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The effects of Ce-Dy co-doping on the crystal structure, optical, dielectric, magnetic properties, and hyperfine interactions of Ni-Co spinel ferrite microspheres synthesized hydrothermally have been studied. A series of ferrites with the general formula Ni0.5-Co0.5CexDyxFe2-2xO4 were synthesized with x values ranging from 0.00 to 0.10. The phase, crystallinity, and morphology of ferrite microspheres were analyzed by X-ray powder diffractometry (XRD), scanning and transmission electron microscopes (SEM and TEM), respectively. The structural analyses of the synthesized ferrite microspheres confirmed their high purity and cubic crystalline phase. The Diffuse reflectance spectroscopic (DRS) measurements were presented to calculate direct optical energy band gaps (E-g) and is found in the range 1.63 eV - 1.84 eV. Fe-57 Mossbauer spectroscopy showed that the hyperfine magnetic field of tetrahedral (A) and octahedral (B) sites decreased with the substitution of Dy3+-Ce3+ ions that preferrentially occupy the B site. The impact of the rare-earth content (x) on the magnetic features of the prepared NiCo ferrite microspheres was investigated by analyzing M-H loops, which showed soft ferrimagnetism. The magnetic features illustrate a great impact of the incorporation of Ce3+-Dy3+ ions within the NiCo ferrite structure. The saturation magnetization (M-s), remanence (M-r), and coercivity (H-c) increased gradually with increasing Ce-Dy content. At x = 0.04, M-s, M-r, and H-c attain maximum values of about 31.2 emu/g, 11.5 emu/g, and 512.4 Oe, respectively. The Bohr magneton (n(B)) and magneto-crystalline anisotropy constant (K-eff) were also determined and evaluated with correlation to other magnetic parameters. Further increase in Ce3+-Dy3+ content (i.e., x >= 0.06) was found to decrease M-s, M-r, and H-c values. The variations in magnetic parameters (M-s, M-r, and H-c) were largely caused by the surface spins effect, the variations in crystallite/particle size, the distribution of magnetic ions into the different sublattices, the evolutions of magneto-crystalline anisotropy, and the variations in the magnetic moment (n(B)). The squareness ratios were found to be lower than the predicted theoretical value of 0.5 for various samples, indicating that the prepared Ce-Dy substituted NiCo ferrite microspheres are composed of NPs with single-magnetic domain (SMD). Temperature and frequency-dependent electrical and dielectric measurements have been done to estimate the ac/dc conductivity, dielectric constant, and tangent loss values for all the samples. The ac conductivity measurements confirmed the power-law rules, largely dependent on Ce-Dy content. Impedance analysis stated that the conduction mechanisms in all samples are mainly due to the grains-grain boundaries. The dielectric constant of NiCo ferrite microspheres give rise to normal dielectric distribution, with the frequency depending strongly on the Ce-Dy content. The observed variation in tangential loss with frequency can be attributed to the conduction mechanism in ferrites, like Koop's phenomenological model. (C) 2021 The Author(s). Published by Elsevier B.V. Deanship for Scientific Research of Imam Abdulrahman Bin Faisal University [2020-164-IRMC] The authors acknowledge the financial supports provided by the Deanship for Scientific Research of Imam Abdulrahman Bin Faisal University (Project application No. 2020-164-IRMC) . WOS:000702874100011 2-s2.0-85112331089

This article belongs to the Special Issue Rational Design and Characterization of Hydrogels to Improve Pharmaceutical and Biomedical Applicability., Modifying hydrogels in order to enhance their conductivity is an exciting field with applications in cardio and neuro-regenerative medicine. Therefore, we have designed hybrid alginate hydrogels containing uncoated and protein-coated reduced graphene oxide (rGO). We specifically studied the adsorption of three different proteins, BSA, elastin, and collagen, and the outcomes when these protein-coated rGO nanocomposites are embedded within the hydrogels. Our results demonstrate that BSA, elastin, and collagen are adsorbed onto the rGO surface, through a non-spontaneous phenomenon that fits Langmuir and pseudo-second-order adsorption models. Protein-coated rGOs are able to preclude further adsorption of erythropoietin, but not insulin. Collagen showed better adsorption capacity than BSA and elastin due to its hydrophobic nature, although requiring more energy. Moreover, collagen-coated rGO hybrid alginate hydrogels showed an enhancement in conductivity, showing that it could be a promising conductive scaffold for regenerative medicine., This study was financially supported by the Basque Country Government [grant number T907-16].

