Magnetochemistry doi: 10.3390/magnetochemistry10030019
Authors: A. T. Apostolov I. N. Apostolova J. M. Wesselinowa
The magnetization, polarization, and band-gap energy in pure and ion-doped KNbO3 (KNO) bulk and nanoparticles (NPs) are investigated theoretically using a microscopic model and Green’s function theory. It is shown that KNO NPs are multiferroic. The size dependence of M and P is studied. The magnetization M increases with decreasing NP size, whereas the polarization P decreases slightly. The properties of KNO can be tuned by ion doping, for example, through the substitution of transition metal ions at the Nb site or Na ions at the K site. By ion doping, depending on the relation between the doping and host ion radii, different strains appear. They lead to changes in the exchange interaction constants, which are inversely proportional to the lattice parameters. So, we studied the macroscopic properties on a microscopic level. By doping with transition metal ions (Co, Mn, Cr) at the Nb site, M increases, whereas P decreases. Doped KNO NPs exhibit the same behavior as doped bulk KNO, but the values of the magnetization and polarization in KNO NPs are somewhat enhanced or reduced due to the size effects compared to the doped bulk KNO. In order to increase P, we substituted the K ions with Na ions. The polarization increases with increasing magnetic field, which is evidence of the multiferroic behavior of doped KNO bulk and NPs. The behavior of the band-gap energy Eg also depends on the dopants. Eg decreases with increasing Co, Mn, and Cr ion doping, whereas it increases with Zn doping. The results are compared with existing experimental data, showing good qualitative agreement.
]]>Magnetochemistry doi: 10.3390/magnetochemistry10030018
Authors: Elliza Tri Maharani Myeong-Won Seo Jung Woo Sohn Jong-Seok Oh Seung-Bok Choi
Magnetorheological fluids (MRFs) are widely used for various kinds of controllable devices since their properties can be controlled by an external magnetic field. Despite many benefits of MRFs, such as fast response time, the sedimentation arisen due to the density mismatch of the compositions between iron particles and carrier oil is still one of bottlenecks to be resolved. Many studies on the sedimentation problem of MR fluids have been carried out considering appropriate additives, nanoparticles, and several carrier oils with different densities. However, a study on the effect of current magnitudes and profiles on the sedimentation is considerably rare. Therefore, this study experimentally investigates sedimentation behaviors due to different current magnitudes and different magnitude profiles such as square and sine waves in different diameters. The evaluation was performed by visual observation to obtain the sedimentation rate. It was found that the average sedimentation rate of the square type of current is slower compared to the sinusoidal type. It has also been identified that the higher intensity of the applied current results in a stronger electromagnetic field, which could slow down the sedimentation. The results achieved in this work can be effectively used to reduce particle sedimentation in the controller design of various application systems utilizing MRFs in which the controller generates a different magnitude and different profile of the external magnetic field.
]]>Magnetochemistry doi: 10.3390/magnetochemistry10030017
Authors: Mario J. Pinheiro
This study explores ground-breaking methods for improving engine efficiency by combining cutting-edge materials, theoretical frameworks, and alternative energy paradigms. The paper primarily offers a cohesive framework, built from our variational method which combines thermal and entropic engines. We investigate the fabrication of hydrophobic and other functionally specific surfaces using nanomaterials and sophisticated surface engineering techniques that efficiently utilize entropy gradient forces. Additionally, this publication explores the fields of quantum-based propulsion systems and information-burning engines, creating a connecting link between theoretical foundations and real-world technical implementations. The study emphasizes the multifaceted character of engine research and its crucial role in shaping a future in which sustainability and efficiency are intimately connected.
]]>Magnetochemistry doi: 10.3390/magnetochemistry10030016
Authors: Kai Nakashima Chihiro Hayami Shino Nakashima Haruo Akashi Masahiro Mikuriya Makoto Handa
The mononuclear and dinuclear ruthenium(III) complexes trans-Ph4P[RuIII(acac)2Cl2] (1), Ph4P[{RuIII(acac)Cl}2(μ-Cl)3] (2) and trans-Ph4P[RuIII(acac)2(NCS)2]·0.5C6H14 (3·0.5C6H14) were synthesized. Single crystals of 1, 2·H2O and 3·CH3CN suitable for X-ray crystal structure analyses were obtained through recrystallization from DMF for 1 and 2·H2O and from acetonitrile for 3·CH3CN. An octahedral Ru with bis-chelate-acac ligands and axial chlorido or κ-N-thiocyanido ligands (for 1 and 3·CH3CN) and triply µ-chlorido-bridged dinuclear Ru2 for 2·H2O were confirmed through the structure analyses. The Ru–Ru distance of 2.6661(2) of 2·H2O is indicative of the existence of the direct metal–metal interaction. The room temperature magnetic moments (μeff) are 2.00 and 1.93 μB for 1 and 3·0.5C6H14, respectively, and 0.66 μB for 2. The temperature-dependent (2–300 K) magnetic susceptibility showed that the strong antiferromagnetic interaction (J ≤ −800 cm−1) is operative between the ruthenium(III) ions within the dinuclear core. In the 1H NMR spectra measured in CDCl3 at 298 K, the dinuclear complex 2 showed signals for the acac ligand protons at 2.50 and 2.39 ppm (for CH3) and 5.93 ppm (for CH), respectively, while 1 and 3·0.5C6H14 showed signals with large paramagnetic shifts; −17.59 ppm (for CH3) and −57.01 ppm (for CH) for 1 and −16.89 and −17.36 ppm (for CH3) and −53.67 and −55.53 ppm (for CH) for 3·0.5C6H14. Cyclic voltammograms in CH2Cl2 with an electrolyte of nBu4N(ClO4) showed the RuIII → RuIV redox wave at 0.23 V (vs. Fc/Fc+) for 1 and the RuIII → RuII waves at −1.39 V for 1 and −1.25 V for 3·0.5C6H14 and the RuIII–RuIII → RuIII–RuIV and RuIII–RuIII → RuIII–RuIV waves at 0.91 V and −0.79 V for 2.
]]>Magnetochemistry doi: 10.3390/magnetochemistry10030015
Authors: Simon Tardieu Hanane Idrir Christophe Verdy Olivier Jay Nelson Ferreira François Debray Anne Joulain Christophe Tromas Ludovic Thilly Florence Lecouturier-Dupouy
High-strength, high-conductivity copper/silver-alloyed materials were prepared by cold-spray (CS) manufacturing. For DC high-field application at room temperature, bulk Cu/Ag (5% vol. Ag) alloys with high mechanical properties and high electrical conductivity can be obtained by CS and post-heat treatments. For pulsed-field application at liquid nitrogen temperature, bulk Cu/Ag (5% vol. Ag) alloys serve as precursors for room-temperature wire drawing. The Cu/Ag-alloyed bulk CS deposit presents a high yield strength of about 510 MPa with a corresponding electrical resistivity of 1.92 µΩ·cm (at 293 K). The Cu/Ag-alloyed wires show a very high ultimate tensile strength (1660 MPa at 77 K or 1370 MPa at 293 K) and low electrical resistivity (1.05 µΩ·cm at 77 K or 2.56 µΩ·cm at 293 K). Microstructural studies via STEM allow us to understand this very high level of mechanical strength. The results evidence that materials developed by CS exhibit very high mechanical properties compared to materials prepared by other routes, due to the high velocity of the deposited particles, which leads to high initial deformation rates and specific microstructural features.
]]>Magnetochemistry doi: 10.3390/magnetochemistry10030014
Authors: Alison Roxburgh Ezio Iacocca
Magnonic crystals are metamaterials whose magnon behavior can be controlled for specific applications. To date, most magnonic crystals have relied on nanopatterning and magnetostatic waves. Here, we analytically and numerically investigate magnonic crystals defined by modulating magnetic parameters at the nanoscale, which predominantly act on exchange-dominated, sub-100 nm magnons. We focus on two cases: the variation in the exchange constant, and the DMI constant. We found that the exchange constant modulation gives rise to modest band gaps in the forward volume wave and surface wave configurations. The modulation of the DMI constant was found to have little effect on the magnonic band structure, leading instead to a behavior expected for unpatterned thin films. We believe that our results will be interesting for future experimental investigations of nano-designed magnonic crystals and magnonic devices, where material parameters can be locally controlled, e.g., by thermal nano-lithography.
]]>Magnetochemistry doi: 10.3390/magnetochemistry10020013
Authors: Jamieson Brechtl Joseph Rendall Mingkan Zhang Michael R. Koehler Kashif Nawaz Ayyoub M. Momen
The heat transfer rate of magnetocaloric regenerators is a topic of extensive research and the cyclability of these regenerators is critical to the operation of systems with a high coefficient of performance (e.g., potentially >22, significantly higher than typical vapor compression cooling technologies). To enable a high operating frequency that will result in a high specific cooling power, the heat transfer fluid should have high thermal conductivity and lower specific heat, i.e., higher thermal diffusivity. Eutectic metal alloys possess these qualities, such as gallium–indium–tin (Galinstan), whose thermal diffusivity has been found to be approximately an order of magnitude higher than water. For this study, the effects of eutectic liquid Galinstan exposure on the phase stability of LaFe13−x−yMnxSiyH1.6 magnetocaloric powders in an active magnetic regenerator device were investigated. The powders were characterized before and after exposure to Galinstan using X-ray diffraction, in which the phases were determined using the Rietveld refinement technique and X-ray fluorescence. It was found that after Galinstan exposure, hydrogen containing phases were present in the powder, suggesting that the hydrogen was lost from the magnetocaloric phase. The magnetocaloric phase degradation indicates that the powder was incompatible with the Galinstan metal in an environment with moisture.
]]>Magnetochemistry doi: 10.3390/magnetochemistry10020012
Authors: Bishal Gautam Saja M. Nabat Al-Ajrash Mohammad Jahid Hasan Abhishek Saini Sarah J. Watzman Esteban Ureña-Benavides Erick S. Vasquez-Guardado
Nanoparticle additives increase the thermal conductivity of conventional heat transfer fluids at low concentrations, which leads to improved heat transfer fluids and processes. This study investigates lignin-coated magnetic nanocomposites (lignin@Fe3O4) as a novel bio-based magnetic nanoparticle additive to enhance the thermal conductivity of aqueous-based fluids. Kraft lignin was used to encapsulate the Fe3O4 nanoparticles to prevent agglomeration and oxidation of the magnetic nanoparticles. Lignin@Fe3O4 nanoparticles were prepared using a pH-driven co-precipitation method with a 3:1 lignin to magnetite ratio and characterized by X-ray diffraction, FT-IR, thermogravimetric analysis, and transmission electron microscopy. The magnetic properties were characterized using a vibrating sample magnetometer. Once fully characterized, lignin@Fe3O4 nanoparticles were dispersed in aqueous 0.1% w/v agar–water solutions at five different concentrations, from 0.001% w/v to 0.005% w/v. Thermal conductivity measurements were performed using the transient line heat source method at various temperatures. A maximum enhancement of 10% in thermal conductivity was achieved after adding 0.005% w/v lignin@Fe3O4 to the agar-based aqueous suspension at 45 °C. At room temperature (25 °C), the thermal conductivity of lignin@Fe3O4 and uncoated Fe3O4 agar-based suspensions was characterized at varying magnetic fields from 0 to 0.04 T, which were generated using a permanent magnet. For this analysis, the thermal conductivity of lignin magnetic nanosuspensions initially increased, showing a 5% maximum peak increase after applying a 0.02 T magnetic field, followed by a decreasing thermal conductivity at higher magnetic fields up to 0.04 T. This result is attributed to induced magnetic nanoparticle aggregation under external applied magnetic fields. Overall, this work demonstrates that lignin-coated Fe3O4 nanosuspension at low concentrations slightly increases the thermal conductivity of agar aqueous-based solutions, using a simple permanent magnet at room temperature or by adjusting temperature without any externally applied magnetic field.
]]>Magnetochemistry doi: 10.3390/magnetochemistry10020011
Authors: Zixing Gu Ping Lu Zihan Zhang Qiang Ma Huaneng Su Qian Xu
The limited photoelectric conversion efficiency poses one of the critical constraints on commercializing solar flow batteries (SFBs). This study compares the chemical and photoelectrochemical properties of three commonly used redox couples. Additionally, magnetic Fe3O4 nanoparticles, for the first time, are introduced to optimize the electrolyte, and they are compared with the original electrolyte. Across different redox couples, the variations in semiconductor flat-band potentials and carrier concentrations result in changes in photoelectric current density. Notably, FeCl2/FeCl3 redox coupled with TiO2 photoelectrodes exhibits the highest photoelectric current density, reaching 75.7 µA cm−2. However, the trade-off of this electrolyte, i.e., providing high photocurrent while being unable to supply sufficient open-circuit voltage, imposes limitations on the practical application of SFBs. Alternatively, for TEMPO and 4-OH-TEMPO electrolytes, which can provide a higher open-circuit voltage, the electrochemical activity is enhanced, and the solution ohmic resistance is reduced by introducing magnetic nanoparticles to form a magnetic nanofluid. As a result, the photoanode’s photocurrent density increases by 36.6% and 17.0%, respectively, in the two electrolytes. The work reported here effectively addresses the current issue of low photocurrent density in SFBs and presents new optimization strategies for SFBs.
]]>Magnetochemistry doi: 10.3390/magnetochemistry10020010
Authors: Javier I. Norambuena Leiva Emilio A. Cortés Estay Eric Suarez Morell Juan M. Florez
One-dimensional (1D) magnetic systems offer rich phenomena in the quantum limit, proving more chemically accessible than zero-dimensional or higher-dimensional frameworks. Single-walled carbon nanotubes (SWCNT) have recently been used to encapsulate trimetric nickel(II) acetylacetonate [Nanoscale, 2019, 11, 10615–10621]. Here, we investigate the magnetization on spin chains based on nickel trimers by Matrix Product State (MPS) simulations. Our findings reveal plateaus in the exchange/magnetic-field phase diagram for three coupling configurations, showcasing effective dimeric and trimeric spin-ordering with similar or staggered entanglement across chains. These ordered states allow the qubit-like tuning of specific local magnetic moments, exhibiting disengagement or uniform coupling in entanglement plateaus. This behavior is consistent with the experimental transition from frustrated (3D) to non-frustrated (1D) molecules, corresponding to large and smaller SWCNT diameters. Our study offers insights into the potential of 1D-confined trimers for quantum computation, extending beyond the confinement of trimetric nickel-based molecules in one dimension.
]]>Magnetochemistry doi: 10.3390/magnetochemistry10020009
Authors: Anna V. Ivanova Nelly S. Chmelyuk Aleksey A. Nikitin Alexander G. Majouga Vladimir P. Chekhonin Maxim A. Abakumov
Magnetic nanoparticles have gained attention as a potential structure for therapy and diagnosing oncological diseases. The key property of the magnetic nanoparticles is the ability to respond to an external magnetic field. It is known that magnetofection causes an increase in the cellular uptake of RNA and DNA in complexes with magnetic nanoparticles in the presence of a permanent magnetic field. However, the influence of a dynamic magnetic field on the internalization of MNPs is not clear. In this work, we propose the idea that applying external low-frequency dynamic magnetic fields may decrease the cellular uptake, such as macrophages and malignant neuroblastoma. Using fluorescence microscopy and atomic emission spectroscopy, we found that oscillating magnetic fields decreased the cellular uptake of magnetic nanoparticles compared to untreated cells by up to 46%. In SH-SY5Y tumor cells and macrophage RAW264.7 cells, the absolute values of Fe per cell differed by 0.10 pg/cell and 0.33 pg/cell between treated and untreated cells, respectively. These results can be applied in the control of the cellular uptake in different areas of biomedicine.
