The manipulation of natural mineral chalcopyrite CuFeS2via mechanochemistry: properties and thermoelectric potential.

In this study, the properties of the natural mineral chalcopyrite CuFeS2 after mechanical activation in a planetary mill were studied. The intensity of mechanical activation was controlled by changing the revolutions of the mill in the range 100-600 min-1. A series of characterization techniques, such as XRD, SEM, TEM, TA (DTA, TG, and DTG), particle size analysis, and UV-vis spectroscopy was applied and reactivity studies were also performed. Several new features were revealed for the mechanically activated chalcopyrite, e.g. the poly-modal distribution of produced nanoparticles on the micrometer scale, agglomeration effects by prolonged milling, possibility to modify the shape of the particles, X-ray amorphization and a shift from a non-cubic (tetragonal) structure to pseudo-cubic structure. The thermoelectric response was evaluated on the "softly" compacted powder via the spark plasma sintering method (very short holding time, low sintering temperature, and moderate pressure) by measuring the Seebeck coefficient and electrical and thermal conductivity above room temperature. The milling process produced samples with lower resistivity compared to the original non-activated sample. The Seebeck data close to zero confirmed the "compensated" character of natural chalcopyrite, reflecting its close-to stoichiometric composition with low concentration of both n- and p-type charge carriers. Alternatively, an evident correlation between thermal conductivity and energy supply by milling was observed with the possibility of band gap manipulation, which is associated with the energy delivered by the milling procedure.

The WC and CrC Coatings Deposited from Carbonyls Using PE CVD Method-Structure and Properties.

This article presents a comparative study of WC and CrC coatings deposited by the plasma-enhanced chemical vapor method using the hexacarbonyls of W and Cr as precursors. The measured thicknesses of the WC and CrC coatings are equal to ca. 1.5 µm. The WC coating consists of microcolumns with a conical end, with gaps between the microcolumns up to approximately 100 nm, and their structure is formed by nanoparticles in the shape of globules with a diameter of up to 10 nm. In the case of the CrC coating, a cauliflower structure with gaps ranging from 20 to 100 nm was achieved. The diameter of cauliflower grains is from 50 nm to 300 nm. The C content in the WC and CrC coating is 66.5 at.% and 75.5 at.%. The W content is 1.4 at.% and the Cr content in the CrC coating is 1.2 at.%. The hardness and Young's modulus of the WC coating are equal to 9.2 ± 1.2 GPa 440.2 ± 14.2 GPa, respectively. The coefficients of friction and wear volume of the WC coating are equal to 0.7 and -1.6 × 106/+3.3 × 106 µm3, respectively. The hardness and Young's modulus of the CrC coating are 7.5 ± 1.2 GPa and 280 ± 18.5 GPa, respectively. The coefficients of friction and wear volume of the CrC coating are 0.72 and -18.84 × 106/+0.35 × 106 µm3, respectively.

The Influence of Manganese Addition on the Properties of Biodegradable Zinc-Manganese-Calcium Alloys.

This study focuses on the preparation and characterization of zinc-based alloys containing magnesium, calcium, and manganese. The alloys were prepared by the melting of pure elements, casting them into graphite molds, and thermo-mechanically treating them via hot extrusion. The phase compositions of the samples were analyzed using X-ray diffraction technique and SEM/EDX analysis. The analysis confirmed that in addition to the Zn matrix, the materials are reinforced by the CaZn13, MgZn2, and Mn-based precipitates. The mechanical properties of the alloys were ascertained by tensile, compressive, and bending tests, measurement of the samples microhardness and elastic modulus. The results indicate that an increase in Mn content leads to an increase in the maximum stress experienced under both tension and compression. However, the plastic deformation of the alloys decreases with increasing Mn content. This study provides valuable insights into the microstructural changes and mechanical behavior of zinc-based alloys containing magnesium, calcium, and manganese, which can be used to design alloys for specific biomedical applications.

Development of Positively Charged Poly-L-Lysine Magnetic Nanoparticles as Potential MRI Contrast Agent.