High-yield monodispersed silver (Ag) nanospheres were modeled, designed, and synthesized by microwave-assisted (MW-assisted) polyol method from AgNO3, polyvinyl pyrrolidone (PVP), and ethylene glycol (EG), as precursors, at 145 °C within a short reaction time of 2 min, and the results were compared to those of conventional polyol method. Maintaining the PVP:AgNO3 molar ratio, the effect of increasing the amounts of AgNO3 and PVP at a constant amount of EG (40 mL) on the final product was evaluated. The synthesized nanoparticles (NPs) were characterized by SEM, UV–Vis spectroscopy, FTIR and DLS analysis. The results showed that with increasing the amount of AgNO3 to 0.5 and 1 g, monodispersed Ag nanoparticles (Ag NPs) with particle sizes of 54 and 61 nm were formed, as per the plasmon absorption peaks at 436 and 442 nm, respectively. Moreover, using 40 mL of the EG solution, we could obtain a high yield of the NPs (~90%). The sub-gram yield was excellently high, offering great opportunities for commercializing the procedure. Also, the proposed study paves a new way for Ag NPs realization for different practical applications ranging from MW to optics.

Reduced energy consumption and environmentally friendly, abundant constituents are gaining more attention for the synthesis of energy materials. A rapid, highly scalable, and process-temperature-sensitive solution synthesis route is demonstrated for the fabrication of thermoelectric Cu2-xSe. The process relies on readily available precursors and microwave-assisted thermolysis, which is sensitive to reaction conditions; yielding Cu1.8Se at 200 C and Cu2Se at 250 C within 6-8 min reaction time. Transmission electron microscopy (TEM) revealed crystalline nature of as-made particles with irregular truncated morphology, which exhibit a high phase purity as identified by X-ray powder diffraction (XRPD) analysis. Temperature-dependent transport properties were characterized via electrical conductivity, Seebeck coefficient, and thermal diffusivity measurements. Subsequent to spark plasma sintering, pure Cu1.8Se exhibited highly compacted and oriented grains that were similar in size in comparison to Cu2Se, which led to its high electrical and low thermal conductivity, reaching a very high power-factor (24 µW/K-2cm-1). Density-of-states (DOS) calculations confirm the observed trends in electronic properties of the material, where Cu-deficient phase exhibits metallic character. The TE figure of merit (ZT) was estimated for the materials, demonstrating an unprecedentedly high ZT at 875 K of 2.1 for Cu1.8Se sample, followed by 1.9 for Cu2Se. Synthetic and processing methods presented in this work enable large-scale production of TE materials and components for niche applications. Funding agencies: The Swedish Energy Agency [Energimyndigheten, 43521-1], Swedish Research Council [VR, 2018-03462]. SB acknowledges support by Scientific and Technological ResearchCouncil of Turkey [TUBITAK, 216M254] and Scientific Research Projects Coordination Unit of Istanbul University[BAP, 21809, 32641 and 35577]. JR acknowledges support from the Swedish Foundation for Strategic Research[SSF, EM16-0004].