]]>Magnetochemistry doi: 10.3390/magnetochemistry10020008
Authors: Devashibhai Adroja Dmitry Filippov
Magnetic materials are an important class of materials for the development of technology as well as for our fundamental understanding of microscopic magnetic interactions [...]
]]>Magnetochemistry doi: 10.3390/magnetochemistry10020007
Authors: Iosif Malaescu Catalin N. Marin Paul C. Fannin
Measurements of complex magnetic permeability, μ(f,H) = μ′(f,H) − iμ″(f,H) and dielectric permittivity ε(f,H) = ε′(f,H) − iε″(f,H), in the frequency range, f of (0.4–7) GHz, and polarizing field, H of (0–135) kA/m, were performed, for a kerosene-based ferrofluid with magnetite nanoparticles. Based on these measurements, the phenomenon of ferromagnetic resonance was highlighted and some microwave propagation parameters of the ferrofluid were determined: the attenuation constant, α(f,H), and the reflection coefficient, R(f,H), at the air-material interface, at the normal incidence. Knowing these parameters we proposed a theoretical model establishing for the first time an equation that allows the calculation of the overall reflection coefficient, Rw(f,H), at the normal incidence of the wave, for a ferrofluid of thickness d, deposited on a totally reflective support, following multiple internal reflections of the electromagnetic wave in the material. The results show that by increasing both, H, and d, the parameter, Rw(f,H) presents a minimum that decreases from 0.90 (for d = 2 mm) to 0.64 (for d = 10 mm), at frequency f = 5 GHz, which indicates an increase in the absorption of the electromagnetic wave by the ferrofluid. The obtained results are useful in the study of some materials that could be used as electromagnetic absorbers in the microwave range, by the determination of the overall reflection coefficient, Rw(f,H), controlled both by the thickness, d, of the absorber and by the external applied field, H.
]]>Magnetochemistry doi: 10.3390/magnetochemistry10010006
Authors: Huangzhe Dai Zheyan Wu Chenxian Meng Chengqian Zhang Peng Zhao
Tactile sensory organs for three-dimensional (3D) force perception are essential for most living organisms and enable them to perform complex and sophisticated tasks to survive and evolve. Magnetic-based tactile sensors have been developed rapidly in recent years due to the exploitability of 3D force decoupling. Here, a method of magnet splicing is introduced, which can be applied to a magnetic tactile sensor to realize 3D self-decoupling of magnets’ displacements. This method enables the magnets to produce a completely consistent magnetic field distribution as the ideal magnetization model within a certain working range, eliminating the compensation and correction of the 3D magnetic flux density signal. This method carves out a new way for the practical application of 3D decoupling theory, showcasing the great potential in the fields of magnetic sensors and magnetic actuators.
]]>Magnetochemistry doi: 10.3390/magnetochemistry10010005
Authors: Zhanmei Zhang Zuqin Zou Xiaoyu Ren Yunxuan Huang Yang Deng Huaili Zheng
A diatomaceous earth (DE)-based adsorbent DE-Ce was prepared and optimized to remove phosphorus from wastewater. DE was modified through purification–cerium loading, improving its phosphorus adsorption capacity and recycling ability. The preparation conditions were optimized using the Box–Behnken design, and the response surface method was employed to analyze the effects of roasting temperature, cerium concentration, and HCl concentration on the preparation of DE-Ce. Scanning electron microscopy, X-ray fluorescence spectrometry, and X-ray photoelectron spectroscopy were used for characterization, with results indicating that HCl washing can effectively remove impurities. Cerium was mainly loaded onto DE in the form of Ce(OH)3, and pore size and capacity increased following cerium loading, with the formation of a macroporous structure. The obtained DE-Ce adsorbent removed 98.30% phosphorous, with the removal process following the secondary kinetic and Langmuir models. According to material characterization and model analysis results, the phosphorus removal mechanism primarily involves electrostatic adsorption, ligand exchange, and precipitation. Overall, the findings indicate that cerium modification can effectively improve the adsorption capacity of DE.
]]>Magnetochemistry doi: 10.3390/magnetochemistry10010004
Authors: Catalin N. Marin Iosif Malaescu
The magnetic permeability (μ), dielectric permittivity (ε) and electrical conductivity (σ) of six elastomer samples obtained by mixing silicone rubber (RTV-530) with a kerosene-based ferrofluid in different volume fractions (φ), 1.31%, 2.59% and 3.84%, were determined using complex impedance measurements over a frequency range of 500 Hz–2 MHz. Three samples (A0, B0 and C0) were manufactured in the absence of a magnetic field, and the other three samples (Ah, Bh and Ch) were manufactured in the presence of a magnetic field, H = 43 kA/m. The component μ″ of the complex effective magnetic permeability of all samples presents a maximum at a frequency, fmax, that moves to higher values by increasing φ, with this maximum being attributed to Brownian relaxation processes. The conductivity spectrum, σ (f), of all samples follows the Jonscher universal law, which allows for both the determination of the static conductivity, σDC, and the barrier energy of the electrical conduction process, Wm. For the same φ, Wm is lower, and σDC is higher in the samples Ah, Bh and Ch than in the samples A0, B0 and C0. The performed study is useful in manufacturing elastomers with predetermined properties and for possible applications such as magneto-dielectric flexible electronic devices, which can be controlled by the volume fraction of particles or by an external magnetic field.
]]>Magnetochemistry doi: 10.3390/magnetochemistry10010003
Authors: Fuqiang Li Wei Dai Qimin Wang Haiqing Li Zhengtao Wu
In the original publication [...]
]]>Magnetochemistry doi: 10.3390/magnetochemistry10010002
Authors: Matus Molcan Andrzej Skumiel Jana Tothova Katarina Paulovicova Peter Kopcansky Milan Timko
High-frequency components such as microprocessors, transistors, antennas, voltage-controlled oscillators, and many others generate a large amount of heat. In the absence of satisfactory cooling, these components may suffer damage or even destruction. Therefore, it is important to find effective ways to cool these components. A possible solution is to use oil-based magnetic fluids. Magnetic fluids contain magnetic particles dispersed in oil, and their properties, including viscosity, affect their cooling capabilities. Viscosity can be changed by adding various additives or by adjusting the concentration of magnetic particles. The advantage of using oil-based magnetic fluids for cooling is that they allow for precise dosing and control of the amount of fluid applied to the component, reducing thermal losses and increasing cooling efficiency. In addition, oil-based magnetic fluids can also act as a dielectric, reducing electrical noise and increasing electromagnetic compatibility with the components. Analyzing the heating rate of magnetic fluids consisting of mineral oils in an alternating magnetic field with a frequency of 500 kHz, we have shown the capability of controlling thermal losses by adjusting the viscosity of the carrier liquid.
]]>Magnetochemistry doi: 10.3390/magnetochemistry10010001
Authors: Laura C. J. Pereira Dulce Belo
In the commemorative Special Issue titled “Insights into Functional Molecular Materials—A Themed Collection Honoring Professor Manuel Almeida on His 70th Birthday”, eminent researchers from around the globe in the field of molecular materials science come together to acknowledge and celebrate the notable scientific contributions of Professor Almeida [...]
]]>Magnetochemistry doi: 10.3390/magnetochemistry9120233
Authors: Yen-Ju Chen Yan-Hom Li Ching-Yao Chen
In comparison to alternative methods for hydrogen production, water electrolysis stands out as the optimal means for obtaining ultra-pure hydrogen. However, its widespread adoption is significantly hampered by its low energy efficiency. It has been established that the introduction of an external magnetic field can mitigate energy consumption, consequently enhancing electrolysis efficiency. While much of the research has revealed that an electrode–parallel magnetic field plays a crucial role in enhancing the bubble detachment process, there has been limited exploration of the effect of electrode–normal magnetic fields. In this work, we compare the water electrolysis efficiency of a circular electrode subjected to electrode–normal magnetic field resulting in a magnet edge effect and electrode edge effect by varying the sizes of the magnet and electrode. The findings indicate that a rotational flow caused by the Lorentz force facilitates the detachment of the hydrogen from the electrode surface. However, the rotation direction of hydrogen gas bubbles generated by the magnet edge effect is opposite to that of electrode edge effect. Furthermore, the magnet edge effect has more significant influence on the hydrogen bubbles’ locomotion than the electrode edge effect. With an electrode gap of 30 mm, employing the magnet edge effect generated by a single magnet leads to an average of 4.9% increase in current density. On the other hand, the multiple magnet effects created by multiple small magnets under the electrode can further result in an average 6.6% increase in current density. Nevertheless, at an electrode spacing of 50 mm, neither the magnet edge effect nor the electrode edge effect demonstrates a notable enhancement in conductivity. In reality, the electrode edge effect even leads to a reduction in conductivity.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9120232
Authors: Lucie Zárybnická Marek Pagáč Radek Ševčík Jaroslav Pokorný Martin Marek
This work aims to characterize 3D-printed structures composed of a thermoplastic material (polylactic acid (PLA)) containing a combination of magnetic particles composed of iron(III) oxide (hematite) and iron(II)–iron (III) oxide (magnetite) with various infill densities and print orientations in regard to their possible processing by Fused Filament Fabrication additive technology. The correct processing temperatures have been determined using thermal analysis, and the paramagnetic and mechanical properties of the samples have been tested. The relative permeability has been identified to be strongly dependent on the topology parameters of the tested samples. The results of the inductance values for the samples without magnetic additives (infill densities 50% and 100%) have been detected to be comparable; nonetheless, the magnetic samples with 100% infill density has been found to be about 50% higher. A similar trend has been observed in the case of the values of the relative permeability, where the magnetic samples with 100% infill density have been measured as having an about 40% increased relative permeability in the comparison with the samples without magnetic additives (infill densities 20–100%). Finite Element Modelling (FEM) simulations have been applied to determine the magnetic field distributions and, moreover, to calculate the holding forces of all the printed samples. The maximum value of the holding force for the minimum distance of the plastic plate has been found to reach a value of almost 300 N (magnetic sample with 100% infill density). The obtained comprehensive characterization of the printed samples may be utilized for designing and tuning the desired properties of the samples needed in various industrial applications.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9110231
Authors: Kai Wang Liqin Yan Youguo Shi Baogen Shen Lunhua He Fangwei Wang Jun Lu Tongyun Zhao Zunming Lu
Among the 5d transition metal iridates, Sr2IrO4, which has a layered chalcogenide structure, has received much attention due to its strong spin–orbit coupling (SOC), which produces Mott insulating states and anomalous physical behaviors. In this paper, the microscopic magnetism of Sr2IrO4 is studied with electron spin resonance (ESR) measurements. The Lande factor g of the ferromagnetic resonance signal of Sr2IrO4 shows anomalous behavior compared to typical ferromagnets. It gradually decreases, and the corresponding resonance field Hr increases, with decreasing temperature. The various physical parameters. including the saturated magnetic field Hs derived from M-H, Hr, ΔHpp, the g factor and the intensity I extracted from ESR spectra, are analyzed in detail. Eventually, it is revealed that the anomalous behavior of the g-factor is induced by in-plane Dzyaloshinsky–Moriya interaction (DMI) rather than the SOC effect.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9110230
Authors: Jihed Horcheni Hamdi Jaballah Essebti Dhahri Lotfi Bessais
In this study, we give a thorough evaluation of the structural, magnetic, and magnetocaloric properties in iron-rich PrFe11Ti intermetallic alloy with ThMn12-type structure using a combination of experimental and theoretical analysis. X-ray diffraction coupled with Rietveld refinement was used to characterize the structure, which revealed a unique tetragonal crystal structure with I4/mmm space group. The 8i site was identified as the preferred site for the Ti atom. This finding was confirmed by various techniques, including XRD, DFT, and Mössbauer spectrometry. Magnetic properties were studied through intrinsic magnetic measurements and magnetocaloric effect analysis. Mössbauer spectroscopy was employed to probe the local magnetic environment and for further characterization of the material’s magnetic properties. The experimental results were complemented by theoretical calculations based on density functional theory (DFT). A promising magnetocaloric effect is observed, with a significant maximum magnetic entropy (−ΔSMmax = 2.5 J·kg−1·K−1) and a relative cooling power about 70 J·kg−1 under low magnetic field change μ0ΔH = 1.5 T. Overall, our results provide a deeper understanding of the structural and magnetic properties of the material under study and demonstrate the effectiveness of the combined experimental and theoretical approach in the investigation of complex materials. The insights gained from this study could have implications for the development of advanced magnetic materials with enhanced properties for potential magnetic applications.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9110229
Authors: Petr Halaš Ivan Nemec Radovan Herchel
The hexacoordinate Co(II) complex [Co(neo)2(cin)][BPh4]·½Me2CO (1·½Me2CO) containing trans-cinnamic acid (Hcin) and neocuproine (neo) was prepared. The compound 1·½Me2CO was characterized via single-crystal X-ray analysis, FT-IR spectroscopy, and magnetic measurements. The coordination polyhedron of the complex cation adopts a deformed octahedron shape, and cinnamate exhibits a bidentate mode of coordination, which is unusual for mononuclear Co(II) cinnamate complexes. The analysis of DC magnetic measurements with zero-field splitting (ZFS) spin Hamiltonian revealed large magnetic anisotropy defined by the axial ZFS parameter D = +53.2 cm−1. AC susceptibility measurements revealed the slow relaxation of magnetization under the applied field; thus, 1·½Me2CO behaves as a field-induced single-molecule magnet. The analysis of magnetic properties was also supported by CASSCF/NEVPT2 calculations.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9110228
Authors: P. A. Chernavskiy A. A. Novakova G. V. Pankina D. A. Pankratov S. I. Panfilov G. A. Petrovskaya
A new method for obtaining nanosized particles of iron oxides using porous silica gel is proposed. In situ magnetometry was used to study the reduction of hematite deposited on silica gel during the thermolysis of glucose. The formed magnetite and maghemite obtained by subsequent oxidation of the magnetite were studied using X-ray diffraction and Mossbauer spectroscopy. It was shown that both the size of the oxide particles and the phase composition significantly depended on the porous structure of the silica gel. In particular, the formation of superparamagnetic maghemite particles on silica gels with pore sizes of 30, 15 and 10 nm was demonstrated.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9110227
Authors: Elena G. Kalinina Nataliya D. Kundikova Dmitrii K. Kuznetsov Maxim G. Ivanov