A colloidal solution of magnetic nanoparticles (MNPs) modified with biocompatible positively charged poly-L-lysine (PLL) with an oleate (OL) layer employed as an initial coating was produced as a potential MRI contrast agent. The effect of various PLL/MNPs' mass ratios on the samples' hydrodynamic diameter, zeta potential, and isoelectric point (IEP) was studied by the dynamic light-scattering method. The optimal mass ratio for MNPs' surface coating was 0.5 (sample PLL0.5-OL-MNPs). The average hydrodynamic particle size in the sample of PLL0.5-OL-MNPs was 124.4 ± 1.4 nm, and in the PLL-unmodified nanoparticles, it was 60.9 ± 0.2 nm, indicating that the OL-MNPs' surface became covered by PLL. Next, the typical characteristics of the superparamagnetic behavior were observed in all samples. In addition, the decrease in saturation magnetizations from 66.9 Am2/kg for MNPs to 35.9 and 31.6 Am2/kg for sample OL-MNPs and PLL0.5-OL-MNPs also confirmed successful PLL adsorption. Moreover, we show that both OL-MNPs and PLL0.5-OL-MNPs exhibit excellent MRI relaxivity properties and a very high r2(*)/r1 ratio, which is very desirable in biomedical applications with required MRI contrast enhancement. The PLL coating itself appears to be the crucial factor in enhancing the relaxivity of MNPs in MRI relaxometry.

Sustainable Synthesis of Cadmium Sulfide, with Applicability in Photocatalysis, Hydrogen Production, and as an Antibacterial Agent, Using Two Mechanochemical Protocols.

CdS nanoparticles were successfully synthesized using cadmium acetate and sodium sulfide as Cd and S precursors, respectively. The effect of using sodium thiosulfate as an additional sulfur precursor was also investigated (combined milling). The samples were characterized by XRD, Raman spectroscopy, XPS, UV-Vis spectroscopy, PL spectroscopy, DLS, and TEM. Photocatalytic activities of both CdS samples were compared. The photocatalytic activity of CdS, which is produced by combined milling, was superior to that of CdS, and was obtained by an acetate route in the degradation of Orange II under visible light irradiation. Better results for CdS prepared using a combined approach were also evidenced in photocatalytic experiments on hydrogen generation. The antibacterial potential of mechanochemically prepared CdS nanocrystals was also tested on reference strains of E. coli and S. aureus. Susceptibility tests included a 24-h toxicity test, a disk diffusion assay, and respiration monitoring. Bacterial growth was not completely inhibited by the presence of neither nanomaterial in the growth environment. However, the experiments have confirmed that the nanoparticles have some capability to inhibit bacterial growth during the logarithmic growth phase, with a more substantial effect coming from CdS nanoparticles prepared in the absence of sodium thiosulfate. The present research demonstrated the solvent-free, facile, and sustainable character of mechanochemical synthesis to produce semiconductor nanocrystals with multidisciplinary application.

Electrochemical behavior, biocompatibility and mechanical performance of biodegradable iron with PEI coating.

Coating of the biodegradable metals represents an effective way of modification of their properties. Insufficient biological, mechanical, or degradation performance of pure metals may be enhanced when the proper type of organic polymer coating is used. In our previous work, the significant effect of the polyethyleneimine (PEI) coating not only on the rate but also on the type of corrosion was discovered. To bring a comprehensive overview of the Fe-PEI system performance, iron-based biodegradable scaffolds with polyethyleneimine coating were studied and their cytocompatibility and hemocompatibility, and mechanical properties were evaluated and discussed in this work. Electrochemical impedance spectroscopy (EIS) measurements were conducted for further study of material behavior. Biological analyses (MTS assay, fluorescent imaging, hemocompatibility tests) showed better cell proliferation on the surface of Fe-PEI samples but not sufficient overall cytocompatibility. Good anti-platelet adhesion properties but higher hemolysis when compared to the pure iron was also observed for the coated samples. Mechanical properties of the prepared Fe-PEI material were enhanced after coating. These findings suggest that the Fe-PEI may be an interesting potential biomaterial after further composition optimization resulting in lower cytotoxicity and better hemocompatibility.