Latest nanotechnology concepts applied in thermoelectric (TE) research have opened many new avenues to improve the ZT value. Low dimensional structures can improve the ZT value as compared to bulk materials by substantial reduction in the lattice thermal conductivity, κL. However, the materials were not feasible for the industrial scale production of macroscopic devices because of complicated and costly manufacturing processes involved. Bulk nanostructured (NS) TEs are normally fabricated using a bulk process rather than a nano-fabrication process, which has the important advantage of producing in large quantities and in a form that is compatible with commercially available TE devices.We developed fabrication strategies for bulk nanostructured skutterudite materials based on FexCo1-xSb3. The process is based on precipitation of a precursor material with the desired metal atom composition, which is then exposed to thermochemical processing of calcination followed by reduction. The resultant material thus formed maintains nanostructured particles which are then compacted using Spark Plasma Sintering (SPS) by utilizing previously optimized process parameters. Microstructure, crystallinity, phase composition, thermal stability and temperature dependent transport property evaluation has been performed for compacted NS FexCo1-xSb3. Evaluation results are presented in detail, suggesting the feasibility of devised strategy for bulk quantities of doped TE nanopowder fabrication.

This article reports convective single-phase heat transfer performance in laminar flow for some selected nanofluids (NFs) in an open small diameter test section. A 0.50 mm inner diameter, 30 cm lon ...

We report a detailed computational and experimental study of the interaction of single-walled carbon nanotubes (SWCNTs) with the drug-metabolizing cytochrome P450 enzyme, CYP3A4. Dose-dependent inhibition of CYP3A4-mediated conversion of the model compound, testosterone, to its major metabolite, 6β-hydroxy testosterone was noted. Evidence for a direct interaction between SWCNTs and CYP3A4 was also provided. The inhibition of enzyme activity was alleviated when SWCNTs were pre-coated with bovine serum albumin. Furthermore, covalent functionalization of SWCNTs with polyethylene glycol (PEG) chains mitigated the inhibition of CYP3A4 enzymatic activity. Molecular dynamics simulations suggested that inhibition of the catalytic activity of CYP3A4 is mainly due to blocking of the exit channel for substrates/products through a complex binding mechanism. This work suggests that SWCNTs could interfere with metabolism of drugs and other xenobiotics and provides a molecular mechanism for this toxicity. Our study also suggests means to reduce this toxicity, eg., by surface modification.

A facile and high yield synthesis route was developed for the fabrication of bulk nanostructured copper selenide (Cu2Se) with high thermoelectric efficiency. Starting from readily available precursor materials and by means of rapid and energy-efficient microwave-assisted thermolysis, nanopowders of Cu2Se were synthesized. Powder samples and compacted pellets have been characterized in detail for their structural, microstructural and transport properties. α to β phase transition of Cu2Se was confirmed using temperature dependent X-ray powder diffraction and differential scanning calorimetry analyses. Scanning electron microscopy analysis reveals the presence of secondary globular nanostructures in the order of 200 nm consisting of

WOS: 000367261600028 Barium hexaferrite with nominal chemical composition BaMnZn2Fe10O19 has been synthesized by sol-gel method, using polymethyl methacrylate (PMMA) as a template. Fourier transform infrared spectroscopy (FT-IR) and X-ray powder diffraction (XRD) were used for approving the formation of barium hexaferrites. In addition, transmission electron microscopy (TEM) and scanning electron microscopy (SEM) were performed to investigate the structural and morphological properties of BaM. The dielectric properties were studied by impedance measurements as a function of frequency (in the range 0.1 Hz-1 MHz). The XRD patterns confirmed the formation of single-phase magnetoplumbite with crystallite size around 73 nm. The results of dielectric parameters and conductivity measurements showed three regions with different behaviors in electrical conduction mechanism. Fatih University [10790]; Swedish Research Council [VR-SRL 2013-6780] This work was supported by Fatih University under BAP Grant no.: 10790 and in part by Swedish Research Council (VR-SRL 2013-6780).

