Leaching of liquation-feeding furnace dross as a first step for germanium recovery.

OBJECTIVE: Germanium, an important component of electronics, is considered by many global economies as a critical raw material. Therefore, investigating its potential new sources is crucial for prospective technology development. This paper presents the investigation results on the leaching of liquation-feeding furnace dross using sulfuric and oxalic acid solutions. RESULTS: The dross contained mostly zinc (68.0% wt.) but also elevated germanium concentration (0.68% wt.). The influence of temperature, time, initial acid concentration, and liquid-to-solid phase ratio (L:S) was examined. It was found that germanium availability via leaching is limited-maximum leaching yields using aqueous solutions of sulfuric and oxalic acids were 60% (80 °C, 2 h, 15% wt. H2SO4, L:S 25:1) and 57% (80 °C, 3 h, 12.5% wt. H2C2O4, L:S 10:1), respectively.

Tuning the Structure of Pd@Ni-Co Nanowires and Their Electrochemical Properties.

One-dimensional transition metal materials are promising supports for precious metals used in energy production processes. Due to their electrochemical properties, 3d-group metals (such as Ni, Co, and Fe) can actively interact with catalysts by a strong metal-support interaction. This study shows that changing the Ni:Co ratio makes it possible to modulate the structure of the catalyst supports, which, in turn, provides a tool for designing their electrical and electrochemical properties. For example, Ni1-Co9 shows the highest electrical conductivity (5.8-10-4 S/cm) among all of the materials examined. On the contrary, the Pd@Ni7-Co3 system presents the highest mass activity (>2000 mA mg-1) at 0.7 V, exceeding by several times that of commercial Pt/C (>300 mA mg-1) at the same potential. Our study opens the gateway for applications of bimetallic transition metal nanowires in catalytic conversion and energy production processes.

Carbon-Coated Iron Oxide Nanoparticles Promote Reductive Stress-Mediated Cytotoxic Autophagy in Drug-Induced Senescent Breast Cancer Cells.

The surface modification of magnetite nanoparticles (Fe3O4 NPs) is a promising approach to obtaining biocompatible and multifunctional nanoplatforms with numerous applications in biomedicine, for example, to fight cancer. However, little is known about the effects of Fe3O4 NP-associated reductive stress against cancer cells, especially against chemotherapy-induced drug-resistant senescent cancer cells. In the present study, Fe3O4 NPs in situ coated by dextran (Fe3O4@Dex) and glucosamine-based amorphous carbon coating (Fe3O4@aC) with potent reductive activity were characterized and tested against drug-induced senescent breast cancer cells (Hs 578T, BT-20, MDA-MB-468, and MDA-MB-175-VII cells). Fe3O4@aC caused a decrease in reactive oxygen species (ROS) production and an increase in the levels of antioxidant proteins FOXO3a, SOD1, and GPX4 that was accompanied by elevated levels of cell cycle inhibitors (p21, p27, and p57), proinflammatory (NFκB, IL-6, and IL-8) and autophagic (BECN1, LC3B) markers, nucleolar stress, and subsequent apoptotic cell death in etoposide-stimulated senescent breast cancer cells. Fe3O4@aC also promoted reductive stress-mediated cytotoxicity in nonsenescent breast cancer cells. We postulate that Fe3O4 NPs, in addition to their well-established hyperthermia and oxidative stress-mediated anticancer effects, can also be considered, if modified using amorphous carbon coating with reductive activity, as stimulators of reductive stress and cytotoxic effects in both senescent and nonsenescent breast cancer cells with different gene mutation statuses.

Structural characterization of newly-developed Al79Ni5Fe5Y11 and Al79Ni11Fe5Y5 alloys with amorphous matrixes.