The Effects of Various Conditions of Short-Term Rejuvenation Heat Treatment on Room-Temperature Mechanical Properties of Thermally Aged P92 Boiler Steel.

In this work, the effects of various conditions of short-term rejuvenation heat treatment on room-temperature mechanical properties of long-term aged P92 boiler steel were investigated. Normalized and tempered P92 steel pipe was thermally exposed at 600 °C for time durations up to 5000 h in order to simulate high-temperature material degradation, as also occurring in service conditions. Thus, thermally embrittled material states of P92 steel were prepared, showing tempered martensitic microstructures with coarsened secondary phase precipitates of Cr23C6-based carbides and Fe2W-based Laves phase. Compared with the initial normalized and tempered material condition, thermally aged materials exhibited a slight decrease in strength properties (i.e., yield stress and ultimate tensile strength) and deformation properties (i.e., total elongation and reduction of area). The hardness values were almost unaffected, whereas the impact toughness values showed a steep decrease after long-term ageing. An idea for designing the rejuvenation heat treatments for restoration of impact toughness was based on tuning the material properties by short-term annealing effects at various selected temperatures somewhat above the long-term ageing temperature of P92 material. Specifically, the proposed heat treatments were performed within the temperature range between 680 °C and 740 °C, employing variable heating up and cooling down conditions. It was revealed that short-term annealing at 740 °C for 1 h with subsequent rapid cooling into water represents the most efficient rejuvenation heat treatment procedure of thermally aged P92 steel for full restoration of impact toughness up to original values of normalized and tempered material state. Microstructural observations clearly indicated partial dissolution of the Laves phase precipitates to be the crucial phenomenon that played a key role in restoring the impact toughness.

Corrosion Behavior of Zn, Fe and Fe-Zn Powder Materials Prepared via Uniaxial Compression.

Powder metallurgy is one of the most prevalent ways for metallic degradable materials preparation. Knowledge of the properties of initial powders used during this procedure is therefore of great importance. Two different metals, iron and zinc, were selected and studied in this paper due to their promising properties in the field of biodegradable implants. Raw powders were studied using scanning electron microscopy (SEM) coupled with energy dispersive spectrometry (EDX). Powders (Fe, Zn and Fe-Zn in a weight ratio of 1:1) were then compressed at the pressure of 545 MPa to the form of pellets with a diameter of 1.7 cm. Surface morphology and degradation behavior in the Hanks´ solution were studied and evaluated. Electrochemical polarization tests along with the static immersion tests carried out for 21 days were employed for corrosion behavior characterization. The highest corrosion rate was observed for pure Zn powder followed by the Fe-Zn and Fe, respectively. A mixed Fe-Zn sample showed similar properties as pure zinc with no signs of iron degradation after 21 days due to the effect of galvanic protection secured by the zinc acting as a sacrificial anode.

Mechanochemistry for Energy Materials: Impact of High-Energy Milling on Chemical, Electric and Thermal Transport Properties of Chalcopyrite CuFeS2 Nanoparticles.

Chalcopyrite CuFeS2 , a semiconductor with applications in chemical sector and energy conversion engineering, was synthetized in a planetary mill from elemental precursors. The synthesis is environmentally friendly, waste-free and inexpensive. The synthesized nano-powders were characterized by XRD, SEM, EDX, BET and UV/Vis techniques, tests of chemical reactivity and, namely, thermoelectric performance of sintered ceramics followed. The crystallite size of ∼13 nm and the strain of ∼17 were calculated for CuFeS2 powders milled for 60, 120, 180 and 240 min, respectively. The evolution of characteristic band gaps, Eg, and the rate constant of leaching, k, of nano-powders are corroborated by the universal evolution of the parameter SBET /X (SBET -specific surface area, X-crystallinity) introduced for complex characterization of mechanochemically activated solids in various fields such as chemical engineering and/or energy conversion. The focus on non-doped semiconducting CuFeS2 enabled to assess the role of impurities, which critically and often negatively influence the thermoelectric properties.

