removing lead from solution was achieved. The cementation precipitate contains Pb, and a certain amount of Cu. Lead is present in the cementation precipitate in the PbO, Pb5O8 and Pb(Cu2O2) phases. The solution after cementation was also refined from copper. The solution can be used for further processing in order to obtain a marketable Zn-based product. The resulting cementation precipitate can be further processed and modified to obtain a lead-based product. A kinetic study of the process of lead cementation from solution was also carried out. Based on experimental measurements, the value of apparent activation energy (Ea) which was found to be ~18.66 kJ·mol−1, indicates that this process is diffusion controlled in the temperature range 293–333 K.

Abstract In this study, we demonstrate a one-pot mechanochemical synthesis of the nanocomposite composed of stannite Cu2FeSnS4 and rhodostannite Cu2FeSn3S8 nanocrystals using a planetary ball mill and elemental precursors (Cu, Fe, Sn, S). By this approach, unique nanostructures with interesting properties can be obtained. Methods of XRD, Raman spectroscopy, UV-Vis, nitrogen adsorption, SEM, EDX, HRTEM, STEM, and SQUID magnetometry were applied. Quaternary tetragonal phases of stannite and rhodostannite with crystallite sizes 18–19 nm were obtained. The dominant Raman peaks corresponding to the tetragonal stannite structure corresponding to A-symmetry optical modes were identified in the spectra. The bandgap 1.25 eV calculated from UV-Vis absorption spectrum is very well-acceptable value for the application of the synthesized material. The SEM micrographs illustrate the clusters of particles in micron and submicron range. The formation of agglomerates is also illustrated on the TEM micrographs. Weak ferromagnetic properties of the synthesized nanocrystals were documented.

The CuInSe2/ZnS multiparticulate nanocomposites were first synthesized employing two-step mechanochemical synthesis. In the first step, tetragonal CuInSe2 crystals prepared from copper, indium and selenium precursors were co-milled with zinc acetate dihydrate and sodium sulfide nonahydrate as precursors for ZnS in different molar ratios by mechanochemical route in a planetary mill. In the second step, the prepared CuInSe2/ZnS nanocrystals were further milled in a circulation mill in sodium dodecyl sulphate (SDS) solution (0.5 wt.%) to stabilize the synthesized nanoparticles. The sodium dodecyl sulphate capped CuInSe2/ZnS 5:0-SDS nanosuspension was shown to be stable for 20 weeks, whereas the CuInSe2/ZnS 4:1-SDS one was stable for about 11 weeks. After sodium dodecyl sulphate capping, unimodal particle size distribution was obtained with particle size medians approaching, respectively, 123 nm and 188 nm for CuInSe2/ZnS 5:0-SDS and CuInSe2/ZnS 4:1-SDS nanocomposites. Successful stabilization of the prepared nanosuspensions due to sodium dodecyl sulphate covering the surface of the nanocomposite particles was confirmed by zeta potential measurements. The prepared CuInSe2/ZnS 5:0-SDS and CuInSe2/ZnS 4:1-SDS nanosuspensions possessed anti-myeloma sensitizing potential assessed by significantly reduced viability of multiple myeloma cell lines, with efficient fluorescence inside viable cells and higher cytotoxic efficacy in CuInSe2/ZnS 4:1-SDS nanosuspension.

Potassium based ceramic materials composed from leucite in which 5 % of Al is exchanged with Fe and 4 % of hematite was synthesized by mechanochemical homogenization and annealing of K2O-SiO2-Al2O3-Fe2O3 mixtures. Synthesized material was characterized by X-ray Powder Diffraction (XRPD) and Scanning Electron Microscopy coupled with Energy Dispersive X-ray spectroscopy (SEM/EDX). The two methods are in good agreement in regard to the specimen chemical composition suggesting that a leucite chemical formula is K0.8Al0.7Fe0.15Si2.25O6. Rietveld structure refinement results reveal that about 20 % of vacancies exist in the position of K atoms. This work is licensed under a Creative Commons Attribution 4.0 International License.