A series of Ni-doped cobalt ferrites NixCo1−xFe2O4 (x = 0.0, 0.4, 0.6, 0.8, and 1.0) were prepared using microwave-induced combustion. Nickel, cobalt, and ferric nitrates were used as starting materials and glycine as fuel. The influence of Ni content on the lattice parameter, stretching vibrations, and magnetization was studied. XRD, FTIR, and SEM were used for structure, composition, and morphology investigation. A porous network structure was observed with average particle size 60–67 nm. All samples had a cubic spinel structure. The unit cell parameter “a” decreases linearly with nickel concentration due to the smaller ionic radius of nickel. Magnetization measurements showed that coercivity decreased as Ni content increased; it increased with decreasing temperature.

A new borophosphate compound with the composition (NH4)χ Mn((3−χ)/2)(H2O)2 [BP2O8]·(1−x)H2O was prepared under mild hydrothermal conditions and characterized by X-ray powder diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) methods. The title compound was synthesized from MnCl2·2H2O, H3BO3, and (NH4)2HPO4 with variable molar ratios by heating at 180 °C for 7 days in an autoclave. The X-ray diffraction data of the water insoluble polycrystalline powder was indexed using the TREOR program in hexagonal system with the unit cell parameters of a = 9.5104, c = 15.7108 Å, Z = 6 and the space group P65 (No.176). (NH4)χ Mn((3−χ)/2)(H2O)2 [BP2O8]·(1−x)H2O is isostructural with (NH4)χ M ((3−χ)2)/II (H2O)2 [BP2O8]·(1−x)H2O (MII = Co, Cd, Mg; x = 0.5–1). Its unit cell parameters and hkl values were in good agreement with the other isostructural compounds. This is the first report presenting both the synthetic details and the indexed X-ray powder diffraction pattern of this compound along with the characterization by FTIR, thermal gravimetric analysis, scanning electron microscopy and EPR.

A nanofluid is a suspension containing nanoparticles in conventional heat transfer fluids. This paper reports on an investigation of alumina (Al2O3) nanoparticles in Antifrogen N, also called AFN, which is a popular antifreeze coolant consisting primarily of ethylene glycol and other additives to impede corrosion. The base carrier fluid is 50% by weight of water and 50% by weight of AFN. We systematically measured the nanomaterials and heat transfer data of nanofluids for four different size particles, namely, 20, 40, 150, and 250 nm alumina particles. The pH of all the nanofluids is adjusted to have a stable dispersion. The material characterizations include SEM and DLS particle measurements. We measured thermal conductivity, viscosity, and heat transfer coefficient in developing flow of the nanofluids. We observed that these nanofluids behave as any other classical fluids in thermally developing flow and classical heat transfer correlations can be used to completely describe the characteristics of these nanofluids.

A novel synthesis route for the fabrication of p-type nanostructured skutterudite, FexCo1-xSb3 in large quantity is reported. This scalable synthesis route provides nano-engineered material with less impact on the environment compared to conventional synthesis procedures. Several Fe substituted compositions have been synthesized to confirm the feasibility of the process. The process consists of a nano-sized precursor fabrication of iron and cobalt oxalate, and antimony oxides by chemical co-precipitation. Further thermochemical processes result in the formation of iron substituted skutterudites. The nanopowders are compacted by Spark Plasma Sintering (SPS) technique in order to maintain nanostructure. Detailed physicochemical as well as thermoelectric transport properties are evaluated. Results reveal strongly reduced thermal conductivity values compared to conventionally prepared counterparts, due to nanostructuring. P-type characteristic was observed from the Seebeck measurements while electrical conductivity is high and shows metallic behavior. The highest TE figure of merit of 0.25 at 800 K has been achieved, which is strongly enhanced with respect to the mother compound CoSb3. This suggests the promise of the utilized method of fabrication and processing for TE applications with improved performance.

