The relationship between the chemical purity of one-size particles and microwave properties in ferromagnetic materials is not clearly studied. Ferromagnetic nanostructured iron powders were synthesized from iron nitrate solution using ultrasonic spray-pyrolysis and then reduced in H2 flow at 350, 400, 450, and 500 °C. A rise in the concentration of solutions of a precursor from 10 to 20 wt. % led to an increase in mean particle size. The interrelationship was studied between chemical composition and the microwave dispersion of the powders obtained. An increase in the temperature of reduction changes the chemical composition and increases the amplitude of complex microwave permeability, which was studied using solid-state physics methods (XRD, STA, SEM, and VNA). It was found that annealing at 400 °C is the optimal treatment that allows the production of iron powders, consisting of about 90% of α-Fe phase, possessing a particle surface with low roughness and porosity, and demonstrating intense microwave absorption. Annealing at a higher temperature (500 °C) causes an even higher increase in permeability but leads to the destruction of nanostructured spheres into smaller particles due to grain growth. This destruction causes an abrupt increase in permittivity and therefore significantly reduces potential applications of the product. The insight into chemical–magnetic relationships of these materials enhances the data for design applications in magnetic field sensing.
A theoretical and numerical investigation of the quality criteria for radar absorbing coatings (RACs) has been conducted. Simple analytical expressions for the minimum of the reflection coefficient of a homogeneous absorbing layer have been obtained. It is shown that this value is not a correct characteristic of radar absorption. To describe the quality of RACs, it is necessary to use either the relative bandwidth of its operating waveband or the ratio of the operating waveband to the layer’s thickness. The former of these quantities may be useful when it is important to achieve a high broadband absorbency, while the latter is useful for achieving a small thickness of an absorber.
Thick dielectric SiO2 shells on the surface of iron particles enhance the thermal and electrodynamic parameters of the iron. A technique to deposit thick, 500-nm, SiO2 shell to the surface of carbonyl iron (CI) particles was developed. The method consists of repeated deposition of SiO2 particles with air drying between iterations. This method allows to obtain thick dielectric shells up to 475 nm on individual CI particles. The paper shows that a thick SiO2 protective layer reduces the permittivity of the ‘Fe-SiO2—paraffin’ composite in accordance with the Maxwell Garnett medium theory. The protective shell increases the thermal stability of iron, when heated in air, by shifting the transition temperature to the higher oxide. The particle size, the thickness of the SiO2 shells, and the elemental analysis of the samples were studied using a scanning electron microscope. A coaxial waveguide and the Nicholson–Ross technique were used to measure microwave permeability and permittivity of the samples. A vibrating-sample magnetometer (VSM) was used to measure the magnetostatic data. A synchronous thermal analysis was applied to measure the thermal stability of the coated iron particles. The developed samples can be applied for electromagnetic compatibility problems, as well as the active material for various types of sensors.
A composite containing about 30% volume of micrometer-size powder of gadolinium in paraffin wax is synthesized mechanochemically. The composite permittivity and permeability are measured within the frequency range from 0.01 to 15 GHz and the temperature range from ~0 °C to 35 °C. The permittivity is constant within the measured ranges. Curie temperature of the composite is close to 15.5 °C, the phase transition is shown to take place within a temperature range about ±10 °C. The effect of temperature deviation from Curie point on reflection and transmission of a composite layer filled with Gd powder is studied experimentally and via simulation. Constitutive parameters of the composite are measured in cooled coaxial lines applying reflection-transmission and open-circuit-short-circuit techniques, and the measured low-frequency permeability is in agreement with the values retrieved from the published magnetization curves. The effect of temperature on permeability spectrum of the composite is described in terms of cluster magnetization model based on the Wiener mixing formula. The model is applied to design a microwave screen with variable attenuation; the reflectivity attenuation of 4.5 mm-thick screen increases from about −2 dB to −20 dB at 3.5 GHz if the temperature decreases from 25 °C to 5 °C.
Hollow ferromagnetic powders of iron were obtained by means of ultrasonic spray pyrolysis. A variation in the conditions of the synthesis allows for the adjustment of the mean size of the hollow iron particles. Iron powders were obtained by this technique, starting from the aqueous solution of iron nitrate of two different concentrations: 10 and 20 wt.%. This was followed by a reduction in hydrogen. An increase in the concentration of the solution increased the mean particle size from 0.6 to 1.0 microns and widened particle size distribution, but still produced hollow particles. Larger particles appeared problematic for the reduction, although admixture of iron oxides did not decrease the microwave permeability of the material. The paraffin wax-based composites filled with obtained powders demonstrated broadband magnetic loss with a complex structure for lesser particles, and single-peak absorption for particles of 1 micron. Potential applications are 5G technology, electromagnetic compatibility designs, and magnetic field sensing.
Morphology, chemical composition, crystal structure, and magnetic circular dichroism of ZnO films doped simultaneously with Co and Al (CAZO) have been studied. The films were deposited on glass substrates by the RF magnetron sputtering of the Zn0.93Co0.05Al0.02O target. Low hydrogen concentrations of 1–4% were used in mixed Ar + H2 atmosphere together with high enough substrate temperature of 450 °C. A tendency to a decrease in the Zn amount and an increase in the relative Co and Al content in the films has been revealed in the presence of hydrogen in the atmosphere. The structural data of the studied films correlate well with those for high-hydrogenated (20–50% H2) CAZO films deposited under the same conditions and studied earlier. The new data indicate the prospect of obtaining ferromagnetic samples based on ZnO without any secondary phases.