Copper(II) selenide, CuSe was prepared from Cu and Se powders in a stoichiometric ratio by a rapid, and convenient one-step mechanochemical synthesis, after 5 and 10 min of milling in a planetary, and an industrial vibratory, mill. The kinetics of the synthesis, and the structural, morphological, optical, and electrical properties of CuSe products prepared in the two types of mill were studied. Their crystal structure, physical properties, and morphology were characterized by X-ray diffraction, specific surface area measurements, particle size distribution, scanning, and transmission electron microscopy. The products crystallized in a hexagonal crystal structure. However, a small amount of orthorhombic phase was also identified. The scanning electron microscopy revealed that both products consist of agglomerated particles of irregular shape, forming clusters with a size ~50 μm. Transmission electron microscopy proved the nanocrystalline character of the CuSe particles. The optical properties were studied using UV–Vis and photoluminescence spectroscopy. The determined band gap energies of 1.6 and 1.8 eV for the planetary- and vibratory-milled product, respectively, were blue-shifted relative to the bulk CuSe. CuSe prepared in the vibratory mill had lower resistivity and higher conductivity, which corresponds to its larger crystallite size in comparison with CuSe prepared in the planetary mill.

The continued decrease in water quality requires new advances in the treatment of wastewater, including the preparation of novel, effective, environmentally friendly, and affordable sorbents of toxic pollutants. We introduce a simple non-conventional mechanochemical synthesis of magnetically responsive materials. Magnetic lignite and magnetic char were prepared by high-energy ball co-milling from either raw Slovak lignite or coal-based char together with a ferrofluid. The products were characterised by X-ray diffraction, electron microscopy, 57Fe Mössbauer spectroscopy, X-ray photoelectron spectroscopy (XPS), volumetric magnetic susceptibility, and low-temperature nitrogen adsorption, and both magnetic carbons were comparatively tested as potential sorbents of As(V) oxyanions and Cd(II) cations in aqueous solutions. The magnetic char was an excellent sorbent of As(V) oxyanions (Qm = 19.9 mg/g at pH 3.9), whereas the magnetic lignite was less effective. The different sorption properties towards arsenic anions may have been due to different oxidation states of iron on the surfaces of the two magnetic composites (determined by XPS), although the overall state of iron monitored by Mössbauer spectroscopy was similar for both samples. Both magnetic composites were effective sorbents for removing Cd(II) cations (Qm (magnetic lignite) = 70.4 mg/g at pH 6.5; Qm (magnetic char) = 58.8 mg/g at pH 6.8).

Thorough kinetic analysis of the magnesia leaching based on measuring the changes in lixiviant composition revealed that there are differences between the actual leaching behaviour and predictions obtained using the non-porous shrinking particle model (NSPM). A detailed study of the morphology of the solid during the leaching process using SEM showed that observed deviations from the NSPM model depend on the particle size; chemical (mineralogical) composition and the polycrystalline nature of magnesia.

Polycyclic aromatic hydrocarbons (PAHs) are a group of serious contaminants of air, water soil and sediments. Persistence and accumulation of PAHs in the environment is due to their hydrophobicity and hence low solubility and bioavailability to microbial action. This work presents an evidence of biodegradation of PAHs in a soil sample taken from a coal gasification plant contaminated with coal tar. The degradation of the contaminant by indigenous microorganisms was studied under aerobic conditions at 15 ºC in a laboratory glass column. The oxidation kinetic of organic carbon was monitored by measuring the oxygen consumption rate and the carbon dioxide production rate. The biodegradation rates observed were in the range of 0.2 to 7 mg C kg-1 h-1. Approximately 14 000 mg kg-1 of the total organic carbon was completely mineralized to CO2 during 6 months. The sum of 16 EPA PAHs decreased from the initial concentration of 21 331 mg kg-1 to the value of 2 774 mg kg-1after 6 months of biodegradation. The thermogravimetric analysis revealed a 34 % weight decrease of organic mater content during the 6-month degradation period.

Sulphidic mineral - tetrahedrite Cu12Sb4S13 was subjected to leaching in a H2SO4 medium. Physico-chemical changes of a mechanically activated mineral were investigated before and after leaching using the infrared spectroscopy and the scanning electron microscopy. The mechanical activation of the mineral resulted in the mechanochemical surface oxidation and the formation of sulphates and iron carbonate. Further, the specific surface area and the crystal structure disordering of the mineral increased. These aspects influence the kinetics and the selectivity of acid leaching of tetrahedrite. The effect of the reaction surface decreases due to the agglomeration during the milling and the formation of iron hydroxyoxides or iron hydroxysulphates from admixed pyrite and adversely affects the extraction rate of metals from tetrahedrite.