Superparamagnetic iron oxide nanoparticles (SPIONs) have emerged as promising contrast agents for magnetic resonance imaging. The influence of different surface coatings on the biocompatibility of SPIONs has been addressed, but the potential impact of the so-called corona of adsorbed proteins on the surface of SPIONs on their biological behavior is less well studied. Here, we determined the composition of the plasma protein corona on silica-coated versus dextran-coated SPIONs using mass spectrometry-based proteomics approaches. Notably, gene ontology (GO) enrichment analysis and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analysis revealed distinct protein corona compositions for the two different SPIONs. Relaxivity of silica-coated SPIONs was modulated by the presence of a protein corona. Moreover, the viability of primary human monocyte-derived macrophages was influenced by the protein corona on silica-coated, but not dextran-coated SPIONs, and the protein corona promoted cellular uptake of silica-coated SPIONs, but did not affect internalization of dextran-coated SPIONs.

Antimony telluride, (Sb2Te3), and its doped derivatives are considered to be among the best p-type thermoelectric (TE) materials for room temperature (300–400 K) applications. However, it is still desirable to develop rapid and economical routes for large-scale synthesis of Sb2Te3 nanostructures. We report herein a high yield, simple and easily scalable synthetic method for polycrystalline Sb2Te3 nanostructures. Prepared samples were compacted into dense pellets by use of spark plasma sintering. The products were characterized by x-ray diffraction and scanning electron microscopy. To investigate the anisotropic behavior of Sb2Te3 TE transport property measurements were performed along and perpendicular to the direction of compaction. Thermal conductivity, electrical conductivity, and Seebeck coefficient measurement over the temperature range 350–525 K showed that the anisotropy of the material had a large effect on TE performance.

Nanostructured powders of thermoelectric (TE) CoSb3 compounds were synthesized using a chemical alloying method. This method involved co-precipitation of oxalate precursors in aqueous solution with controlled pH, followed by thermochemical treatments including calcination and reduction to produce stoichiometric nanostructured CoSb3. Moreover, CoSb3 nanoparticles were consolidated by spark plasma sintering (SPS) with a very brief processing time. Very high compaction densities (>95%) were achieved and the grain growth was almost negligible during consolidation. An iterative procedure was developed to maintain pre-consolidation particle size and to compensate Sb evaporation during reduction. Significant changes in particle size and morphology were observed, and the post-reduction cooling was found to be an important stage in the process. The spark plasma sintering (SPS) parameters were optimized to minimize the grain growth while achieving sufficient densification. Grain sizes in the range of 500 nm to 1 mu m, with compaction density of 95-98% were obtained. Preliminary measurements of thermal diffusivity and conductivity showed the dependence on grain size as well as on porosity. TE transport properties were measured in the temperature range of 300-650 K. Sample showed p-type behavior with a positive Seebeck coefficient, which increases with increasing temperature. Electrical conductivity measurements indicate metallic behavior and it decreases with increasing temperature. Thermal conductivity also decreases with increasing temperature and major contribution is due to the lattice component. A TE figure of merit of 0.15 was achieved for high purity CoSb3 nanostructured TE material at 650 K and these results are comparable with the values reported for the best unfilled/undoped CoSb3 in the literature. QC 20140909

Eosinophil peroxidase (EPO) is one of the major oxidant-producing enzymes during inflammatory states in the human lung. The degradation of single-walled carbon nanotubes (SWCNTs) upon incubation with human EPO and H2O 2 is reported. Biodegradation of SWCNTs is higher in the presence of NaBr, but neither EPO alone nor H2O2 alone caused the degradation of nanotubes. Molecular modeling reveals two binding sites for SWCNTs on EPO, one located at the proximal side (same side as the catalytic site) and the other on the distal side of EPO. The oxidized groups on SWCNTs in both cases are stabilized by electrostatic interactions with positively charged residues. Biodegradation of SWCNTs can also be executed in an ex vivo culture system using primary murine eosinophils stimulated to undergo degranulation. Biodegradation is proven by a range of methods including transmission electron microscopy, UV-visible-NIR spectroscopy, Raman spectroscopy, and confocal Raman imaging. Thus, human EPO (in vitro) and ex vivo activated eosinophils mediate biodegradation of SWCNTs: an observation that is relevant to pulmonary responses to these materials. Human eosinophil peroxidase (EPO) is able to degrade SWCNTs in vitro in the presence of H2O2. EPO is one of the major oxidant-generating enzymes present in human lungs during inflammatory states. The biodegradation of SWCNTs is evidenced also in an ex vivo culture system using primary murine eosinophils stimulated to undergo degranulation. These results are relevant to potential respiratory exposure to carbon nanotubes. QC 20131113