In this work, the possibility of fabricating composite magneto-optical ceramics by electrophoretic deposition (EPD) of nanopowders and high-temperature vacuum sintering of the compacts was investigated. Holmium oxide was chosen as a magneto-optical material for the study because of its transparency in the mid-IR range. Nanopowders of magneto-optical (Ho0.95La0.05)2O3 (HoLa) material were made by self-propagating high-temperature synthesis. Nanopowders of (Y0.9La0.1)2O3 (YLa) were made by laser synthesis for an inactive matrix. The process of formation of one- and two-layer compacts by EPD of the nanopowders from alcohol suspensions was studied in detail. Acetylacetone was shown to be a good dispersant to obtain alcohol suspensions of the nanopowders, characterized by high zeta potential values (+29–+80 mV), and to carry out a stable EPD process. One-layer compacts were made from the HoLa and YLa nanopowders with a density of 30–43%. It was found out that the introduction of polyvinyl butyral (PVB) into the suspension leads to a decrease in the mass and thickness of the green bodies deposited, but does not significantly affect their density. The possibility of making two-layer (YLa/HoLa) compacts with a thickness of up to 2.6 mm and a density of up to 46% was demonstrated. Sintering such compacts in a vacuum at a temperature of 1750 °C for 10 h leads to the formation of ceramics with a homogeneous boundary between the YLa/HoLa layers and a thickness of the interdiffused ion layer of about 30 μm.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9110226
Authors: Roman Boča Cyril Rajnák Ján Titiš
The involvement of spin symmetry in the evaluation of zero-field energy levels in polynuclear transition metal and lanthanide complexes facilitates the division of the large-scale Hamiltonian matrix referring to isotropic exchange. This method is based on the use of an irreducible tensor approach. This allows for the fitting of the experimental data of magnetic susceptibility and magnetization in a reasonable time for relatively large clusters for any coupling path. Several examples represented by catena-[AN} and cyclo-[AN] systems were modeled. Magnetic data for 20 actually existing endohedral clusters were analyzed and interpreted.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9110225
Authors: Masato Fukuda Ken Eguchi Kazuma Matsumoto Ko Yoneda Yasunori Yamada Haruka Yoshino Yuki Imamura Naoya Yamamoto Masaaki Ohba Masayuki Koikawa
A mononuclear Ni(II) complex, [Ni(HL1)2], (1) and a novel tetranuclear heterometal Mn-Ni complex, [Mn3Ni(L1)4Cl2(EtOH)2], (2) [H2L1 = N-(2-hydroxymethylphenyl)salicylideneimine], have been synthesized and characterized via X-ray crystal structure analyses, infrared spectra, and elemental analyses. The structure analyses revealed that the tridentate ligand, H2L1, coordinates in a facial mode for Ni and a mer mode for Mn, respectively. Complex 2 includes Mn(II)Mn(III)2Ni(II) tetranuclear metal core bridged by μ-phenoxo and μ-alkoxo oxygens. Magnetic measurements for 2 indicate that weak ferromagnetic interactions (JMn(III)Ni(II) = 2.23, JMn(III)Mn(II) = 0.46, JMn(II)Ni(II) = 1.78, and JMn(III)Mn(III) = 0.58 cm−1) dominate in the tetranuclear core. Additionally, in alternating current (AC) magnetic measurements, frequency-dependent out-of-phase responses were observed.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9110224
Authors: Alexander Moskvin
A wide class of materials with different crystal and electronic structures including quasi-2D unconventional superconductors, such as cuprates, nickelates, ferropnictides/chalcogenides, ruthenate Sr2RuO4, and 3D systems, such as manganites RMnO3, ferrates (CaSr)FeO3, nickelates RNiO3, silver oxide AgO, are based on Jahn–Teller 3d and 4d ions. These unusual materials, called Jahn–Teller (JT) magnets, are characterized by an extremely rich variety of phase states, spanning from non-magnetic and magnetic insulators to unusual metallic and superconducting states. The unconventional properties of JT magnets can be attributed to the instability of their highly symmetric Jahn–Teller “progenitors” with the ground orbital E-state with repect to charge transfer, anti-Jahn–Teller d-d disproportionation, and the formation of a system of effective local composite spin–singlet or spin–triplet, electronic, or hole S-type bosons moving in a non-magnetic or magnetic lattice. We consider specific features of the anti-JT-disproportionation reaction, properties of the electron–hole dimers, possible phase states and effective Hamiltonians for single- and two-band JT magnets, concluding with a short overview of physical properties for actual JT magnets.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9110223
Authors: M. Zaid Zaz Thilini K. Ekanayaka Ruihua Cheng Peter A. Dowben
Here, we examine the conductance changes associated with the change in spin state in a variety of different structures, using the example of the spin crossover complex [Fe(H2B(pz)2)2(bipy)] (pz = (pyrazol-1-yl)-borate and bipy = 2,2′-bipyridine) and [Fe(Htrz)2(trz)](BF4)] (Htrz = 1H-1,2,4-triazole) thin films. This conductance change is highly variable depending on the mechanism driving the change in spin state, the substrate, and the device geometry. Simply stated, the choice of spin crossover complex used to build a device is not the only factor in determining the change in conductance with the change in spin state.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9100222
Authors: Valentina Zhukova Alfonso García-Gómez Alvaro Gonzalez Margarita Churyukanova Sergey Kaloshkin Paula Corte-Leon Mihail Ipatov Jesus Olivera Arcady Zhukov
We studied the magnetostriction coefficients, λs, Curie temperature, Tc, and their dependence on annealing conditions in Fe47Ni27Si11B13C2 and Co67Fe3.9Ni1.5B11.5Si14.5Mo1.6 amorphous glass-coated microwires with rather different character of hysteresis loops. A positive λs ≈ 20 × 10−6 is observed in as-prepared Fe47Ni27Si11B13C2, while low and negative λs ≈ −0.3 × 10−6 is obtained for Co67Fe3.9Ni1.5B11.5Si14.5Mo1.6 microwire. Annealing affects the magnetostriction coefficients and Curie temperatures, Tc, of both Fe47Ni27Si11B13C2 and Co67Fe3.9Ni1.5B11.5Si14.5Mo1.6 glass-coated microwires in a similar way. Observed dependencies of hysteresis loops, λs and Tc on annealing conditions are discussed in terms of superposition of internal stresses relaxation and structural relaxation of studied microwires. We observed linear λs dependence on applied stress, σ, in both studied microwires. A decrease in the magnetostriction coefficient upon applied stress is observed for Co-rich microwires with low and negative magnetostriction coefficient. On the contrary, for Fe-Ni-rich microwires with a positive magnetostriction coefficient, an increase in the magnetostriction coefficient with applied stress is observed. The observed results are discussed considering the internal stresses relaxation and short range atomic rearrangements induced by annealing on hysteresis loops, magnetostriction coefficients and Curie temperatures of studied microwires.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9100221
Authors: Eisuke Chikayama Stephan J. Ginthör Matthias Bechmann Norbert Müller
Radio amplification using stimulated emission of radiation (RASER) effects in the NMR can increase NMR signals over time due to a feedback loop between the sample magnetization and the probe coil coupled with radiation damping (RD). Previously, RD rates had been directly observed only for the 1H, 3He, 17O and 129Xe nuclei. We report that experimental direct measurements of an NMR RASER to determine RD time constants for the three heteronuclei (133Cs (I = 7/2), 7Li (I = 3/2) and 31P (I = 1/2)) in a highly concentrated solution from the NMR RASER emissions using a conventional NMR probe. Under conditions where the RD rate exceeds the transverse relaxation rate (i.e., the NMR RASER condition is fulfilled), we recorded both the transverse NMR RASER response to imperfect inversion and the recovery of longitudinal magnetization. The data were directly evaluated based on the well-known Bloom model as estimated RD rate constants of 8.0, 1.8 and 25 Hz for 133Cs, 7Li and 31P, respectively. The proposed method can be applied to observe RD rate constants for the other nuclei as well.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9100220
Authors: Petr Kharitonskii Elena Sergienko Andrey Ralin Evgenii Setrov Timur Sheidaev Kamil Gareev Alexander Ustinov Nikita Zolotov Svetlana Yanson Danil Dubeshko
Artificial glasses containing nanoscale inclusions of iron oxides, including magnetite and hematite, were obtained via the method of the high-temperature melting of rocks. The main factors influencing the magnetic properties of glasses are the composition of the initial charge and the conditions of cooling of the melt. The data of magnetic granulometry and frequency-field dependencies of magnetic susceptibility showed the presence of a sufficiently large superparamagnetic fraction in the samples. Coordinated theoretical modeling using two independent models that take into consideration possible the chemical inhomogeneity of particles and magnetostatic interaction between them made it possible to calculate hysteresis characteristics corresponding to the experiment and to estimate ferrimagnetic concentrations in the samples, including the superparamagnetic fraction.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9100219
Authors: Daniil Popov Ruslan Batulin Mikhail Cherosov Farit Vagizov Almaz Zinnatullin Tatiana Chupakhina Yuliya Deeva Tanmoy Maiti Rushana Eremina
The ceramic perovskite Sr2FeNbO6-δ was synthesized via the solution combustion precursor method. X-ray phase analysis showed that the sample is single-phase and does not contain impurities. The specific heat capacity and the Mössbauer spectra were measured for the Sr2FeNbO6-δ ceramic in the temperature range of 4–300 K. The observation of an asymmetric doublet in the Mössbauer spectra and the literature data on the magnetic susceptibility indicated the presence of two magnetic subsystems in Sr2FeNbO6-δ with antiferromagnetic exchange interactions. Based on the analysis of the temperature dependence of the specific heat capacity, we determined the Debye and Einstein temperatures.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9100218
Authors: Irina O. Dzhun Andrey V. Gerasimenko Alexander A. Ezhov Stanislav I. Bezzubov Valeria V. Rodionova Christina A. Gritsenko Nikolai G. Chechenin
Thin film ferromagnet/antiferromagnet (F/AF) exchange biased structures that are widely used in GMR spin valves are considered nowadays as promising systems for antiferromagnetic spintronic and spin-orbitronic devices. Here, the temperature dependences of magnetization dynamics in Co/IrMn and Co/FeMn F/AF structures are investigated using ferromagnetic resonance (FMR) in comparison to a free Co layer. A strong additional decrease in the resonance field was observed in Co/IrMn with a temperature decrease attributed to the rotatable anisotropy increase, which almost vanished at room temperature. In contrast to Co/IrMn, the contribution of the rotatable anisotropy in Co/FeMn is much weaker, even though it exists at RT, it is negative, and slightly varies with the temperature and resonance field shift in Co/FeMn. This is mainly due to unidirectional exchange anisotropy. FMR linewidth for the free Co layer increases with decreasing temperature and is accompanied with a slow relaxation process, while the additional contribution to FMR line broadening in Co/IrMn and Co/FeMn structures is correlated with variation in the exchange anisotropy. The observed results are discussed based on structural and surface morphology and magnetization reversal characterization using X-ray diffraction, atomic force microscopy, and vibrating sample magnetometry data.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9100217
Authors: Athanassios K. Boudalis
The weak intramolecular magnetic interactions within a series of CuII3 complexes based on the trinucleating 2,4,6-tris(di-2-pyridylamino)-1,3,5-triazine (dipyatriz) ligand were investigated via Electron Paramagnetic Resonance (EPR) spectroscopy. X- and Q-band EPR spectroscopy in powders and frozen solutions were recorded and the Q-band spectra were interpreted by a multispin Hamiltonian model comprising exchange, dipolar and hyperfine interactions. The described methodology is suitable for the elucidation of weak intramolecular interactions which are not amenable to analysis via magnetic susceptibility studies.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9100216
Authors: Radu Jubleanu Dumitru Cazacu
The superconducting magnet energy storage (SMES) has become an increasingly popular device with the development of renewable energy sources. The power fluctuations they produce in energy systems must be compensated with the help of storage devices. A toroidal SMES magnet with large capacity is a tendency for storage energy because it has great energy density and low stray field. A key component in the creation of these superconducting magnets is the material from which they are made. The present work describes a comparative numerical analysis with finite element method, of energy storage in a toroidal modular superconducting coil using two types of superconducting material with different properties bismuth strontium calcium copper oxide (BSCCO) and yttrium barium copper oxide (YBCO). Regarding the design of the modular torus, it was obtained that for a 1.25 times increase of the critical current for the BSCCO superconducting material compared with YBCO, the dimensions of the BSCCO torus were reduced by 7% considering the same stored energy. Also, following a numerical parametric analysis, it resulted that, in order to maximize the amount of energy stored, the thickness of the torus modules must be as small as possible, without exceeding the critical current. Another numerical analysis showed that the energy stored is maximum when the major radius of the torus is minimum, i.e., for a torus as compact as possible.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9100215
Authors: Gui-Ping Zhu Shi-Hua Wu Shu-Ze Zheng Lai Li Nam-Trung Nguyen
A significant growth of research on digital microfluidics has been achieved over the past several decades, and the field is still attracting increasing attention for fulfilling relevant mechanisms and potential applications. Numerous studies have been devoted to actively manipulating droplets in a variety of fundamental and applicational scenarios. In this work, the deformation of ferromagnetic fluid droplets is studied under an external uniform magnetic field. The droplets are precisely dispersed on the bottom surface of a container assembled with polymer methacrylate (PMMA) plates. Mineral oil is applied instead of air as the surrounding medium for easy stretching and preventing water solvent evaporation in ferrofluid. The design and processing of the container are firstly carried out to observe the shape and characterize the wettability of the droplets in the immiscible mineral oil medium. Furthermore, the droplets’ deformation and the working mechanism are given under the action of the horizontal uniform magnetic field. At different magnetic field intensities, the droplet is stretched in the horizontal direction parallel to the applied field. Due to volume conservation, the dimension in the height reduces correspondingly. With the coupling effect of magnetic force, viscous force and interfacial tension, the contact angle first increases with the magnetic field and then basically remains unchanged upon magnetization saturation. Consistent with the experimental results, the numerical method clearly reveals the field coupling mechanism and the nonlinear deformation of the sessile droplet.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9100214
Authors: Aiyu Dou Ru Bai Yucheng Sun Jiakun Tu Chuanjia Kou Xin Xie Zhenghong Qian
Magnetic tunnel junction (MTJ) sensors have been one of the excellent candidates for magnetic field detection due to their high sensitivity and compact size. In this paper, we design a magnetometer with in situ magnetic feedback consisting of an MTJ sensor. To analyze and evaluate the detectivity of the MTJ magnetometer, a noise model of the MTJ sensor in the magnetometer without magnetic feedback is first developed. Then, the noise model of the MTJ magnetometer with in situ magnetic feedback is also established, including the noises of the MTJ sensor and the signal conditioning circuit, as well as the feedback circuit. The equivalent noise model of the MTJ magnetometer with in situ magnetic feedback is evaluated through nonlinear fitting for the noise voltage spectrum. Although the noise generated by the MTJ sensor is much greater than that of the signal conditioning circuit, the noise introduced by the feedback coils into the MTJ sensor is slightly more than twice that generated by the MTJ sensor itself. The measurement results show that the detectivity of the MTJ magnetometer with in situ magnetic feedback reaches 526 pT/Hz1/2 at 10 Hz. The equivalent noise analysis method presented in this paper is suitable for the detectivity analysis of magnetometers with magnetic feedback.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9100213
Authors: Gulsara D. Kugabaeva Kamila A. Kydralieva Lyubov S. Bondarenko Rose K. Baimuratova Dmitry Yu. Karpenkov Ekaterina A. Golovkova Pavel N. Degtyarenko Nina D. Golubeva Igor E. Uflyand Gulzhian I. Dzhardimalieva