The low glass-forming ability of aluminium-based metallic glasses significantly limits their development and preparation. This paper updates the current state of knowledge by presenting the results of structural studies of two newly-developed Al79Ni5Fe5Y11 and Al79Ni11Fe5Y5 alloys with a reduced aluminium content (< 80 at.%). The alloys were produced by conventional casting (ingots) and melt-spinning (ribbons). Structural characterization was carried out for bulk ingots first, and then for the melt-spun ribbons. The ingots possessed a multiphase crystalline structure, as confirmed by X-ray diffraction and scanning electron microscopy observations. The amorphous structure of the melt-spun ribbons was determined by X-ray diffraction and transmission electron microscopy. SEM observations and EDX element maps of the cross-section of melt-spun ribbons indicated a homogeneous elemental composition. Neutron diffraction revealed the presence of nanocrystals in the amorphous matrix of the melt-spun ribbons. DSC data of the melt-spun ribbons showed exothermic events corresponding to the first crystallization at temperatures of 408 °C and 387 °C for Al79Ni5Fe5Y11 and Al79Ni11Fe5Y5, respectively.

Influence of the modifiers in polyol method on magnetically induced hyperthermia and biocompatibility of ultrafine magnetite nanoparticles.

Magnetite nanoparticles (Fe3O4 NPs) are widely tested in various biomedical applications, including magnetically induced hyperthermia. In this study, the influence of the modifiers, i.e., urotropine, polyethylene glycol, and NH4HCO3, on the size, morphology, magnetically induced hyperthermia effect, and biocompatibility were tested for Fe3O4 NPs synthesized by polyol method. The nanoparticles were characterized by a spherical shape and similar size of around 10 nm. At the same time, their surface is functionalized by triethylene glycol or polyethylene glycol, depending on the modifiers. The Fe3O4 NPs synthesized in the presence of urotropine had the highest colloidal stability related to the high positive value of zeta potential (26.03 ± 0.55 mV) but were characterized by the lowest specific absorption rate (SAR) and intrinsic loss power (ILP). The highest potential in the hyperthermia applications have NPs synthesized using NH4HCO3, for which SAR and ILP were equal to 69.6 ± 5.2 W/g and 0.613 ± 0.051 nHm2/kg, respectively. Their application possibility was confirmed for a wide range of magnetic fields and by cytotoxicity tests. The absence of differences in toxicity to dermal fibroblasts between all studied NPs was confirmed. Additionally, no significant changes in the ultrastructure of fibroblast cells were observed apart from the gradual increase in the number of autophagous structures.

Evaluation of the biocompability and corrosion activity of resorbable CaMgZnYbBAu alloys.

Calcium-based alloys can be promising candidates for use as biodegradable implants because of attractive properties as mechanical, corrosive, and biocompatible. In the work, the biocompatibility authors discussed the results of the Ca32Mg12Zn38Yb18-xBx (x = 0, 1, 2, 3 at.%) and Ca32Mg12Zn38Yb18-2xBxAux (x = 1, 2 at.%) alloys. The tests were performed using a MTT assay. The corrosion behavior of such Ca-based alloys in PWE fluid at 37 °C was studied and compared with the results in Ringer's solution from previous works. Electrochemical tests were presented by open circuit potential and potentiodynamic curves. Different concentrations of boron and gold in the alloys caused changes in the corrosion results. The best corrosion resistance in PWE solution was observed for the Ca-based alloy with 2 at.% Au due to the lowest value of the corrosion current density (jcorr), equal to 10.6 µA·cm-2. A slightly higher value of jcorr was obtained for the Ca32Mg12Zn38Yb15B3 alloy with the lowest roughness values. The results of the cytotoxicity tests also showed that the alloy with 3 at.% boron was characterized by the highest cell viability. The investigation results discussed in the work allow us to suggest that the presented calcium alloys with 3 at.% of B, and 2 at.% of Au addition may be promising materials for the use in implantology.

Magnetite Nanoparticles in Magnetic Hyperthermia and Cancer Therapies: Challenges and Perspectives.