Mechanochemistry as an Alternative Method of Green Synthesis of Silver Nanoparticles with Antibacterial Activity: A Comparative Study.

This study shows mechanochemical synthesis as an alternative method to the traditional green synthesis of silver nanoparticles in a comparative manner by comparing the products obtained using both methodologies and different characterization methods. As a silver precursor, the most commonly used silver nitrate was applied and the easily accessible lavender (Lavandula angustofolia L.) plant was used as a reducing agent. Both syntheses were performed using 7 different lavender:AgNO3 mass ratios. The synthesis time was limited to 8 and 15 min in the case of green and mechanochemical synthesis, respectively, although a significant amount of unreacted silver nitrate was detected in both crude reaction mixtures at low lavender:AgNO3 ratios. This finding is of particular interest mainly for green synthesis, as the potential presence of silver nitrate in the produced nanosuspension is often overlooked. Unreacted AgNO3 has been removed from the mechanochemically synthesized samples by washing. The nanocrystalline character of the products has been confirmed by both X-ray diffraction (Rietveld refinement) and transmission electron microscopy. The latter has shown bimodal size distribution with larger particles in tens of nanometers and the smaller ones below 10 nm in size. In the case of green synthesis, the used lavender:AgNO3 ratio was found to have a decisive role on the crystallite size. Silver chloride has been detected as a side-product, mainly at high lavender:AgNO3 ratios. Both products have shown a strong antibacterial activity, being higher in the case of green synthesis, but this can be ascribed to the presence of unreacted AgNO3. Thus, one-step mechanochemical synthesis (without the need to prepare extract and performing the synthesis as separate steps) can be applied as a sustainable alternative to the traditional green synthesis of Ag nanoparticles using plants.

The Effect of Electrolytic Hydrogenation on Mechanical Properties of T92 Steel Weldments under Different PWHT Conditions.

In the present work, the effects of electrolytic hydrogen charging of T92 steel weldments on their room-temperature tensile properties were investigated. Two circumferential weldments between the T92 grade tubes were produced by gas tungsten arc welding using the matching Thermanit MTS 616 filler material. The produced weldments were individually subjected to considerably differing post-welding heat treatment (PWHT) procedures. The first-produced weldment was conventionally tempered (i.e., short-term annealed below the Ac1 critical transformation temperature of the T92 steel), whereas the second one was subjected to its full renormalization (i.e., appropriate reaustenitization well above the T92 steel Ac3 critical transformation temperature and subsequent air cooling), followed by its conventional subcritical tempering. From both weldments, cylindrical tensile specimens of cross-weld configuration were machined. The room-temperature tensile tests were performed for the individual welds' PWHT states in both hydrogen-free and electrolytically hydrogen-charged conditions. The results indicated higher hydrogen embrittlement susceptibility for the renormalized-and-tempered weldments, compared to the conventionally tempered ones. The obtained findings were correlated with performed microstructural and fractographic observations.

The Influence of Laser Surface Remelting on the Tribological Behavior of the ECAP-Processed AZ61 Mg Alloy and AZ61-Al2O3 Metal Matrix Composite.

This paper deals with the tribological study of the laser remelted surfaces of the ECAP-processed AZ61 magnesium alloy and AZ61-Al2O3 metal matrix composite with 10 wt.% addition of Al2O3 nanoparticles. The study included the experimental optimization of the laser surface remelting conditions for the investigated materials by employing a 400 W continual wave fiber laser source. Tribological tests were performed in a conventional "ball-on-disc" configuration with a ceramic ZrO2 ball under a 5 N normal load and a sliding speed of 100 mm/s. The results showed that both the incorporation of Al2O3 nanoparticles and the applied laser treatments led to recognizable improvements in the tribological properties of the studied AZ61-Al2O3 composites in comparison with the reference AZ61 alloy. Thus, the best improvement has been obtained for the laser modified AZ61-10 wt.% Al2O3 nanocomposite showing about a 48% decrease in the specific wear rate compared to the laser untreated AZ61 base material.