Bimetallic FeCo and FeNi nanoparticles attract much attention due to their promising magnetic properties and a wide range of practical applications as recording and storage media, catalytic systems in fuel cells, supercapacitors, lithium batteries, etc. In this paper, we propose an original approach to the preparation of FeCo- and FeNi/N-doped carbon nanocomposites by means of a coupled process of frontal polymerization and thermolysis of molecular co-crystallized acrylamide complexes. The phase composition, structure, and microstructure of the resulting nanocomposites are studied using XRD, IR spectroscopy, elemental and thermal analysis, and electron microscopy data. The main magnetic characteristics of the synthesized nanocomposites, including the field dependences and the ZFC-FC curves peculiarities, are studied. It is shown that the obtained FeCo/N-C nanocomposites exhibit exchange bias behavior at low temperatures. In turn, FeNi/N-C nanocomposites are ferromagnetically ordered.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9100212
Authors: Andrey N. Dmitriev Elena A. Vyaznikova Galina Yu. Vitkina Antonina I. Karlina
To study the influence of sinter basicity on the microstructure, phase composition, and physicochemical and metallurgical properties, samples of agglomerates with different basicities were sintered and investigated. A comprehensive study of the structure, composition, chemical, and metallurgical properties of the sinter was conducted, and the optimum values for these properties were determined. The results of the mineralogical transformations that occurred during the sintering process are also presented. The magnetite contained in the concentrate partially dissolves in the silicate component and flux during agglomeration, forming a complex silicate SFCA with the general formula M14O20 (M–Ca, Si, Al, and Mg), which is the binder of the ore phases of the agglomerate. The proportion of ferrosilicates of calcium and aluminum in the sinter depends on the basicity of the sinter charge, and the morphology of the SFCA phase depends on the cooling rate of the sinter. The more CaO in the sinter charge, the more SFCA phase is formed in the sinter, and slow cooling results in the growth of large lamellar and dendritic SFCA phases.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9090211
Authors: Linh Doan
As novel methylene blue adsorbents, polyvinyl alcohol and activated charcoal were used to modify the surface of superparamagnetic iron oxide nanoparticles. The adsorption capacity after 69 h was 26.50 ± 0.99–40.21 ± 1.30 mg/g, depending on the temperature (333.15, 310.15, and 298.15 K) and the initial concentration of methylene blue, which was between 0.017 and 0.020 mg/mL. Based on thermodynamics parameters, the adsorption process can be considered to be spontaneous endothermic physisorption. Kinetics studies show that the pseudo-second-order model was the best-fitted model. Adsorption isotherm studies show that the best-fitted models were the Langmuir, Langmuir, and Temkin and Pyzhev isotherm models when adsorbing MB at 333.15, 310.15, and 298.15 K, respectively.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9090210
Authors: Dmitry A. Estyunin Anna A. Rybkina Konstantin A. Kokh Oleg E. Tereshchenko Marina V. Likholetova Ilya I. Klimovskikh Alexander M. Shikin
We investigated the magnetic properties of the antiferromagnetic (AFM) topological insulator MnBi2Te4 with a partial substitution of Mn atoms by non-magnetic elements (AIV = Ge, Pb, Sn). Samples with various element concentrations (10–80%) were studied using SQUID magnetometry. The results demonstrate that, for all substitutes the type of magnetic ordering remains AFM, while the Néel temperature (TN) and spin-flop transition field (HSF) decrease with an increasing AIV = Ge, Pb, Sn concentration. The rate of decrease varies among the elements, being highest for Pb, followed by Sn and Ge. This behavior is attributed to the combined effects of the magnetic dilution and lattice parameter increase on magnetic properties, most prominent in (Mn1−xPbx)Bi2Te4. Besides this, the linear approximation of the experimental data of TN and HSF suggests higher magnetic parameters for pure MnBi2Te4 than observed experimentally, indicating the possibility of their non-monotonic variation at low concentrations and the potential for enhancing magnetic properties through doping MnBi2Te4 with small amounts of nonmagnetic impurities. Notably, the (Mn1−xPbx)Bi2Te4 sample with 10% Pb substitution indeed exhibits increased magnetic parameters, which is also validated by local-probe analyses using ARPES. Our findings shed light on tailoring the magnetic behavior of MnBi2Te4-based materials, offering insights into the potential applications in device technologies.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9090209
Authors: Joana Soares Regadas Sílvia Rodrigues Gavinho Sílvia Soreto Teixeira Juliana Vieira de Jesus Ana Sofia Pádua Jorge Carvalho Silva Susana Devesa Manuel Pedro Fernandes Graça
Bioglasses have been used throughout the past century as a biomaterial in the bone regeneration field. However, recent studies have attempted to use them as a therapeutic material as well, mainly in the treatment of osteosarcomas. The most widely recognized bioglass is the 45S5 Bioglass, invented by Larry Hench et al., which presents higher bioactivity. A possible application of this bioglass in the treatment of osteosarcomas can be accomplished by adding specific ions, such as iron, that will allow the use of magnetic hyperthermia and Fenton reaction as therapeutic mechanisms. In this study, a 45S5 Bioglass containing 10%mol of Fe2O3 was produced using the melt-quenching method. A group of samples was prepared by changing the overall ball milling time, from 1 h up to 48 h, to analyze the effects of iron in the bioactive glass matrix and evaluate the influence of particle size on their physical and biological properties. The studied bioglasses showed no evidence of changes in the amorphous structural nature compared to the 45S5 Bioglass. The data of the impedance spectroscopy study revealed that the addition of Fe2O3 can increase the standard rate constant of the Electro-Fenton reaction, with the sample milled for 12 h showing the most promising results. The reduction in the particle size influenced the cytotoxicity and the bioactivity. The samples with lower particle sizes showed a higher level of cytotoxicity.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9090208
Authors: Bolin Yang Yifan Xu Zhihong Chen Hang Yang Yuchen Hu Haoqin Wu Mingfeng Xing Jianguo Guan Wei Li
Soft magnetic metallic absorbents suffer from severe oxidation, reduction in permeability and deterioration in microwave absorption when exposed to high temperatures. In this study, we prepared flaky 304 stainless-steel powders as new microwave absorbents via deformation-induced ferromagnetism. The 304 stainless-steel powders showed significant increases in saturation magnetization (Ms) from 1.03 to 82.46 emu/g when their shape was changed from spheroids to flakes; the Ms further increased to 92.29 emu/g after heat treatment at 500 °C in air. The permeability of 304 alloy powders also showed an obvious increase after ball milling and remained roughly stable after heat treatment at 500 °C in air. Moreover, the permittivity exhibited a sharp decrease after heat treatment, enabling the improvement of impedance matching and microwave absorption. After heat treatment at 500 °C in air for 100 h, the simulated reflection loss of 304 stainless-steel powders with wax still showed attractive levels, giving a minimum value of −22 dB and remaining below −6 dB over 8.5–16.5 GHz at a thickness of 2 mm. Our work can help to include paramagnetic alloy systems as new microwave absorbents for working in harsh environments.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9090207
Authors: Yurii I. Dikansky Andrey S. Drozdov Inna V. Eskova Elena S. Beketova
Electrophoretic nanostructuring is a promising approach for the creation of functional surfaces and active layers. The potency of this approach may be further enhanced by additional factors of various natures, such as magnetic fields. In this work, we have studied the process of electrophoresis in thin layers of water- and kerosene-based magnetic liquids and the effect of additional magnetic fields on the occurring processes. It was found that the electrophoresis process can be significantly affected by inhomogeneous magnetic fields. The possibility of compensating electrophoresis processes in such systems by means of inhomogeneous magnetic field influence was shown. Structural changes in magnetic colloids on hydrocarbon bases under the influence of an electric field have been studied. The role of electrohydrodynamic flows arising in this process is considered, and the influence of the magnetic field on the configuration of the formed labyrinth structure is studied. The dependence of the threshold value of the electric field strength corresponding to the emergence of the structure on the temperature and additionally applied magnetic field has been established. The obtained results could contribute to the development of an original method for determining the charge and magnetic moment of a single nanoparticle.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9090206
Authors: Jennifer R. Soliz Smriti Ranjit Joshua J. Phillips Richard A. Rosenberg Adam J. Hauser
A dire need for real-time detection of toxic chemical compounds exists in both civilian and military spheres. In this paper, we demonstrate that inexpensive, commercially available Fe2O3 nanoparticles are capable of selective sensing of chemical warfare agents (CWAs) using frequency-dependent impedance spectroscopy, with additional potential as an orthogonal magnetic sensor. X-ray magnetic circular dichroism analysis shows that Fe2O3 nanoparticles possess moderately lowered moment upon exposure to 2-chloroethyl ethyl sulfide (2-CEES) and diisopropyl methylphosphonate (DIMP) and significantly lowered moment upon exposure to dimethyl methylphosphonate (DMMP) and dimethyl chlorophosphate (DMCP). Associated X-ray absorption spectra confirm a redox reaction in the Fe2O3 nanoparticles due to CWA structural analog exposure, with differentiable energy-dependent features that suggest selective sensing is possible, given the correct method. Impedance spectroscopy performed on samples dosed with DMMP, DMCP, and tabun (GA, chemical warfare nerve agent) showed strong, differentiable, frequency-dependent responses. The frequency profiles provide unique “shift fingerprints” with which high specificity can be determined, even amongst similar analytes. The results suggest that frequency-dependent impedance fingerprinting using commercially available Fe2O3 nanoparticles as a sensor material is a feasible route to selective detection.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9090205
Authors: Nisar Ahmad Ping Zhu Chao Shen Ahmad Ali Shiyong Zeng
In this paper, we study the effects of viscosity on the evolution of the double tearing mode (DTM) in a pair of adjacent Harris sheets based on the resistive MHD model in the NIMROD code. Similar to the tearing mode in the conventional single Harris sheet, a transition is observed in the generation of both normal and monster plasmoids at Prandtl number Pr=1. In the Pr<1 regime of the DTM, normal plasmoids (small plasmoids) are generated along with monster plasmoid, whereas in the single tearing mode (STM) cases, such a generation is not observed. When Pr is above the critical value, the generation of monster plasmoid is halted. Correspondingly, in the Pr<1 regime, a quadrupolar flow advects along the poloidal direction, but in the Pr>1 regime this flow advection is inhibited.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9080204
Authors: Hujun Wang Jinqiu Zhao Zhuo Luo Zhenkun Li
Traditional printed products have to some extent affected the development of smart structures and their application in multiple fields, especially in harsh environments, due to their complex mechanisms and control principles. The 4D printing technology based on magnetically controlled smart materials exploits the advantages of magnetically controlled smart materials with good operability and security, and its printed smart structures can be obtained under magnetic field drive for unfettered remote manipulation and wireless motion control, which expands the application of printed products in complex environments, such as sealed and narrow, and has broad development prospects. At present, magnetically controlled smart material 4D printing technology is still in its infancy, and its theory and application need further in–depth study. To this end, this paper introduces the current status of research on magnetically controlled smart material 4D printing, discusses the printing process, and provides an outlook on its application prospects.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9080203
Authors: Qu Wu Wenquan Sun Kinjal J. Shah Yongjun Sun
As an abundant potentially dangerous waste, red mud (RM) requires a straightforward method of resource management. In this paper, an RM catalyst loaded with cobalt (Co-RM) was prepared by the coprecipitation method for the efficient activation of persulfate (PS). Its degradation performance and mechanism of ofloxacin (OFL) were investigated. The characterization results of scanning electron microscopy, X-ray diffractometer, and energy dispersive spectrometer showed cobalt was successfully loaded onto the surface of RM, and the catalyst produced could effectively activate PS. Under the conditions of 15 mg/L OFL, 0.4 g/L Co-RM, 4 g/L PDS, 3.0 pH, and 40 °C temperature, the maximum removal rate of OFL by the Co-RM/PDS system was 80.06%. Free radical scavenging experiments confirmed sulfate radicals were the main active substances in the reaction system. The intermediates in OFL degradation were further identified by gas chromatography-mass spectrometry, and a possible degradation pathway was proposed. Finally, the relationship between defluorination rate and time in the Co-RM/PDS degradation OFL system was described by the first-order kinetic equation. This work reports an economical, environmental solution to the use of waste RM and provides a research basis for the further exploration of RM-based catalysts.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9080202
Authors: Sebastián Salazar Sandoval Daniel Santibáñez Ana Riveros Fabián Araneda Tamara Bruna Nataly Silva Nicolás Yutronic Marcelo J. Kogan Paul Jara
Magnetite/gold core-shell nanoparticles (magnetite/gold NPs) have important optical and magnetic properties that provide potential for applications, especially biomedical ones. However, their preparation is not exempt from difficulties that might lead to unexpected or undesired structures. This work reports the synthesis and characterization of magnetite/gold NPs using tetramethylammonium hydroxide (TMAH) to promote the formation of a continuous interface between the magnetite core and the thin gold shell. The synthesized magnetite/gold NPs were characterized using transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS), field emission scanning electron microscope (FE-SEM), ζ-potential, vibrating sample magnetometer (VSM), selected area electron diffraction (SAED), UV-Visible spectroscopy, and dynamic light scattering (DLS), confirming the core-shell structure of the NPs with narrow size distribution while evidencing its plasmonic and superparamagnetic properties as well. Further, the magnetite/gold NPs were associated and stabilized with a β-cyclodextrin nanosponge (β-CDNSs), obtaining a versatile magneto-plasmonic system for potential applications in the encapsulation and controlled release of drugs.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9080201
Authors: Rafael A. Raimundo Vinícius D. Silva Luciena S. Ferreira Francisco J. A. Loureiro Duncan P. Fagg Daniel A. Macedo Uílame U. Gomes Márcio M. Soares Rodinei M. Gomes Marco A. Morales
In this study, Ni-Fe alloy nanoparticles were prepared using the proteic sol–gel method, followed by a reduction in H2 at 500 and 700 °C, namely hereafter as NiFe-500 and NiFe-700, respectively. The morphological, structural, and magnetic properties were tuned via the thermal treatment in H2. The samples were studied using XPS, TEM, Mössbauer spectroscopy, DC magnetic measurements, and electrochemical measurements. Ritveld refinements showed that the sample NiFe-500 has FCC (face-centered cubic) and BCC (body-centered cubic) NiFe alloys, while the sample NiFe-700 has only FCC NiFe alloy. For both samples, magnetization measurements in the range of 300–900 K showed the presence of the Griffiths phase, indicating the formation of clusters of either Fe or Ni-Fe alloys rich in Fe. The sample NiFe-500 presented ferromagnetic (FM) transitions at 533, 700, and 834 K, assigned to the alloys Ni37Fe63-FCC, Ni46Fe54-FCC, and Ni55Fe45-FCC, respectively. In contrast, we could not observe the FM transition of the BCC Ni-Fe alloy because of limitations in our experimental setup (T ≤ 900 K). Meanwhile, three FM transitions were observed for the sample NiFe-700 at 480, 655, and 825 K, attributed to the alloys Ni34Fe66-FCC, Ni43Fe57-FCC, and Ni54Fe46-FCC, respectively. At 5 K, the samples NiFe-500 and NiFe-700 have saturation magnetizations of 164.2 and 173.6 emu g−1, respectively. For application in Oxygen Evolution Reaction catalysis, the samples NiFe-500 and NiFe-700 showed different overpotentials of 319 and 307 mV at 10 mA cm−2. These low overpotential values indicate a higher electrochemical activity of the FCC Ni-Fe alloy and, for both samples, a superior electrocatalytic activity in comparison to RuO2 e IrO2 conventional catalysts. Furthermore, the samples showed high electrochemical stability in chrono potentiometric studies for up to 15 h. This current work highlights that the Ni-Fe alloys produced via the proteic sol–gel and with a reduction in H2 methods can be promising for OER systems due to their good performance and low costs.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9080200