Until now, strategies used to treat cancer are imperfect, and this generates the need to search for better and safer solutions. The biggest issue is the lack of selective interaction with neoplastic cells, which is associated with occurrence of side effects and significantly reduces the effectiveness of therapies. The use of nanoparticles in cancer can counteract these problems. One of the most promising nanoparticles is magnetite. Implementation of this nanoparticle can improve various treatment methods such as hyperthermia, targeted drug delivery, cancer genotherapy, and protein therapy. In the first case, its feature makes magnetite useful in magnetic hyperthermia. Interaction of magnetite with the altered magnetic field generates heat. This process results in raised temperature only in a desired part of a patient body. In other therapies, magnetite-based nanoparticles could serve as a carrier for various types of therapeutic load. The magnetic field would direct the drug-related magnetite nanoparticles to the pathological site. Therefore, this material can be used in protein and gene therapy or drug delivery. Since the magnetite nanoparticle can be used in various types of cancer treatment, they are extensively studied. Herein, we summarize the latest finding on the applicability of the magnetite nanoparticles, also addressing the most critical problems faced by smart nanomedicine in oncological therapies.

Study of crystallization mechanism of Al-based amorphous alloys by in-situ high temperature X-ray diffraction method.

The role of transition metals (TMs) addition on the formation and crystallization of amorphous Al85TMs10Y5 alloys was described using in-situ high-temperature X-ray diffraction. The structural results were compared with differential scanning calorimetry and dynamical mechanical analysis to obtain detailed information about the nucleation and growth of crystalline phases. The performed analysis confirmed that Fe and Cu addition drastically changes the crystallization temperature and the phase composition of the fully crystallized alloys. While for Al85Ni10Y5 alloy, the second crystallization step is related to the formation of Al19Ni5Y3 phase, for Al85(Ni, Fe)10Y5 and Al85(Ni, Fe, Cu)10Y5 alloys crystallization of Al15Fe9Y2 phase was observed. Interestingly, the performed analysis showed that forming a homogenous amorphous phase is not necessary to obtain the best corrosion resistance. It was noted that the precipitation of the YCr2Al20 phase in the Cu-rich amorphous matrix should be a much more interesting approach.

Structure and Magnetic Properties of Thermodynamically Predicted Rapidly Quenched Fe85-xCuxB15 Alloys.

In this work, based on the thermodynamic prediction, the comprehensive studies of the influence of Cu for Fe substitution on the crystal structure and magnetic properties of the rapidly quenched Fe85B15 alloy in the ribbon form are performed. Using thermodynamic calculations, the parabolic shape dependence of the ΔGamoprh with a minimum value at 0.6% of Cu was predicted. The ΔGamoprh from the Cu content dependence shape is also asymmetric, and, for Cu = 0% and Cu = 1.5%, the same ΔGamoprh value is observed. The heat treatment optimization process of all alloys showed that the least lossy (with a minimum value of core power losses) is the nanocomposite state of nanocrystals immersed in an amorphous matrix obtained by annealing in the temperature range of 300-330 °C for 20 min. The minimum value of core power losses P10/50 (core power losses at 1T@50Hz) of optimally annealed Fe85-xCuxB15 x = 0,0.6,1.2% alloys come from completely different crystallization states of nanocomposite materials, but it strongly correlates with Cu content and, thus, a number of nucleation sites. The TEM observations showed that, for the Cu-free alloy, the least lossy crystal structure is related to 2-3 nm short-ordered clusters; for the Cu = 0.6% alloy, only the limited value of several α-Fe nanograins are found, while for the Cu-rich alloy with Cu = 1.2%, the average diameter of nanograins is about 26 nm, and they are randomly distributed in the amorphous matrix. The only high number of nucleation sites in the Cu = 1.2% alloy allows for a sufficient level of grains' coarsening of the α-Fe phase that strongly enhances the ferromagnetic exchange between the α-Fe nanocrystals, which is clearly seen with the increasing value of saturation induction up to 1.7T. The air-annealing process tested on studied alloys for optimal annealing conditions proves the possibility of its use for this type of material.