Polyacrylonitrile (PAN) textiles with 2 mm thickness are coated with magnetic nanoparticles in coating baths with Ni, Co and their alloys via an electroless metal deposition method. The crystal structure, morphology and magnetic nature of composites are investigated by X-ray Powder diffraction, Scanning Electron Microscopy, and dc magnetization measurement techniques. The frequency dependent microwave absorption measurements have been carried out in the frequency range of 12.4-18 GHz (X and P bands). Diamagnetic and ferromagnetic properties are also investigated. Finally, the microwave absorption of composites is found strongly dependent on the coating time. One absorption peak is observed between 14.3 and 15.8 GHz with an efficient absorption bandwidth of 3.3-4.1 GHz (under -20 dB reflection loss limit). The Reflection loss (RL) can be achieved between -30 and -50 dB. It was found that the RL is decreasing and absorption bandwidth is decreasing with increasing coating time. While absorption peak moves to lower frequencies in Ni coated PAN textile, it goes higher frequencies in Co coated ones. The Ni-Co alloy coated composites have fluctuating curve of absorption frequency with respect to coating time. These results encourage further development of magnetic nanoparticle coated textile absorbers for broadband applications. Crown Copyright (c) 2012 Published by Elsevier B.V. All rights reserved.

Recently magnesium silicide (Mg2Si) has received great interest from thermoelectric (TE) society because it is non-toxicity, environmental friendliness, comparatively abundance and low production cost material as compared to other TE systems. Also it has exhibited promising TE properties such as: high electrical conductivity and low thermal conductivity, which improved the overall performance (ZT). In this work Mg2Si powder was obtained through ball milling under inert atmosphere, starting from commercial magnesium silicide pieces (99,99%, Alfa Aesar). The Mg2Si powder was filled in the graphite die to perform spark plasma sintering (SPS) and the process parameters like temperature, heating rate, holding time and applied pressure were studied in details. The aim of this study is to optimize SPS consolidation parameters in order to achieve high density of compacts with improved mechanical properties and to maintain the nanostructured grains. X Ray diffraction (XRD) was utilized to investigate the crystalline phase of compacted samples and Scanning Electron Microscopy (SEM) coupled with Energy Dispersive Spectroscopy (EDS) used to evaluate the detailed microstructural and chemical composition respectively. All compacted samples have shown the compaction density up to 99%. Temperature dependent TE characteristics of compacted Mg2Si such as thermal conductivity, electrical conductivity and Seebeck coefficient were measured over temperature range of 300 - 900 K.

The properties of Te-doped Co(Sb 1-yTe y) 3 and Te-Ni double-doped Co 1-xNi x(Sb 1-yTe y) 3 nanostructured skutterudites were evaluated by means of x-ray powder diffraction, and transport properties measured on the synthesized samples have been compared with ab initio theoretical modeling. Theoretical optimal dopant contents have been evaluated according to the maximum value of the power factor, calculating the electronic transport properties from the ab initio material band structure using semiclassical Boltzmann transport theory. The samples have been synthesized by chemical alloying with Te substitution for Sb up to 2.5 at.% and Ni substitution for Co up to 2.0 at.%. X-ray powder diffraction has been performed on all samples to reveal information about phase purity and Rietveld refinement was performed for the phase composition and cell parameter. The thermoelectric properties of the resulting consolidates were investigated in a temperature range from 300 to 723 K using various measurement facilities. A standardization and round robin program was started among the participating evaluation laboratories in order to ensure reliability of the data obtained. The significant reduction in thermal conductivity, when compared to highly annealed CoSb 3, could be proved which is caused by the nanostructuring, resulting in a high concentration of grain boundaries. A combination of substitution levels for Ni and Te has been found resulting in the largest ZT value of 0.65 at 680 K among unfilled skutterudite materials. © 2005 American Institute of Physics.