Authors: Jessica R. P. Oliveira Laura S. Ribas Jose S. Napoli Eduardo Abreu Jose L. Diaz de Tuesta Helder T. Gomes Angelo M. Tusset Giane G. Lenzi
This study describes the synthesis of an innovative nanomaterial (patent application number BR 1020210000317) composed of cobalt ferrite functionalized in niobium pentoxide CoFe2O4@Nb5O2 (CFNb), synthesized via green synthesis using tangerine peel extract. The material emphasizes the combination of a magnetic material (which allows for easy recovery after application) with niobium pentoxide (a metal which is abundant in Brazil). CFNb was applied as a catalyst for the paracetamol (PCT) degradation by photocatalysis. The new materials were characterized through surface and pore analysis (SBET, SEXT, Smic, Vmic, and VTOTAL), photoacoustic spectroscopy (PAS), zero charge point (pHPZC, scanning electron microscopy (SEM/EDS), and X-ray diffraction (XRD). The reaction parameters studied included pH and catalyst concentration. The results indicated that the CFNb nanocatalysts were efficient in the paracetamol degradation, presenting better results in conditions of low pH (close to 2) and low catalyst concentration under irradiation of the 250 W mercury vapor lamp (greater than 28 mW·cm−2) at 60 min of reaction.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9080199
Authors: Loic Temdie Vincent Castel Timmy Reimann Morris Lindner Carsten Dubs Gyandeep Pradhan Jose Solano Romain Bernard Hicham Majjad Yves Henry Matthieu Bailleul Vincent Vlaminck
We propose an experimental method for the unidirectional excitation of spin waves. By structuring Au nanowire arrays within a coplanar waveguide onto a thin yttrium iron garnet (YIG) film, we observe a chiral coupling between the excitation field geometry of the nanowire grating and several well-resolved propagating magnon modes. We report a propagating spin wave spectroscopy study with unprecedented spectral definition, wavelengths down to 130 nm and attenuation lengths well above 100 μm over the 20 GHz frequency band. The proposed experiment paves the way for future non-reciprocal magnonic devices.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9080198
Authors: Anatoly Ye. Yermakov Mikhail A. Uimin Danil W. Boukhvalov Artem S. Minin Nadezhda M. Kleinerman Sergey P. Naumov Aleksey S. Volegov Denis V. Starichenko Kirill I. Borodin Vasily S. Gaviko Sergey F. Konev Nikolay A. Cherepanov
In this paper, the electron and magnetic state of iron placed either on the surface or in the core of TiO2 nanoparticles were investigated using magnetometric methods, electron paramagnetic resonance (EPR) and Mössbauer spectroscopy. It was demonstrated that the EPR spectra of TiO2 samples with iron atoms localized both on the surface and in the core of specific features depending on the composition and size of the nanoparticles. Theoretical calculations using the density functional theory (DFT) method demonstrated that the localization of Fe atoms on the surface is characterized by a considerably larger set of atomic configurations as compared to that in the core of TiO2 nanoparticles. Mössbauer spectra of the samples doped with Fe atoms both on the surface and in the core can be described quite satisfactorily using two and three doublets with different quadrupole splitting, respectively. This probably demonstrates that the Fe atoms on particle surface and in the bulk are in different unlike local surroundings. All iron ions, both on the surface and in the core, were found to be in the Fe3+ high-spin state.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9080197
Authors: Dariya Kalyuzhnaya Evgeniy Sokolov Anastasia Vasilyeva Irina Sutarina Irina Shabanova Petr Ryapolov
The microfluidics of magnetic fluids is gaining popularity due to the possibility of the non-contact control of liquid composite systems using a magnetic field. The dynamics of non-magnetic droplets and gas bubbles in magnetic fluids were investigated for various configurations of magnetic fields, coatings, and channel geometries, as well as the rate of component supply and their physical properties. Optimal regimes for forming droplet and bubble flows were determined. The mechanism for non-contact control of the size of droplets and bubbles using a magnetic field is proposed in this article. The dependences of the sizes of non-magnetic inclusions in magnetic liquids on the continuous phase flow rate and the displacement of magnets were obtained. The obtained dependences of the volume of non-magnetic inclusions on the flow rate of the continuous phase follow the classic dependences. Changing the size of air bubbles can be achieved by shifting the magnet from −5 mm to +2 mm. The ratio of the maximum and minimum breakaway inclusion varies from 5 to 2 depending on the flow rates of the continuous phase. The range of changing the size of oil droplets with the displacement of magnets is from 1.1 to 1.51. These studies show how, with the help of various mechanisms of influence on microfluidic flows, it is possible to control the size of bubbles and droplets forming in microchannels. The obtained data can be applied for controlled microfluidic dosing and counting devices.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9080196
Authors: Anastasia Sedelnikova Yuliya Poletaeva Victor Golyshev Alexey Chubarov Elena Dmitrienko
Hybrid magnetic molecularly imprinted polymers (MMIPs) have the advantages of the technology of molecularly imprinted material and magnetic nanoparticles. The magnetic properties of MMIPs allow easy magnetic separation of various pollutants and analytes. A convenient and simple approach has been developed for the preparation of MMIPs based on polyamide (nylon-6) and magnetic nanoparticles. The polymer matrix was formed during the transition of nylon-6 from a dissolved state to a solid state in the presence of template molecules and Fe3O4 nanoparticles in the initial solution. Methylene blue (MB) was used as a model imprinted template molecule. The MMIPs exhibited a maximum adsorption amount of MB reached 110 µmol/g. The selectivity coefficients toward MB structural analogs were estimated to be 6.1 ± 0.6 and 2.1 ± 0.3 for 15 μM hydroxyethylphenazine and toluidine blue, which shows high MMIP selectivity. To prove the MMIPs’ specificity in MB recognition, magnetic nonimprinted polymers (MNIPs) were synthesized without the presence of a template molecule. MMIPs exhibited much higher specificity in comparison to MNIPs. To show the remarkable reusability of the MMIP sorbent, more than four MB absorption and release cycles were carried out, demonstrating almost the same extraction capacity step by step. We believe that the proposed molecular imprinting technology, shown in the MB magnetic separation example, will bring new advances in the area of MMIPs for various applications.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9080195
Authors: Do Hung Manh Tran Minh Thi Nguyen Thi Ngoc Anh Vu Hong Ky Nguyen Manh Nghia Tran Dang Thanh
Nanocomposites of polyaniline (PANI)/Fe2.85Ni0.15O4 (PFN) were successfully prepared using the co-precipitation method combined with an in-situ polymerization process. The FN and PFN nanocatalysts were characterized using various methods for the photocatalytic degradation of Rhodamine B (RhB). The XRD, Raman, TEM, and DTA-DTG analyses suggest that the FN nanoparticles (NPs) were effectively coated by PANI and that there were interactions between FN and PANI. Magnetic measurements indicated that PFN nanocomposites exhibited good superparamagnetic behavior and high saturation magnetization (39.5–57.6 emu/g), which are suitable for separating photocatalysts from solution for reuse. Adsorption-desorption analysis showed that the specific surface area of PFN was higher than that of FN. The UV-vis absorption spectra of FN and PFN nanocomposites exhibited strong absorption of visible light, attributed to the doping of Ni, which resulted in the reduction of the band-gap energy (Eg) of Fe3O4 to 2.4 eV. PFN nanocomposites with different mass ratios of PANI demonstrated superior photocatalytic activity compared to FN NPs. Furthermore, it was observed that PFN with a 10% mass ratio of PANI exhibited the highest RhB degradation efficiency, achieving a rate of approximately 98% after 300 min of irradiation. Finally, the possible photocatalytic degradation mechanisms of the PFN nanocomposites on RhB were discussed. PFN photocatalysts with good photocatalytic activity, inexpensive materials, and easy preparation could be potential candidates for wastewater purification applications.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9080194
Authors: Navruzbek N. Habibullayev Nikolay G. Naumov Alexander N. Lavrov Natalia V. Kuratieva Aleksandr S. Aleksandrovsky Aleksandr S. Oreshonkov Maxim S. Molokeev Irina V. Palamarchuk Ilya O. Yurev Yuriy G. Denisenko Oleg V. Andreev Alena D. Zakharova
SrLnCuSe3 (Ln = Dy, Ho, Er, Tm) compounds crystallize in the Pnma and Cmcm orthorhombic space group and belong to the Eu2CuS3 and KCuZrS3 structural type, respectively. According to a single-crystal XRD study, the SrTmCuSe3 unit cell parameters are a = 4.0631 (4), b = 13.4544 (14), c = 10.4430 (10) Å, and V = 570.88 (10) Å3. All the studied SrLnCuSe3 samples in the temperature range of 1.77–300 K demonstrate paramagnetic behavior without any features pointing to magnetic ordering. The measured Curie constants coincide with the values expected for Ln3+ ions with good accuracy, which confirms the stoichiometric composition of the samples and the non-magnetic state of the copper ions, Cu1+ (S = 0). The conducted optical absorption study showed that the polycrystalline SrLnCuSe3 (Ln = Dy, Ho, Er, Tm) samples are semiconductors with a direct bandgap ranging from 2.14 eV to 2.31 eV. Two indirect bandgaps were revealed and explained by the presence of optical transitions to highly dispersive subbands in the conduction band. The compounds demonstrate two reversible phase transitions α⇆β, β⇆γ and an incongruent melting at 1606 K (Dy), 1584 K (Ho), 1634 K (Er), and 1620 K (Tm) associated with the formation of solid solutions of SrSe, Cu2-XSe, and Ln2Se3 binary compounds.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9080193
Authors: Jamil Kazmi Jamal Kazmi Syed Raza Ali Raza Babar Nazir Raja Azhar Saeed Khan Mohd Ambri Mohamed Mohsin Rafique
In this study, we grew pristine and Ni-doped vertically aligned zinc oxide nanowires (NWs) on a glass substrate. Both the doped and pristine NWs displayed dominant 002 peaks, confirming their vertical alignment. The Ni-doped NWs exhibited a leftward shift compared to the pristine NWs. TEM measurements confirmed the high crystallinity of individual NWs, with a d-spacing of ~0.267 nm along the c-axis. Ni-doped NWs had a higher density, indicating increased nucleation sites due to nickel doping. Doped NW films on glass showed enhanced absorbance in the visible region, suggesting the creation of sub-gap defect levels from nickel doping. Magnetization vs. magnetic field measurements revealed a small hysteresis loop, indicative of soft ferromagnetic behavior. Current transient plots demonstrated an increase in current with an applied magnetic field. Two-terminal devices exhibited a photo response that intensified with magnetic field application. This increase was attributed to parallel grain alignment, resulting in enhanced carrier concentration and photo response. In the dark, transport properties displayed negative magnetoresistance behavior. This magneto-transport effect and enhanced photo response (under an LED at ~395 nm) were attributed to giant magnetoresistance (GMR) in the aligned NWs. The observed behavior arose from reduced carrier scattering, improved transport properties, and parallel spin alignment in the magnetic field.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9080192
Authors: Hadeel Moustafa Flemming H. Larsen Anders Ø. Madsen Stephan P. A. Sauer
In this work we present a systematic, theoretical investigation of the 13C NMR chemical shifts for several mono-, di- and trisaccharides in the solid state. The chemical shifts have been calculated using density functional theory (DFT) together with the gauge including the projector augmented wave (GIPAW) method as implemented in the CASTEP program. We studied the changes in the 13C NMR chemical shifts in particular due to the formation of one or two glycosidic linkages and due to crystal water. The largest changes, up to 14 ppm, are observed between the mono- and disaccharides and typically for the glycosidic linkage atoms, but not in all cases. An analysis of the bond angles at the glycosidic linkage and the observed changes in chemical shifts displays no direct correlation between them. Somewhat smaller changes in the range of 2 to 5 ppm are observed when single crystal water molecules are close to some of the atoms. Relating the changes in the chemical shifts of the carbon atoms closest to the crystal water to the distance between them does, however, not lead to a simple relation between them.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9080191
Authors: Ibtissem Benguettat-El Mokhtari David S. Schmool
This review article aims to provide a comprehensive overview of recent FMR studies on magnetic oxide nanoparticles and their potential applications. The use of the FMR technique is a powerful tool to study the magnetic properties of magnetic nanoparticles and can provide valuable information on their behavior. For this, we will start by discussing the purpose of these magnetic nanoparticles and their application in various fields, including biomedical applications, energy storage, and environmental remediation. We will then discuss the methods used to prepare magnetic nanoparticles and the theory behind FMR including the superparamagnetic effect. Additionally, we will present the most recent studies on FMR for magnetic oxide nanoparticles by highlighting the effect of temperature and doping on the magnetic properties of these nanoparticles.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070190
Authors: Fabio Manna Mariangela Oggianu Narcis Avarvari Maria Laura Mercuri
Lanthanide metal–organic frameworks (Ln-MOFs) showing single-molecule magnet (SMM) properties are an ever-growing family of materials where the magnetic properties can be tuned by various interrelated parameters, such as the coordinated solvent, temperature, organic linkers, lanthanide ions and their coordination environment. An overview of the general synthetic methodologies to access MOFs/Ln-MOFs and the peculiarities and parameters to control and/or fine-tune their SMM behavior is herein presented. Additionally, diverse challenging strategies for inducing SMM/SIM behavior in an Ln-MOF are discussed, involving redox activity and chirality. Furthermore, intriguing physical phenomena such as the CISS effect and CPL are also highlighted.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070189
Authors: Susana Aberturas José Luis Olazagoitia Miguel Ángel García Antonio Hernando
In the automobile sector, energy recovery and sustainability are becoming more and more important, and energy-harvesting suspension systems (EHSAs) have a lot of promise to improve vehicle efficiency. This investigation expands on prior work that investigated the viability of an EHSA that uses permanent magnets and amorphous core coils. The performance of the proposed system is demonstrated and enhanced in the current study through the development and optimization of a prototype. A thorough testing of the prototype is performed to determine design improvements for boosting the system’s overall performance and to quantify the recovered energy. In previous work, a method was proposed to find the dependence of the magnetic flux with the relative position between the primary and secondary elements to obtain the optimal position for the system. This method is applied to optimize the energy harvesting coil by testing different configurations in terms of the placement and type of amorphous or nonamorphous core inside the energy harvesting coil. This is a crucial area of attention in order to maximize energy recovery while solving the low-frequency problem that suspension systems have (on the order of 10 Hz).