Influence of Magnetite Nanoparticles Shape and Spontaneous Surface Oxidation on the Electron Transport Mechanism.

The spontaneous oxidation of a magnetite surface and shape design are major aspects of synthesizing various nanostructures with unique magnetic and electrical properties, catalytic activity, and biocompatibility. In this article, the roles of different organic modifiers on the shape and formation of an oxidized layer composed of maghemite were discussed and described in the context of magnetic and electrical properties. It was confirmed that Fe3O4 nanoparticles synthesized in the presence of triphenylphosphine could be characterized by cuboidal shape, a relatively low average particle size (9.6 ± 2.0 nm), and high saturation magnetization equal to 55.2 emu/g. Furthermore, it has been confirmed that low-frequency conductivity and dielectric properties are related to surface disordering and oxidation. The electric energy storage possibility increased for nanoparticles with a disordered and oxidized surface, whereas the dielectric losses in these particles were strongly related to their size. The cuboidal magnetite nanoparticles synthesized in the presence of triphenylphosphine had an ultrahigh electrical conductivity (1.02 × 10-4 S/cm at 10 Hz) in comparison to the spherical ones. At higher temperatures, the maghemite content altered the behavior of electrons. The electrical conductivity can be described by correlated barrier hopping or overlapping large polaron tunneling. Interestingly, the activation energies of electrons transport by the surface were similar for all the analyzed nanoparticles in low- and high-temperature ranges.

Glass-Forming Ability and Corrosion Resistance of Al88Y8-xFe4+x (x = 0, 1, 2 at.%) Alloys.

The effect of iron and yttrium additions on glass forming ability and corrosion resistance of Al88Y8-xFe4+x (x = 0, 1, 2 at.%) alloys in the form of ingots and melt-spun ribbons was investigated. The crystalline multiphase structure of ingots and amorphous-crystalline structure of ribbons were examined by a number of analytical techniques including X-ray diffraction, Mössbauer spectroscopy, and transmission electron microscopy. It was confirmed that the higher Fe additions contributed to formation of amorphous structures. The impact of chemical composition and structure of alloys on their corrosion resistance was characterized by electrochemical tests in 3.5% NaCl solution at 25 °C. The identification of the mechanism of chemical reactions taking place during polarization test along with the morphology and internal structure of the surface oxide films generated was performed. It was revealed that the best corrosion resistance was achieved for the Al88Y7Fe5 alloy in the form of ribbon, which exhibited the lowest corrosion current density (jcorr = 0.09 µA/cm2) and the highest polarization resistance (Rp = 96.7 kΩ∙cm2).

Influence of Cu Content on Structure, Thermal Stability and Magnetic Properties in Fe72-xNi8Nb4CuxSi2B14 Alloys.

The effect of substitution of Fe by Cu on the crystal structure and magnetic properties of Fe72-xNi8Nb4CuxSi2B14 alloys (x = 0.6, 1.1, 1.6 at.%) in the form of ribbons was investigated. The chemical composition of the materials was established on the basis of the calculated minima of thermodynamic parameters: Gibbs free energy of amorphous phase formation ΔGamorph (minimum at 0.6 at.% of Cu) and Gibbs free energy of mixing ΔGmix (minimum at 1.6 at.% of Cu). The characteristic crystallization temperatures Tx1onset and Tx1 of the alpha-iron phase together with the activation energy Ea for the as-spun samples were determined by differential scanning calorimetry (DSC) with a heating rate of 10-100 °C/min. In order to determine the optimal soft magnetic properties, the wound cores were subjected to a controlled isothermal annealing process in the temperature range of 340-640 °C for 20 min. Coercivity Hc, saturation induction Bs and core power losses at B = 1 T and frequency f = 50 Hz P10/50 were determined for all samples. Moreover, for the samples with the lowest Hc and P10/50, the magnetic losses were determined in a wider frequency range 50 Hz-400 kHz. The real and imaginary parts of the magnetic permeability µ', µâ€³ along with the cut-off frequency were determined for the samples annealed at 360, 460, and 560 °C. The best soft magnetic properties (i.e., the lowest value of Hc and P10/50) were observed for samples annealed at 460 °C, with Hc = 4.88-5.69 A/m, Bs = 1.18-1.24 T, P10/50 = 0.072-0.084 W/kg, µ' = 8350-10,630 and cutoff frequency at 8-9.3 × 104 Hz. The structural study of as-spun and annealed ribbons was carried out using X-ray diffraction (XRD) and a transmission electron microscope (TEM).