The high concentration of grain boundaries provided by nanostructuring is expected to lower the thermal conductivity of thermoelectric materials, which favors an increase in their thermoelectric figure-of-merit, ZT. A novel chemical alloying method has been used for the synthesis of nanoengineered-skutterudite CoSb3. The CoSb3 powders were annealed for different durations to obtain a set of samples with different particle sizes. The samples were then compacted into pellets by uniaxial pressing under various conditions and used for the thermoelectric characterization. The transport properties were investigated by measuring the Seebeck coefficient and the electrical and thermal conductivities in the temperature range 300 K to 650 K. A substantial reduction in the thermal conductivity of CoSb3 was observed with decreasing grain size in the nanometer region. For an average grain size of 140 nm, the thermal conductivity was reduced by almost an order of magnitude compared to that of a single crystalline or highly annealed polycrystalline material. The highest ZT value obtained was 0.17 at 611 K for a sample with an average grain size of 220 nm. The observed decrease in the thermal conductivity with decreasing grain size is quantified using a model that combines the macroscopic effective medium approaches with the concept of the Kapitza resistance. The compacted samples exhibit Kapitza resistances typical of semiconductors and comparable to those of Si-Ge alloys.

Nanostructured skutterudite Co12xNixSb3 has been synthesized by chemical alloying with Ni substitution for Co up to 27.5 at. %. High concentration of grain boundaries provided by nanostructuring is expected to lower the thermal conductivity of thermoelectric materials and could thus increase their thermoelectric dimensionless figure-of-merit ZT. Material preparation comprises two key stages, coprecipitation of the precursor, and thermal processing to produce the skutterudite. By modeling the chemistry of the metal ions in aqueous solution, optimum coprecipitation conditions were achieved. The precipitated precursor consists of a solid solution of the different intermediate compounds, and exhibits high reactivity. Calcination and reduction of the precursor resulted in the alloying of these elements and in the formation of skutterudite at a temperature as low as 723-773 K. Unfilled CoSb3 skutterudites were prepared by chemical precipitation from aqueous solutions to achieve powders with a very small grain size ~;40 nm!. Compacted samples were produced from this powder by uniaxial pressing under various conditions. Thermal conductivity, electrical resistivity and Seebeck coefficient of the resulting compacts were measured in a temperature range from 150 to 575 K. Measurement procedures were standardized for absolute accuracy and reproducibility between the DLR, Cologne and NEDO, Cardiff Laboratories. It was found that the thermal conductivity can be decreased by almost an order of magnitude at the highest concentration of grain boundaries compared to highly annealed CoSb3 . Scanning Seebeck microthermoprobe examination, facilitated spatially resolved measurement of Seebeck coefficient S, providing information on samples' homogeneity and on its effect on local S. Indications on the formation of an additional Ni containing phase were found. The electronic structure of Ni-doped skutterudites has been investigated by means of fully periodic density functional theory calculations and a topological analysis of the resulting electron densities. Ni substitution for Co doubles the electronic charge transfer from the pnicogen ring to the metal frame and fills the region of the CoSb3 band gap with occupied states, thus explaining the increase of electrical conductivity observed experimentally. The effect of the Ni substitution on the thermal conductivity is analyzed. The computed changes of the cell parameter with rising Ni content differ with those found by x-ray powder diffraction, thereby suggesting that the structural hypothesis of Ni replacing Co in the cubic frame of the skutterudite is only approximate or possibly incorrect.