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070188
Authors: Kaushik Sarkar Madison Jordan Abebe Kebede Steve Kriske Frank Wise Dhananjay Kumar
The magnetocaloric effect (MCE) in iron (Fe) nanoparticles incorporated within a titanium nitride (TiN) thin-film matrix grown using pulsed laser deposition (PLD) is investigated in this study. The study demonstrates the ability to control the entropy change across the magnetic phase transition by varying the size of the Fe nanoparticles. The structural characterization carried out using X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and scanning transmission electron (TEM) showed that TiN films are (111) textured, while the Fe-particles are mostly spherical in shapes, are single-crystalline, and have a coherent structure with the surrounding TiN thin-film matrix. The TiN thin-film matrix was chosen as a spacer layer since it is nonmagnetic, is highly corrosion-resistive, and can serve as an excellent conduit for extracting heat due to its high thermal conductivity (11 W/m K). The magnetic properties of Fe–TiN systems were investigated using a superconducting quantum interference device (SQUID) magnetometer. In-plane magnetic fields were applied to record magnetization versus field (M–H) and magnetization versus temperature (M–T) curves. The results showed that the Fe–TiN heterostructure system exhibits a substantial isothermal entropy change (ΔS) over a wide temperature range, encompassing room temperature to the blocking temperature of the Fe nanoparticles. Using Maxwell’s relation and analyzing magnetization–temperature data under different magnetic fields, quantitative insights into the isothermal entropy change (ΔS) and magnetocaloric effect (MCE) were obtained for the Fe–TiN heterostructure system. The study points out a considerable negative change in ΔS that reaches up to 0.2 J/kg K at 0.2 T and 300 K for the samples with a nanoparticle size on the order of 7 nm. Comparative analysis revealed that Fe nanoparticle samples demonstrate higher refrigeration capacity (RC) in comparison to Fe thin-film multilayer samples, with the RC increasing as the Fe particle size decreases. These findings provide valuable insights into the potential application of Fe–TiN heterostructures in solid-state cooling technologies, highlighting their enhanced magnetocaloric properties.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070187
Authors: Natália Andrýsková Paul Sourivong Melánia Babincová Peter Babinec Mária Šimaljaková
Dithranol is one of the oldest and most efficient drugs used in the treatment of psoriasis. One of the challenges with using dithranol is its photostability, because it easily degrades when exposed to light. This study investigated the potential of coaxial core-sheath PCL/PVA nanofibers as a dual-functional system for enhancing dithranol photostability and remote-controlled drug delivery for psoriasis therapy. We have shown that coaxial nanofibers with titanium oxide nanoparticles (reflecting and absorbing ultra-violet light) in the PVA-based sheath part of the nanofibers can increase dithranol photostability. Incorporation of dithranol and magnetic nanoparticles into a PCL-based core of the nanofibers enables dithranol release control via an external radio-frequency field. The application of a radio-frequency field generates heat that can be used to control the release rate of drugs. Our approach therefore offers a non-invasive and remotely controlled drug release system that hold promise for the development of new topical formulations for psoriasis treatment using dithranol.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070186
Authors: Pavel Varlamov Anna Semisalova Anh Dung Nguyen Michael Farle Yannis Laplace Michele Raynaud Olivier Noel Paolo Vavassori Vasily Temnov
In this study, we present a novel investigation into the magnetic and morphological properties of equiatomic B2-ordered FeRh thin films irradiated with single high-intensity ultrashort laser pulses. The goal is to elucidate the effect of femtosecond laser ablation on the magnetic properties of FeRh. We employed Scanning Magneto-Optical Kerr Effect (S-MOKE) microscopy to examine the magnetic phase after laser processing, providing high spatial resolution and sensitivity. Our results for the first time demonstrated the appearance of a magneto-optical signal from the bottom of ablation craters, suggesting a transition from antiferromagnetic to ferromagnetic behavior. Fluence-resolved measurements clearly demonstrate that the ablation threshold coincides with the threshold of the antiferromagnet-to-ferromagnet phase transition. The existence of such a magnetic phase transition was independently confirmed by temperature-dependent S-MOKE measurements using a CW laser as a localized heat source. Whereas the initial FeRh film displayed a reversible antiferromagnet-ferromagnet phase transition, the laser-ablated structures exhibited irreversible changes in their magnetic properties. This comprehensive analysis revealed the strong correlation between the femtosecond laser ablation process and the magnetic phase transformation in FeRh thin films.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070185
Authors: Evgeniy D. Chernov Alexey V. Lukoyanov
In this theoretical study, we investigate the effect of electron correlations on the electronic structure and magnetic properties of the full Heusler alloy Mn2NiAl in the framework of first-principles calculations. We investigate the electron correlation effect as employed within hybrid functional (HSE) and also within the DFT+U method with varied values of parameters between 0.9 and 6 eV. The XA-crystal structure was investigated with antiferromagnetic orderings of the magnetic moments of the manganese. It was found that with a growth of the Coulomb interaction parameter, the manganese ions magnetic moment increases, and it reaches the value of 4.15–4.46 μB per Mn. In addition, the total magnetic moment decreases because of the AFM ordering of the Mn ions and a small magnetic moment of Ni. The calculated total magnetic value agrees well with recent experiments demonstrating a low value of magnetization. This experimental value is most closely reproduced for the moderate values of the Coulomb parameter, also calculated in constrained LDA, while previous DFT studies substantially overestimated this value. It is also worth noticing that for all values of the Coulomb interaction parameter, this compound remains metallic in its electronic structure in agreement with transport measurements.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070184
Authors: Tudor-Gabriel Mocioi Antonia Ghita Vasily V. Temnov
Using valid experimental parameters, we quantify the magnitude of resonantly phonon-driven precession of exchange magnons in freestanding ferromagnetic nickel thin films on their thickness L. Analytical solutions of acoustically driven equations for magnon oscillators display a nonmonotonous dependence of the peak magnetization precession on the film thickness. It is explained by different L-dependence of multiple prefactors entering in the expression for the total magnetization dynamics. Depending on the ratio of acoustic and magnetic (Gilbert) damping constants, the magnetization precession is shown to be amplified by a Q-factor of either the phonon or the magnon resonance. The increase in the phonon mode amplitude for thinner membranes is also found to be significant. Focusing on the magnetization dynamics excited by the two first acoustic eigenmodes with p=1 and p=2, we predict the optimum thicknesses of nickel membranes to achieve large amplitude magnetization precession at multi 100 GHz frequencies at reasonably low values of an external magnetic field. By extending the study to the case of Ni-Si bilayers, we show that these resonances are achievable at even higher frequencies, approaching the THz range.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070183
Authors: Michele Segantini Gianluca Marcozzi Denis Djekic Anh Chu Daniel Amkreutz Cham Thi Trinh Sebastian Neubert Bernd Stannowski Kerstin Jacob Ivo Rudolph Joseph E. McPeak Jens Anders Boris Naydenov Klaus Lips
Electrically detected magnetic resonance (EDMR) is a spectroscopic technique that provides information about the physical properties of materials through the detection of variations in conductivity induced by spin-dependent processes. EDMR has been widely applied to investigate thin-film semiconductor materials in which the presence of defects can induce the current limiting processes. Conventional EDMR measurements are performed on samples with a special geometry that allows the use of a typical electron paramagnetic resonance (EPR) resonator. For such measurements, it is of utmost importance that the geometry of the sample under assessment does not influence the results of the experiment. Here, we present a single-board EPR spectrometer using a chip-integrated, voltage-controlled oscillator (VCO) array as a planar microwave source, whose geometry optimally matches that of a standard EDMR sample, and which greatly facilitates electrical interfacing to the device under assessment. The probehead combined an ultrasensitive transimpedance amplifier (TIA) with a twelve-coil array, VCO-based, single-board EPR spectrometer to permit EDMR-on-a-Chip (EDMRoC) investigations. EDMRoC measurements were performed at room temperature on a thin-film hydrogenated amorphous silicon (a-Si:H) pin solar cell under dark and forward bias conditions, and the recombination current driven by the a-Si:H dangling bonds (db) was detected. These experiments serve as a proof of concept for a new generation of small and versatile spectrometers that allow in situ and operando EDMR experiments.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070182
Authors: José F. Malta Marta S. C. Henriques José A. Paixão António P. Gonçalves
GaMo4Se8, is a lacunar spinel where skyrmions have been recently reported. This compound belongs to the GaM4X8 family, where M is a transition metal (V or Mo) and X is a chalcogenide (S or Se). In this work, we have obtained pure GaMo4Se8 in polycrystalline form through an innovative two-step synthetic route. Phase purity and chemical composition were confirmed through the Rietveld refinement of the powder XRD pattern, the sample characterisation having been complemented with SEM analysis. The magnetic phase diagram was investigated using DC (VSM) and AC magnetometry, which disclosed the presence of cycloidal, skyrmionic and ferromagnetic phases in polycrystalline GaMo4Se8.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070181
Authors: Xiaogang Yu Renpeng Yang Chengwei Wu Bo Liu Wei Zhang
Zn0.6Mg0.4CrxFe2−xO4 (0 ≤ x ≤ 0.4) nanoparticles were synthesized using a hydrothermal technique. The obtained magnetic nanoparticles (MNPs) exhibited a spinel structure, where the lattice constant decreased with the Cr3+ ion content. The doping of Cr3+ ion (x = 0.1) increased the specific saturation magnetization to 46.4 emu/g but decreased to 20.0 emu/g with the further increase in the Cr3+ ion content to x = 0.4. The decrement in Curie temperature was ascribed to the weakened super-exchange interaction between the metal ions located at A-sites and B-sites, which arose from the doping of the Cr3+ ion. The T2-weighted images gradually darkened with the increase in Zn0.6Mg0.4Cr0.1Fe1.9O4 nanoparticles concentration, suggesting that the nanoparticles can enhance the image contrast. Zn0.6Mg0.4CrxFe2−xO4 (0 ≤ x ≤ 0.4) nanoparticles were able to heat the agar phantom to the hyperthermia temperature under the safe alternating magnetic field, which showed their potential in the magnetic induction hyperthermia.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070180
Authors: Hiroyuki Tajima Takeshi Oda Tomofumi Kadoya
This paper presents the concept and experimental evidence for the nonthermal equilibrium (NTE) process of charge carrier extraction in metal/insulator/organic semiconductor/metal (MIOM) capacitors. These capacitors are structurally similar to metal/insulator/semiconductor/(metal) (MIS) capacitors found in standard semiconductor textbooks. The difference between the two capacitors is that the (organic) semiconductor/metal contacts in the MIOM capacitors are of the Schottky type, whereas the contacts in the MIS capacitors are of the ohmic type. Moreover, the mobilities of most organic semiconductors are significantly lower than those of inorganic semiconductors. As the MIOM structure is identical to the electrode portion of an organic field-effect transistor (OFET) with top-contact and bottom-gate electrodes, the hysteretic behavior of the OFET transfer characteristics can be deduced from the NTE phenomenon observed in MIOM capacitors.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070179
Authors: Cristina Favieres
The Special Issue Soft and Hard Magnetic Materials: Latest Advances and Prospects aims to provide researchers with an overview of some aspects of the current research in magnetic materials from theoretical studies to their applications, including their fabrication and characterization [...]
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070178
Authors: Chengfang Shi Laiwei Gao Martin Baumgarten Dongdong Wei Zhipeng Xu Wenping Wang Di Wang
In contrast to diradical linked by π-conjugation, there have been only a limited number of studies reported for those linked by homoconjugation systems. Bis(nitronyl nitroxide) diradicals and monoradical connected by a core non-rigid triptycene unit were synthesized. EPR spectroscopy and SQUID were employed to investigate the magnetic exchange interactions. The results demonstrate that the values of ΔEST are 0.19 kcal/mol (J = 34.4 cm−1) for 2,6-TP-NN and −0.21 kcal/mol (J = −36.9 cm−1) for 2,7-TP-NN, indicating ferromagnetic interaction and antiferromagnetic interaction, respectively. The spin polarization rule is not a precise predictor of the behavior of triptycene diradicals, and therefore, we improve the model. The experimental findings indicate that homoconjugation can function directly as a coupling pathway between the two spin centers, which is in qualitative agreement with the DFT theoretical calculations and the Borden rule. This research has found a special means of achieving spin coupling in non-rigid aromatics by means of homoconjugation.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070177
Authors: Elena V. Fomenko Galina V. Akimochkina Yuriy V. Knyazev Sergey V. Semenov Vladimir V. Yumashev Leonid A. Solovyov Alexander G. Anshits
The recycling of hazardous industrial waste into high-tech materials with desired properties is of considerable interest since it provides optimal alternatives for its final disposal. Coal fly ash, the major waste generated by coal-fired power plants, contains significant quantities of dispersed microspheres with a diameter smaller than 10 μm, which are anthropogenic atmospheric pollutants PM10. Due to their composition and fine-grained powder morphology, they can be converted into sintered products. In this study, dispersed microspheres from class C fly ash were directly sintered without any additive to form high-strength glass-ceramics with magnetic properties. The optimum processing conditions were achieved at a temperature of 1200 °C, at which samples with a compressive strength of 100.6 MPa were obtained. Sintering reduces the quantity of the glass phase and promotes the formation of larnite, Fe-spinel, ye’elimite, and ternesite. Mössbauer measurements show that the relative concentration of the magnetic phase compared to the paramagnetic one rises almost in order. The sintered sample demonstrates a narrower distribution of the hyperfine magnetic field and a significantly lower value of the coercive field of 25 Oe, which allows proposing such materials as soft magnetic materials. The presented results demonstrate promising industrial applications of hazardous PM10 to minimize solid waste pollution.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070176
Authors: V. S. Gornakov I. V. Shashkov O. A. Tikhomirov Yu. P. Kabanov
Domain wall mobility as a function of nonmagnetic interlayer thickness and temperature was studied in ultrathin exchange-coupled ferromagnetic layers using magneto-optic Kerr microscopy. The system under study is a Pt/Co/Pt/Co/Pt heterostructure having perpendicular magnetic anisotropy and a middle Pt layer with spatially variable thickness. The ferromagnetic interaction between the Co layers is observed when the Pt interlayer thickness varies from 5 to 6 nm in a temperature range of 200–300 K. There is a certain interval of Pt layer thickness where domain walls in both ferromagnetic layers move independently. Nonlinear dependence of the domain wall displacement on the applied field was measured. It is shown that an equilibrium position of the relaxed domain wall depends on field, temperature, and the nonmagnetic interlayer thickness. This position is determined by the energy balance: (i) domain wall displacement provided by the applied field, (ii) interlayer exchange interaction in the area swept by the domain wall, and (iii) domain wall coercivity. The mechanism of domain wall stabilization in terms of independent wall motion near critical thickness was considered. It is found that both the coercivity of the Co layer and the critical thickness decrease at higher temperature, while the interlayer exchange constant J is changed weakly.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070175
Authors: Carlos Cruz Nathalie Audebrand Dayán Páez-Hernández Verónica Paredes-García
A new trinuclear CuII compound {[Cu3(HL′)2(H2O)2](ClO4)4}·(H2O)4 (1) was obtained and presented a trapped chiral hemiaminal (HL2′ = [(5-amino-4H-1,2,4-triazol-3-yl)amino](1H-imidazol-4-yl)methanol)). Compound 1 shows an almost flat cationic structure [Cu3(HL′)2(H2O)2]4+ with a Cu3 linear core reached by the double Cu-OR/NN-Cu triazole/alkoxo bridge of the hemiaminal molecule. The CuII spin carriers are antiferromagnetically coupled, presenting a spin doublet ground state (S = 1/2) with a magnetic coupling constant of −179 cm−1. Moreover, DTF calculations show that the planarity of the compound permits a sigma-type overlapping between the unpaired electrons of the spin carriers and the p-type orbitals of the coordinated N and O atoms producing an electronic delocalization through the bridging ligand responsible for the strong antiferromagnetic interactions observed experimentally.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070174