Broadband dielectric spectroscopy for monitoring temperature-dependent chloride ion motion in BiOCl plates.

The dielectric properties and electrical conduction mechanism of bismuth oxychloride (BiOCl) plates synthesized using chloramine-T as the chloride ion source were investigated. Thermally-activated structure rebuilding was monitored using broadband dielectric spectroscopy, which showed that the onset temperature of this process was 283 K. This rebuilding was related to the introduction of free chloride ions into [Bi2O2]2+ layers and their growth, which increased the intensity of the (101) diffraction peak. The electrical conductivity and dielectric permittivity were related to the movement of chloride ions between plates (in the low-frequency region), the interplanar motion of Cl- ions at higher frequencies, vibrations of these ions, and charge carrier hopping at frequencies above 10 kHz. The influence of the free chloride ion concentration on the electrical conductivity was also described. Structure rebuilding was associated with a lower concentration of free chloride ions, which significantly decreased the conductivity. According to the analysis, the BiOCl plate conductivity was related to the movement of Cl- ions, not electrons.

Influence of Cu Content on Structure and Magnetic Properties in Fe86-xCuxB14 Alloys.

Influence of Cu content on thermodynamic parameters (configurational entropy, Gibbs free energy of mixing, Gibbs free energy of amorphous phase formation), crystallization kinetics, structure and magnetic properties of Fe86-xCuxB14 (x = 0, 0.4, 0.55, 0.7, 1) alloys is investigated. The chemical composition has been optimized using a thermodynamic approach to obtain a minimum of Gibbs free energy of amorphous phase formation (minimum at 0.55 at.% of Cu). By using differential scanning calorimetry method the crystallization kinetics of amorphous melt-spun ribbons was analyzed. It was found that the average activation energy of α-Fe phase crystallization is in the range from 201.8 to 228.74 kJ/mol for studied samples. In order to obtain the lowest power core loss values, the isothermal annealing process was optimized in the temperature range from 260 °C to 400 °C. Materials annealed at optimal temperature had power core losses at 1 T/50 Hz-0.13-0.25 W/kg, magnetic saturation-1.47-1.6 T and coercivity-9.71-13.1 A/m. These samples were characterized by the amorphous structure with small amount of α-Fe nanocrystallites. The studies of complex permeability allowed to determine a minimum of both permeability values at 0.55 at.% of Cu. At the end of this work a correlation between thermodynamic parameters and kinetics, structure and magnetic properties were described.

Effect of the Thickness of TiO2 Films on the Structure and Corrosion Behavior of Mg-based Alloys.

This article discusses the influence of the thickness of TiO2 films deposited onto MgCa2Zn1 and MgCa2Zn1Gd3 alloys on their structure, corrosion behavior, and cytotoxicity. TiO2 layers (about 200 and 400 nm thick) were applied using magnetron sputtering, which provides strong substrate adhesion. Such titanium dioxide films have many attractive properties, such as high corrosion resistance and biocompatibility. These oxide coatings stimulate osteoblast adhesion and proliferation compared to alloys without the protective films. Microscopic observations show that the TiO2 surface morphology is homogeneous, the grains have a spherical shape (with dimensions from 18 to 160 nm). Based on XRD analysis, it can be stated that all the studied TiO2 layers have an anatase structure. The results of electrochemical and immersion studies, performed in Ringer's solution at 37 °C, show that the corrosion resistance of the studied TiO2 does not always increase proportionally with the thickness of the films. This is a result of grain refinement and differences in the density of the titanium dioxide films applied using the physical vapor deposition (PVD) technique. The results of 24 h immersion tests indicate that the lowest volume of evolved H2 (5.92 mL/cm2) was with the 400 nm thick film deposited onto the MgCa2Zn1Gd3 alloy. This result is in agreement with the good biocompatibility of this TiO2 film, confirmed by cytotoxicity tests.