Nano-engineered skutterudite CoSb/sub 3/ was synthesized by a chemical alloying method. A set of samples with different grain size were processed upon annealing. The physicochemical characterizations of these samples were carried out with respect to their phase purity and microstructure, particularly the porosity and grain size. Their transport properties were characterized by measuring Seebeck coefficient, electrical and thermal conductivities in a temperature range of 300 - 650 K. The measurement procedures were standardized for absolute accuracy and reproducibility carried out in two laboratories. It has been observed that the measurement data of transport properties have a significant dependence upon the grain size of the samples as it reduced toward the nano-scale.,he thermal conductivity data have demonstrated the significant size dependence, with a decrease by an order of,magnitude for nano-grained samples, compared to the literature value of /spl kappa/ = 10 W/m.K for highly annealed sample with micron grain size. The electrical conductivity has shown a similar reduction, but to a less extent, upon decreasing the grain size. On the other hand, the size dependence of Seebeck coefficient is less remarkable though notable. As a result, ZT value is still enhanced with decreasing the gain size. The highest ZT value obtained at 611 K was 0.17, much higher than the literature value of 0.1 for a single crystal and polycrystalline samples with micron grain size.

The electronic structure of the Te doped CoSb/sub 3/ skutterudite is investigated by means of fully periodic density functional theory (DFT) calculations. Since the geometrical structure of a material may strongly affect its properties, Te substituted for Sb (Co/sub 4/Sb/sub 11/Te) and Te fully filled (TeCo/sub 4/Sb/sub 12/) cobalt skutterudite are both studied in order to understand where Te atom is sitting. From the analysis of the geometry and electronic structure properties, the Te filled system is ruled out. The extent of the change transfer among Co, Sb and Te atoms is evaluated using the Quantum Theory of Atom in Molecules (QTAIM). Te substitution for Sb yields a conductor with Fermi energy lying in the conduction bands zone of unsubstituted CoSb/sub 3/. The Seebeck coefficient S and the electrical conductivity /spl sigma/ are calculated using the semiclassical Boltzmann monoelectronic transport theory. Computed S values agree with experimental evaluations on nanostructured Te doped CoSb/sub 3/ samples when the frozen band approximation is used for low Te doping and the Co/sub 4/Sb/sub 11/Te band structure is adopted for high Te content.

Here, we report on the synthesis of PEG-Mn3O4 nanocomposite (NP’s) via a hydrothermal route by using Mn(acac)2, ethanol, NH3 and PEG-400. The crystalline phase was identified as Mn3O4. The crystallite size of the PEG-Mn3O4 nanocomposite was calculated as 12±5 nm from X-ray line profile fitting and the average particle size from TEM was obtained as 200 nm. This reveals polycrystalline character of Mn3O4 NP’s. The interaction between PEG-400 and the Mn3O4 NP’s was investigated by FTIR. Temperature independent AC conductivity of PEG-Mn3O4 nanocomposite beyond 20 kHz provides a strong evidence of ionic conduction through the structure. The conductivity and permittivity measurements strongly depend on the secondary thermal transition of nanocomposite beyond 100°C. Above that temperature, Mn3O4 particles may interact with each other yielding a percolated path that will facilitate the conduction. On the other hand, the relatively lower activation energy (Ea=0.172 eV) for relaxation process suggests that polymer segmental motions of PEG and electrons hopping between Mn2+ and Mn3+ may be coupled in the sample below 100°C. Room temperature magnetization curve of the sample does not reach to a saturation, which indicates the superparamagnetic character of the particles. As the temperature increases, the frequency at which (ε″) reaches a maximum shifted towards higher frequencies. The maximum peak was observed at 1.4 kHz for 20°C while the maximum was detected at 23.2 kHz for 90°C.

An effective, eco-friendly and easily scalable nanosilver-based technology offers affordable and broad-spectrum antimicrobial solutions against SARS-CoV-2 and Escherichia coli.