Authors: Reizo Kato Takao Tsumuraya
Single-component molecular conductors exhibit a strong connection to the Dirac electron system. The formation of Dirac cones in single-component molecular conductors relies on (1) the crossing of HOMO and LUMO bands and (2) the presence of nodes in the HOMO–LUMO couplings. In this study, we investigated the possibility of Dirac cone formation in two single-component molecular conductors derived from nickel complexes with extended tetrathiafulvalenedithiolate ligands, [Ni(tmdt)2] and [Ni(btdt)2], using tight-biding models and first-principles density-functional theory (DFT) calculations. The tight-binding model predicts the emergence of Dirac cones in both systems, which is associated with the stretcher bond type molecular arrangement. The DFT calculations also indicate the formation of Dirac cones in both systems. In the case of [Ni(btdt)2], the DFT calculations, employing a vdW-DF2 functional, reveal the formation of Dirac cones near the Fermi level in the nonmagnetic state after structural optimization. Furthermore, the DFT calculations, by utilizing the range-separated hybrid functional, confirm the antiferromagnetic stability in [Ni(btdt)2], as observed experimentally.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070173
Authors: Vladislav D. Kochev Seidali S. Seidov Pavel D. Grigoriev
Most high-Tc superconductors are spatially inhomogeneous. Usually, this heterogeneity originates from the interplay of various types of electronic ordering. It affects various superconducting properties, such as the transition temperature, the magnetic upper critical field, the critical current, etc. In this paper, we analyze the parameters of spatial phase segregation during the first-order transition between superconductivity (SC) and a charge- or spin-density wave state in quasi-one-dimensional metals with imperfect nesting, typical of organic superconductors. An external pressure or another driving parameter increases the transfer integrals in electron dispersion, which only slightly affects SC but violates the Fermi surface nesting and suppresses the density wave (DW). At a critical pressure Pc, the transition from a DW to SC occurs. We estimate the characteristic size of superconducting islands during this phase transition in organic metals in two ways. Using the Ginzburg–Landau expansion, we analytically obtain a lower bound for the size of SC domains. To estimate a more specific interval of the possible size of the superconducting islands in (TMTSF)2PF6 samples, we perform numerical calculations of the percolation probability via SC domains and compare the results with experimental resistivity data. This helps to develop a consistent microscopic description of SC spatial heterogeneity in various organic superconductors.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070172
Authors: Matheus G. R. Gomes Andréa L. F. De Souza Hélio F. Dos Santos Wagner B. De Almeida Diego F. S. Paschoal
In the present study, we benchmark computational protocols for predicting Co-59 NMR chemical shift. Quantum mechanical calculations based on density functional theory were used, in conjunction with our NMR-DKH basis sets for all atoms, including Co, which were developed in the present study. The best protocol included the geometry optimization at BLYP/def2-SVP/def2-SVP/IEF-PCM(UFF) and shielding constant calculation at GIAO-LC-ωPBE/NMR-DKH/IEF-PCM(UFF). This computational scheme was applied to a set of 34 Co(III) complexes, in which, Co-59 NMR chemical shift ranges from +1162 ppm to +15,100 ppm, and these were obtained in distinct solvents (water and organic solvents). The resulting mean absolute deviation (MAD), mean relative deviation (MRD), and coefficient of determination (R2) were 158 ppm, 3.0%, and 0.9966, respectively, suggesting an excellent alternative for studying Co-59 NMR.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070171
Authors: Shahzad Ahmad Qureshi Haroon Aman Romana Schirhagl
The worldwide death toll claimed by Acute Respiratory Syndrome Coronavirus Disease 2019 (SARS-CoV), including its prevailed variants, is 6,812,785 (worldometer.com accessed on 14 March 2023). Rapid, reliable, cost-effective, and accurate diagnostic procedures are required to manage pandemics. In this regard, we bring attention to quantum spin magnetic resonance detection using fluorescent nanodiamonds for biosensing, ensuring the benefits of artificial intelligence-based biosensor design on an individual patient level for disease prediction and data interpretation. We compile the relevant literature regarding fluorescent nanodiamonds-based SARS-CoV-2 detection along with a short description of viral proliferation and incubation in the cells. We also propose a potentially effective strategy for artificial intelligence-enhanced SARS-CoV-2 biosensing. A concise overview of the implementation of artificial intelligence algorithms with diamond magnetic nanosensing is included, covering this roadmap’s benefits, challenges, and prospects. Some mutations are alpha, beta, gamma, delta, and Omicron with possible symptoms, viz. runny nose, fever, sore throat, diarrhea, and difficulty breathing accompanied by severe body pain. The recommended strategy would deliver reliable and improved diagnostics against possible threats due to SARS-CoV mutations, including possible pathogens in the future.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070170
Authors: Roman Atanasov Ecaterina Brinza Rares Bortnic Razvan Hirian Gabriela Souca Lucian Barbu-Tudoran Iosif Grigore Deac
Here we report the synthesis and investigation of bulk and nano-sized La0.7Ba0.3−xCaxMnO3 (x = 0, 0.15, 0.2 and 0.25) compounds that are promising candidates for magnetic refrigeration applications. We compare the structural and magnetic properties of bulk and nano-scale polycrystalline La0.7Ba0.3−xCaxMnO3 for potential use in magnetic cooling systems. Solid-state reactions were implemented for bulk materials, while the sol–gel method was used for nano-sized particles. Structurally and morphologically, the samples were investigated by X-ray diffraction (XRD), optical microscopy and transmission electron microscopy (TEM). Oxygen stoichiometry was investigated by iodometry. Bulk compounds exhibit oxygen deficiency, while nano-sized particles show excess oxygen. Critical magnetic behavior was revealed for all samples using the modified Arrott plot (MAP) method and confirmed by the Kouvel–Fisher (KF) method. The bulk polycrystalline compound behavior was better described by the tricritical field model, while the nanocrystalline samples were governed by the mean-field model. Resistivity in bulk material showed a peak at a temperature Tp1 attributed to grain boundary conditions and at Tp2 associated with a Curie temperature of Tc. Parent polycrystalline sample La0.7Ba0.3MnO3 has Tc at 340 K. Substitution of x = 0.15 of Ca brings Tc to 308 K, and x = 0.2 brings it to 279 K. Nanocrystalline samples exhibit a very wide effective temperature range in the magnetocaloric effect, up to 100 K. Bulk compounds exhibit a high and sharp peak in magnetic entropy change, up to 7 J/kgK at 4 T at Tc for x = 0.25. To compare the magnetocaloric performances of the studied compounds, both relative cooling power (RCP) and temperature-averaged entropy change (TEC) figures of merit were used. RCP is comparable for bulk polycrystalline and nano-sized samples of the same substitution level, while TEC shows a large difference between the two systems. The combination of bulk and nanocrystalline materials can contribute to the effectiveness and improvement of magnetocaloric materials.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070169
Authors: Shaogang Li Nachuan Ju Jinyang Wang Rongyu Zou Shaochuan Lin Minghui Yang
SiO2 has been extensively studied as a superior insulating layer for innovative Fe-based soft magnetic composites (SMCs). During the preparation process of SMCs, appropriate heat treatment can effectively alleviate internal stress, reduce dislocation density, decrease coercivity, and enhance permeability. Maintaining the uniformity and integrity of SiO2 insulating layers during heat treatment is a challenging task. Hence, it is crucial to explore the heat-treatment process and its effects on the magnetic properties of SMCs and their insulating layers. Herein, Fe–Si/SiO2 particles were prepared using chemical vapor deposition (CVD), and Fe–Si/SiO2 SMCs having a core–shell heterostructure were synthesized through hot-press sintering, and investigations were conducted into how heat-treatment temperature affected the microstructure of SMCs. This study thoroughly investigated the relationship between the evolution of SiO2 insulating layers and the magnetic properties. Additionally, the impact of the heat-treatment time on the magnetic properties of Fe-Si/SiO2 SMCs was evaluated. The results showed that in the temperature range of 823–923 K, the core–shell heterostructures grew more homogeneous and uniform. Concurrently, the stress and defects inside the Fe-Si/SiO2 SMCs were eliminated. When the temperature was raised over 973 K, the core–shell heterostructure was disrupted, and SiO2 began to disperse. After following a heat-treatment process (923 K) lasting up to 60 min, the resulting SMCs had high resistivity (1.04 mΩ·cm), the lowest hysteresis loss (P10 mt/100 kHz of 344.3 kW/m3), high saturation magnetization (191.2 emu/g). This study presents a new technique for producing SMCs using ceramic oxide as insulating layers. This study also includes a comprehensive analysis of the relationship between microstructure, magnetic properties, and heat treatment process parameters. These findings are crucial in expanding the potential applications of ceramic oxide.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070168
Authors: Evgeniy V. Korotaev Mikhail M. Syrokvashin Veronica S. Sulyaeva Irina Yu. Filatova
The magnetic properties (magnetic susceptibility, magnetic moment) and Weiss constant for lanthanum-doped CuCr1−xLaxS2 (x = 0; 0.005; 0.01; 0.015; 0.03) solid solutions were studied using static magnetochemistry at 80–750 K. The samples were characterized by both powder X-ray diffraction and energy-dispersive X-ray spectroscopy. It was shown that synthesized samples are single-phased up to x ≤ 0.01. The presence of the additional phase in the solid solutions with x > 0.015 caused deviation from the simple isovalent Cr3+→Ln3+ cationic substitution principle. It was found that magnetic susceptibility and the Weiss constant are significantly affected by both magnetic properties and lanthanum concentration for the solid solutions doped up to x = 0.01. The largest magnetic moment value of 3.88 µB was measured for the initial CuCrS2-matrix. The lowest value of 3.77 µB was measured for the CuCr0.99La0.01S2 solid solution. The lowest Weiss constant value of −147 K was observed for the initial matrix; the highest one was observed for CuCr0.99La0.01S2 (−139 K). The largest Seebeck coefficient value of 373 µV/K was measured for CuCr0.985La0.015S2 at 500 K; the obtained value was 3.3 times greater compared to the initial CuCrS2-matrix. The field dependence of the magnetic susceptibility allowed one to conclude the absence of ferromagnetic contributions in the total magnetic susceptibility of CuCr1−xLaxS2. The data on magnetic properties can be successfully utilized to investigate the limits of doping atom suitability and order–disorder phase transition temperature in CuCrS2-based solid solutions.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070167
Authors: Ekta Yadav Ketan S. Navale Gulloo L. Prajapati Krushna R. Mavani
Anti-site disorder, arising due to the similar size of Fe and Mo ions in Sr2FeMoO6 (SFMO) double perovskites, hampers spintronic applicability by deteriorating the magnetic response of this double perovskite system. A higher degree of anti-site disorder can also completely destroy the half-metallicity of the SFMO system. To study the effects of different process gas conditions on the anti-site disorder, we have prepared a series of SFMO thin films on SrTiO3 (001) single-crystal substrate using a pulsed laser deposition (PLD) technique. The films are grown either under vacuum or under N2/O2 partial gas pressures. The vacuum-grown SFMO film shows the maximum value of saturation magnetization (MS) and Curie temperature (TC), signaling the lowest anti-site disorder in this series. In other words, there is a long-range Fe/Mo-O-Mo/Fe ferrimagnetic exchange in the vacuum-grown thin film, thereby enhancing the magnetization. Further, all the SFMO films show a semiconducting state with a systematic increase in overall resistivity with the increased anti-site disorder. The electrical conduction mechanism is defined by the variable-range hopping model at low temperatures. Raman spectra show a weak Fano peak, suggesting the presence of electron–phonon coupling in SFMO thin films. These results show the significance of the process gas in causing anti-site disorder, tuning the degree of this disorder and therefore its influence on the structural, magnetic, electrical, and vibrational properties of SFMO thin films.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070166
Authors: Morkos A. Henen Natasia Paukovich Rytis Prekeris Beat Vögeli
Dynein, a homodimeric protein complex, plays a pivotal role in retrograde transportation along microtubules within cells. It consists of various subunits, among which the light intermediate chain (LIC) performs diverse functions, including cargo adaptor binding. In contrast to the vertebrate LIC homolog LIC1, LIC2 has received relatively limited characterization thus far, despite partially orthogonal functional roles. In this study, we present a near-to-complete backbone NMR chemical shift assignment of the C-terminal region of the light intermediate chain 2 of human dynein 1 (LIC2-C). We perform a comparative analysis of the secondary structure propensity of LIC2-C with the one previously reported for LIC1-C and show that the two transient helices in LIC1 that interact with motor adaptors are also present in LIC2.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070165
Authors: Andy D. Zapata-Escobar Alejandro F. Maldonado Jose L. Mendoza-Cortes Gustavo A. Aucar
In this article, we delve into the intricate behavior of electronic mechanisms underlying NMR magnetic shieldings σ in molecules containing heavy atoms, such as cadmium, platinum, and mercury. Specifically, we explore PtXn−2 (X = F, Cl, Br, I; n = 4, 6) and XCl2Te2Y2H6 (X = Cd, Hg; Y = N, P) molecular systems. It is known that the leading electronic mechanisms responsible for the relativistic effects on σ are well characterized by the linear response with elimination of small components model (LRESC). In this study, we present the results obtained from the innovative LRESC-Loc model, which offers the same outcomes as the LRESC model but employs localized molecular orbitals (LMOs) instead of canonical MOs. These LMOs provide a chemist’s representation of atomic core, lone pairs, and bonds. The whole set of electronic mechanisms responsible of the relativistic effects can be expressed in terms of both non-ligand-dependent and ligand-dependent contributions. We elucidate the electronic origins of trends and behaviors exhibited by these diverse mechanisms in the aforementioned molecular systems. In PtX4−2 molecules, the predominant relativistic mechanism is the well-established one-body spin–orbit (σSO(1)) mechanism, while the paramagnetic mass–velocity (σMv) and Darwin (σDw) contributing mechanisms also demand consideration. However, in PtX6−2 molecules, the σ(Mv/Dw) contribution surpasses that of the SO(1) mechanism, thus influencing the overall ligand-dependent contributions. As for complexes containing Cd and Hg, the ligand-dependent contributions exhibit similar magnitudes when nitrogen is substituted with phosphorus. The only discrepancy arises from the σSO(1) contribution, which changes sign between the two molecules due to the contribution of bond orbitals between the metal and tellurium atoms.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070164
Authors: Amit Pokhriyal Abyay Ghosh Smritijit Sen Haranath Ghosh