Effect of Co Substitution on Crystallization and Magnetic Behavior of Fe85.45-xCoxCu0.55B14 Metallic Glass.

The effects of Co for Fe substitution on magnetic properties, thermal stability and crystal structure of Fe85.45-xCoxCu0.55B14 (x = 0, 2.5, 5, 7.5, 10) melt spun amorphous alloys were investigated. The Cu content was firstly optimized to minimize the energy of amorphous phase formation by the use of a thermodynamic approach. The formation of crystalline α-Fe type phase has been described using differential scanning calorimetry, X-ray diffractometry and transmission electron microscopy. The classical heat treatment process (with heating rate 10 °C/min) in vacuum for wound toroidal cores was optimized in the temperature range from 280 to 430 °C in order to obtain the best magnetic properties (magnetic saturation Bs and coercivity Hc obtained from the B(H) dependencies) at 50 Hz frequency. For optimal heat-treated samples, the complex magnetic permeability in the frequencies 104-108 Hz at room temperature was measured. Finally, magnetic core losses were obtained for 1 T/50 Hz and 1.5 T/50 Hz values for samples annealed at T = 310 °C. An analysis of transmission electron microscope images and electron diffraction patterns confirmed that high magnetic parameters are related to the coexistence of the amorphous and nanocrystalline phases.

Dielectric and electromagnetic interference shielding properties of high entropy (Zn,Fe,Ni,Mg,Cd)Fe2O4 ferrite.

The new (Zn,Mg,Ni,Fe,Cd)Fe2O4 high entropy ferrite with average crystallite size 11.8 nm was synthesized in two stages by annealing of co-precipitated amorphous precursor. The dielectric spectroscopy confirms, that the electrical conductivity and polarization processes are associated with the mobility of electrons in the structure of ferrite. It was concluded, that the both, high frequency complex dielectric permittivity as well as complex magnetic permeability are strongly temperature and frequency dependent. The AC electrical conductivity is associated with quantum mechanical tunneling of electrons and related to the transfer of charge carriers between Fe2+ and Fe3+ ions. Moreover, the microwave absorption properties were determined. The best microwave absorption properties have been confirmed in the frequency range 1.9 to 2.1 GHz for a layer which is 0.8-1 cm thick. For this range, reflection loss (RL) is lower than -25 dB and shielding effectiveness (SE) lower than -50 dB.

Electrical Conduction Mechanism and Dielectric Properties of Spherical Shaped Fe3O4 Nanoparticles Synthesized by Co-Precipitation Method.

On the basis of dielectric measurements performed in a wide temperature range (173⁻373 K), a comprehensive analysis of the dielectric and electrical properties of magnetite nanoparticles electrical conduction mechanism of compressed spherical shaped Fe3O4 nanoparticles was proposed. The electrical conductivity of Fe3O4 nanoparticles was related to two different mechanisms (correlated barrier hopping and non-overlapping small polaron tunneling mechanisms); the transition between them was smooth. Additionally, role of grains and grain boundaries with charge carrier mobility and with observed hopping mechanism was described in detail. It has been confirmed that conductivity dispersion (as a function of frequencies) is closely related to both the long-range mobility (conduction mechanism associated with grain boundaries) and to the short-range mobility (conduction mechanism associated with grains). Calculated electron mobility increases with temperature, which is related to the decreasing value of hopping energy for the tunneling of small polarons. The opposite scenario was observed for the value of electron hopping energy.