We present detailed first-principles density functional theory-based studies on RbRE2Fe4As4O2 (RE = Sm, Tb, Dy, Ho) hybrid 12442-type iron-based superconducting compounds with particular emphasis on competing magnetic interactions and their effect on possible magneto-structural coupling and electronic structure. The stripe antiferromagnetic (sAFM) pattern across the xy plane emerges as the most favorable spin configuration for all the four compounds, with close competition among the different magnetic orders along the z-axis. The structural parameters, including arsenic heights, Fe-As-Fe angle, and other relevant factors that influence superconducting Tc and properties, closely match the experimental values in stripe antiferromagnetic arrangement of Fe spins. Geometry optimization with inclusion of explicit magnetic ordering predicts a spin–lattice coupling for all the four compounds, where a weak magneto–structural transition, a tetragonal-to-orthorhombic structural transition, takes place in the relaxed stripe antiferromagnetic spin configuration. Absence of any experimental evidence of such structural transition is possibly an indication of nematic transition in RE-12442 compounds. As a result of structural distortion, the lattice contracts (expands) along the direction with parallel (anti-parallel) alignment of Fe spins. Introduction of stripe antiferromagnetic order in Fe sub-lattice reconstructs the low-energy band structure, which results in significantly reduced number of bands crossing the Fermi level. Moreover, the dispersion of bands and their orbital characteristics also are severely modified in the stripe antiferromagnetic phase similar to BaFe2As2. Calculations of exchange parameters were performed for all the four compounds. Exchange coupling along the anti-parallel alignment of Fe spins J1a is larger than that for the parallel aligned spins J1b. A crossover between the super-exchange-driven in-plane next-nearest-neighbor exchange coupling J2 and in-plane exchange coupling J1a due to lanthanide substitution was found. A large super-exchange-driven next-nearest-neighbor exchange interaction is justified using the construction of 32 maximally localized Wannier functions, where the nearest-neighbor Fe-As hopping amplitudes were found to be larger than the nearest- and the next-nearest-neighbor Fe-Fe hopping amplitudes. We compare the hopping parameters in the stripe antiferromagnetic pattern with non-magnetic configuration, and increased hopping amplitude was found along the anti-parallel spin alignment with more majority-spin electrons in Fe dxz and dxy but not in Fe dyz. On the other hand, the hopping amplitudes are increased in stripe antiferromagnetic phase along the parallel spin alignment with more majority-spin electrons in only Fe dyz. This difference in hopping amplitudes in the stripe antiferromagnetic order enables more isotropic hopping.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070163
Authors: Simona Gabriela Muntean Liliana Halip Maria Andreea Nistor Cornelia Păcurariu
The toxicity of metal ions on ecosystems has led to increasing amounts of research on their removal from wastewater. This paper presents the efficient application of a carbon magnetic nanocomposite as an adsorbent for the elimination of metal ions (copper, lead and zinc) from aqueous solutions. A Box–Behnken factorial design combined with the response surface methodology was conducted to investigate the effect and interactions of three variables on the pollutant removal process. Highly significant (p < 0.001) polynomial models were developed for each metal ion: the correlation coefficient was 0.99 for Cu(II) and Pb(II), and 0.96 for Zn(II) ion removal. The experimental data were in agreement and close to the theoretical results, which supports the applicability of the method. Working at the natural pH of the solutions, with a quantity of carbon magnetic nanocomposite of 1 g/L and a metal ions’ concentration of 10 mg/L, for 240 min, removal efficiencies greater than 75% were obtained. The kinetic study indicated that a combination of kinetic models pseudo-second order and intraparticle diffusion were applied appropriately for copper, lead and zinc ion adsorption on carbon magnetic nanocomposite. The maximum adsorption capacities determined from the Langmuir isotherm model were 81.36, 83.54 and 57.11 mg/g for copper, lead and zinc ions. The average removal efficiency for five adsorption–desorption cycles was 82.21% for Cu(II), 84.50% for Pb(II) and 72.68% for Zn(II). The high adsorption capacities of metal ions, in a short time, as well as the easy separation of the nanocomposite from the solution, support the applicability of the magnetic carbon nanocomposite for wastewater treatment.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070162
Authors: Sirine El Arni Mohammed Hadouchi Abderrazzak Assani Mohamed Saadi Mimoun El Marssi Abdelilah Lahmar Lahcen El Ammari
A novel pyrophosphate Na7Ni3Fe(P2O7)4 was synthesized in two distinct forms, single-crystal and powder. Single-crystal X-ray diffraction was used to determine the crystal structure, and powder X-ray diffraction and scanning electron microscopy were used to examine the purity and morphology of the elaborated powder. This phosphate crystallizes in the P1¯ space group of the triclinic system with a = 6.3677 (2) Å, b = 9.3316 (4) Å, c = 10.8478 (4) Å, α = 65.191 (1)°, β = 80.533 (1)° and γ = 73.042 (1)°. The crystal framework is assembled from the linkage of centro-symmetrical clusters Ni2(Ni/Fe)2P4O28. Each cluster consists of two (Fe1/Ni1)O6 octahedra, two Ni2O6 octahedra and two P2O7 units. The linkage of these clusters is provided by two other P2O7 units to generate a three-dimensional structure with distinct tunnels in the [100], [010] and [001] directions, housing the Na+ cations. The infrared and Raman analyses show the characteristic bands of the pyrophosphate anion P2O74−. Remarkably, the magnetic investigations revealed the coexistence of two magnetic transitions at ~29 K and ~4.5 K with dominating antiferromagnetic interactions.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9070161
Authors: Sofia Gonçalves Vivian Andrade Célia T. Sousa João P. Araújo João H. Belo Arlete Apolinário
Iron–cobalt (FeCo) alloys are highly desirable for their exceptional and adjustable physicochemical properties, particularly in the form of thin films. This study focuses on the growth of iron–cobalt (FeCo) alloy thin films using potentiostatic electrodeposition. The effects of applied voltage and FeCo stoichiometry on the morphology, structure, and magnetic properties of the films are investigated. The results indicate that the electrodeposition potential does not affect the overall stoichiometry or the structural and magnetic properties. However, it does impact film thickness and grain sizes. Higher applied potentials lead to thicker films with faster growth rates, as well as smoother and more homogeneous films with smaller grains. Films with different Fe:Co ratios (Fe90Co10, Fe50Co50, and Fe10Co90) are obtained, and their compositions have a direct impact on morphology, with the amount of Fe influencing film thickness, growth rates, and grain sizes. Increasing Fe content (50, 90%) leads to thicker films and smaller grains. Films with low Fe content (10%) exhibit a face-centered cubic (fcc) structural phase instead of the typical body-centered cubic (bcc) structure. All FeCo alloys display soft magnetic properties with characteristic coercivities, and the low Fe (10%) sample with the fcc structure exhibits the highest coercivity among all the samples. The nucleation and growth mechanisms are investigated using electrodeposition curves and the Scharifker and Hills model. Increasing the applied potential leads to thicker films and higher growth rates, with the nucleation mechanism identified as instantaneous nucleation in the diffusion-controlled regime.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9060160
Authors: Evelina P. Domashevskaya Sergey A. Ivkov Pavel V. Seredin Dmitry L. Goloshchapov Konstantin A. Barkov Stanislav V. Ryabtsev Yrii G. Segal Alexander V. Sitnikov Elena A. Ganshina
The aim of this work is a comprehensive study of the effect of variable atomic composition and structural-phase state of (CoFeZr)x(MgF2)100−x nanocomposites (NCs) on their nonlinear electronic and magnetic/magneto-optical properties. Micrometer-thick nanocomposite layers on the glass substrates were obtained by ion-beam sputtering of a composite target in the argon atmosphere in a wide range of compositions x = 9–51 at·%. The value of the resistive percolation threshold, xper = 34 at·%, determined from the concentration dependencies of the electrical resistance of NCs, coincides with the beginning of nucleation of metallic nanocrystals CoFeZr in MgF2 dielectric matrix. The absolute value of maximum magnetoresistance of NCs is 2.4% in a magnetic field of 5.5 kG at x = 25 at·%, up to the percolation threshold. Two maxima appear in the concentration dependencies of magneto-optical transversal Kerr effect, one of which, at x = 34 at·%, corresponds to the formation of CoFeZr alloy nanocrystals of a hexagonal structure, and the second one at x = 45 at·% corresponds to the phase transition of nanocrystals from a hexagonal to a cubic body-centered structure. The magnetic percolation threshold in (CoFeZr)x(MgF2)100−x system at xfm = 34 at·%, with the appearance of a hysteresis loop and a coercive force of Hc ≈ 8 Oe, coincides with the resistive percolation threshold xper = 34 at·%. Concentration dependence of the coercive force showed that at low contents of metallic alloy x < 30 at·%, NCs are superparamagnetic (Hc = 0). With an increase of the alloy content, in the region of magnetic and resistive percolation thresholds, NCs exhibit a magnetically soft ferromagnetic character and do not change it far beyond the percolation threshold, with the maximum value of the coercive force Hc < 30 Oe.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9060159
Authors: Tatiana G. Prokhorova Denis V. Korchagin Gennady V. Shilov Alexei I. Dmitriev Mikhail V. Zhidkov Eduard B. Yagubskii
The first mononuclear anionic erbium complex [Er(hfac)4]− (hfac = hexafluoroacetylacetone) with an organic ammonium cation [(CH3)4N+] as the counterion was synthesized and structurally and magnetically characterized. The coordination geometries around the Er ions are square antiprisms with pseudo-D4d symmetry. The complex shows distinct field-induced slow magnetization relaxation, which is described by a combination of Orbach (Ueff/kB~28.54(8) K.) and direct mechanisms. Quantum chemical calculations were performed to analyze the magnetic properties of the complex under consideration.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9060158
Authors: Pietro Micaletti Federico Montoncello
We present a micromagnetic investigation of the spin dynamics at remanence (zero applied field) in a periodic square artificial spin ice (ASI) prepared four different microstates (i.e., with zero, two or four magnetic charges at the vertex). The ASI elements consist of permalloy elliptical dots with a fixed long axis, and a variable width and interdot separation. For each vertex configuration, we compute the equilibrium ground state at zero applied field by relaxing a previously set magnetic configuration (microstate). After the excitation of such ground state, we perform a Fourier analysis obtaining frequency spectra and space phase profiles. We discuss the behavior of the spectra in changing the system’s microstate and geometry, with reference to the spin mode space profiles, magnetization configuration, and effective internal field. Our results draw a correlation between ASI macrospin orientation at vertex and a few important dynamic properties like a phase-shift in the mode profiles or the frequency gap between the edge and fundamental modes. We suggest a few specific experiments to validate of our predictions, as well as applications in the field of interferometric magnonic devices. We believe that our results can help, from the fabrication stage, in tailoring the appropriate ASI geometry for specific application purposes.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9060157
Authors: Hajer Tlili Anis Elaoud Nedra Asses Karima Horchani-Naifer Mounir Ferhi Gerardo F. Goya Jesús Antonio Fuentes-García
Many of the current strategies for removing pollutants from water are based on nanomaterials and nanotechnology. Lower values of Biological Oxygen Demand (BOD5) and Chemical Oxygen Demand (COD) in water results in reduction in the amount of oxidizable pollutants. We present a study on the reduction of COD and BOD5 in water from Wadi El Bey River (Tunisia), using magnetite nanoparticles (MNPs) and magnetic fields. The COD and BOD5 removal reached values higher than 50% after 60 min, with optimum efficiency at pH values of ≈8 and for MNPs concentrations of 1 g/L. The use of a permanent magnetic field (0.33 T) showed an increase of COD and BOD5 removal from 61% to 76% and from 63% to 78%, respectively. This enhancement is discussed in terms of the MNPs coagulation induced by the magnetic field and the adsorption of ionic species onto the MNPs surface due to Fe3O4 affinity.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9060156
Authors: Nilima Maji Harmanjit Singh Dosanjh
Ferrites have excellent magnetic, electric, and optical properties that make them an indispensable choice of material for a plethora of applications, such as in various biomedical fields, magneto–optical displays, rechargeable lithium batteries, microwave devices, internet technology, transformer cores, humidity sensors, high-frequency media, magnetic recordings, solar energy devices, and magnetic fluids. Recently, magnetically recoverable nanocatalysts are one of the most prominent fields of research as they can act both as homogeneous and heterogenous catalysts. Nano-ferrites provide a large surface area for organic groups to anchor, increase the product and decrease reaction time, providing a cost-effective method of transformation. Various organic reactions were reported, such as the photocatalytic decomposition of a different dye, alkylation, dehydrogenation, oxidation, C–C coupling, etc., with nano-ferrites as a catalyst. Metal-doped ferrites with Co, Ni, Mn, Cu, and Zn, along with the metal ferrites doped with Mn, Cr, Cd, Ag, Au, Pt, Pd, or lanthanides and surface modified with silica and titania, are used as catalysts in various organic reactions. Metal ferrites (MFe2O4) act as a Lewis acid and increase the electrophilicity of specific groups of the reactants by accepting electrons in order to form covalent bonds. Ferrite nanocatalysts are easily recoverable by applying an external magnetic field for their reuse without significantly losing their catalytic activities. The use of different metal ferrites in different organic transformations reduces the catalyst overloading and, at the same time, reduces the use of harmful solvents and the production of poisonous byproducts, hence, serving as a green method of chemical synthesis. This review provides insight into the application of different ferrites as magnetically recoverable nanocatalysts in different organic reactions and transformations.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9060155
Authors: Walter Cañón-Mancisidor Patricio Hermosilla-Ibáñez Evgenia Spodine Verónica Paredes-García Carlos J. Gómez-García Diego Venegas-Yazigi
The synthesis and structural characterization of a new triangular Cu3–μ3OH pyrazolato complex of formula, [Cu3(μ3−OH)(pz)3(Hpz)3][BF4]2 (1−Cu3), Hpz = pyrazole, is presented. The triangular unit forms a quasi-isosceles triangle with Cu–Cu distances of 3.3739(9), 3.3571(9), and 3.370(1) Å. This complex is isostructural to the hexanuclear complex [Cu3(μ3−OH)(pz)3(Hpz)3](ClO4)2]2 (QOPJIP). A comparative structural analysis with other reported triangular Cu3–μ3OH pyrazolato complexes has been carried out, showing that, depending on the pyrazolato derivative, an auxiliary ligand or counter-anion can affect the nuclearity and/or the dimensionality of the system. The magnetic properties of 1−Cu3 are analyzed using experimental data and DFT calculation. A detailed analysis was performed on the magnetic properties, comparing experimental and theoretical data of other molecular triangular Cu3–μ3OH complexes, showing that the displacement of the μ3−OH− from the Cu3 plane, together with the type of organic ligands, influences the nature of the magnetic exchange interaction between the spin-carrier centers, since it affects the overlap of the magnetic orbitals involved in the exchange pathways. Finally, a detailed comparison of the magnetic properties of 1−Cu3 and QOPJIP was carried out, which allowed us to understand the differences in their magnetic properties.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9060154
Authors: Debpriyo Goswami Shanti Gopal Patra Debashis Ray
A selection of dimeric Cu(II) complexes with bidentate N,N′ ligands with the general formula [Cu(L)(X)(μ-OH)]2·nH2O and [Cu(L)(μ-OH)]2X2·nH2O were magneto-structurally analyzed using the Density Functional Theory (DFT). A Broken Symmetry-Density Functional Theory (BS-DFT) study was undertaken for these complexes with relevant decomposition schemes that gave insight into the effect of the nature of the ligand and coordination environment on the DFT-predicted coupling constants (J). The impact of the spin population, which correlates well with the Cu-O-Cu bridging angles and the calculated coupling constant (J) values, was studied. The models were further refined using a complete active space self-consistent field (CASSCF) while expanding the active space from 2 orbitals 2 electrons (2,2) to 10 orbitals 18 electrons (18,10). These models were approximated using multireference methods (n-electron valence state perturbation theory and difference dedicated configuration interaction), and a better approximation of J values was found as expected. Orbitals involved in the superexchange pathway were also visualized.
]]>Magnetochemistry doi: 10.3390/magnetochemistry9060153
Authors: Ryuhei Oka Keishi Ohara Kensuke Konishi Ichiro Yamane Toshihiro Shimada Toshio Naito
Materials containing Dirac fermions (DFs) have been actively researched because they often alter electrical and magnetic properties in an unprecedented manner. Although many studies have suggested the transformation between standard fermions (SFs) and DFs, the non-availability of appropriate samples has prevented the observation of the transformation process. We observed the interconversion process of DFs and SFs using organic charge-transfer (CT) salts. The samples are unique in that the constituents (the donor D and acceptor A species) are particularly close to each other in energy, leading to the temperature- and D-A-combination-sensitive CT interactions in the solid states. The three-dimensional weak D–A CT interactions in low-symmetry crystals induced the continuous reshaping of flat-bottomed bands into Dirac cones with decreasing temperature; this is a characteristic shape of bands that converts the behavior of SFs into that of DFs. Based on the first-principles band structures supported by the observed electronic properties, round-apex-Dirac-cone-like features appear and disappear with temperature variation. These band-structure snapshots are expected to add further detailed understanding to the related research fields.
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