This work is devoted to the study of magnetic Fe3O4 nanoparticles doubly coated with carbon. First, Fe3O4@C nanoparticles were synthesized by thermal decomposition. Then these synthesized nanoparticles, 20–30 nm in size were processed in a solution of glucose at 200 °C during 12 h, which led to an unexpected phenomenon—the nanoparticles self-assembled into large conglomerates of a regular shape of about 300 nm in size. The morphology and features of the magnetic properties of the obtained hybrid nanoparticles were characterized by transmission electron microscopy, differential thermo-gravimetric analysis, vibrating sample magnetometer, magnetic circular dichroism and Mössbauer spectroscopy. It was shown that the magnetic core of Fe3O4@C nanoparticles was nano-crystalline, corresponding to the Fe3O4 phase. The Fe3O4@C@C nanoparticles presumably contain Fe3O4 phase (80%) with admixture of maghemite (20%), the thickness of the carbon shell in the first case was of about 2–4 nm. The formation of very large nanoparticle conglomerates with a linear size up to 300 nm and of the same regular shape is a remarkable peculiarity of the Fe3O4@C@C nanoparticles. Adsorption of organic dyes from water by the studied nanoparticles was also studied. The best candidates for the removal of dyes were Fe3O4@C@C nanoparticles. The kinetic data showed that the adsorption processes were associated with the pseudo-second order mechanism for cationic dye methylene blue (MB) and anionic dye Congo red (CR). The equilibrium data were more consistent with the Langmuir isotherm and were perfectly described by the Langmuir–Freundlich model.
Composite materials filled with ferromagnetic inclusions are useful in the development of various microwave devices. The performance of such devices is determined both by material properties (such as the saturation magnetization and the permeability) and by the demagnetization effects. The paper is devoted to the study of the demagnetization effect on the permeability measurements of composites under external magnetic bias. The microwave permeability of composites filled with flake sendust (Fe-Si-Al alloy) particles is measured as a function of frequency and the external magnetic field. The measurements are carried out by the Nicolson–Ross–Weir technique in a 7/3 coaxial line in the frequency range of 0.1 to 20 GHz by a vector network analyzer. It is found that the magnetic loss peak is split under external fields of more than 1.5 kOe. The main aim of this paper is to study the causes of this splitting and to interpret the observed magnetic loss peaks. To study this effect, the samples of various thicknesses and the samples with isotropic and anisotropic orientations of particles are measured. The particles in the anisotropic samples are oriented by a strong uniform magnetic field. At a small fraction of inclusions, the permanent magnetic field is demagnetized on the individual particles rather than the whole sample. The splitting of the magnetic loss peak of the isotropic sample is caused by different orientations of particles in the sample. At a high fraction of inclusions, the permanent magnetic field is demagnetized on the whole sample and the magnetic loss peak of the isotropic sample is not split. The saturation magnetization of the material is found by measurements under the external magnetic field of the anisotropic sample.
The frequency dependencies of microwave permeability of composites filled with flake-shaped sendust (Fe-Al-Si alloy) powder particles are measured. A technique for determining the physical mechanisms resulting in the appearance of magnetic loss peaks is proposed. The technique consists in analysis of the data on microwave permeability obtained under external magnetic field. It is shown that the mixing rule, which correctly retrieves the intrinsic permeability in the absence of the external field, is not valid under magnetic bias. Based on the measured data, the physical mechanisms leading to the appearance of loss peaks are determined, and the invalidity of mixing rules under magnetic bias is explained. It is shown that the main peak of magnetic loss is attributed to the Polder-Smith modes. An increase in the external field leads to vanishing of the domain structure and to an increase in the interaction between powder particles. The permeability under bias should be described by mixing rules that take into account the interaction between inclusions. The found frequencies of the Polder-Smith modes are in good agreement with the permeability data.
Fe3O4@SiO2 core-shell nanoparticles (NPs) were synthesized with the co-precipitation method and functionalized with NH2 amino-groups. The nanoparticles were characterized by X-ray, FT-IR spectroscopy, transmission electron microscopy, selected area electron diffraction, and vibrating sample magnetometry. The magnetic core of all the nanoparticles was shown to be nanocrystalline with the crystal parameters corresponding only to the Fe3O4 phase covered with a homogeneous amorphous silica (SiO2) shell of about 6 nm in thickness. The FT-IR spectra confirmed the appearance of chemical bonds at amino functionalization. The magnetic measurements revealed unusually high saturation magnetization of the initial Fe3O4 nanoparticles, which was presumably associated with the deviations in the Fe ion distribution between the tetrahedral and octahedral positions in the nanocrystals as compared to the bulk stoichiometric magnetite. The fluorescent spectrum of eosin Y-doped NPs dispersed in water solution was obtained and a red shift and line broadening (in comparison with the dye molecules being free in water) were revealed and explained. Most attention was paid to the adsorption properties of the nanoparticles with respect to three dyes: methylene blue, Congo red, and eosin Y. The kinetic data showed that the adsorption processes were associated with the pseudo-second order mechanism for all three dyes. The equilibrium data were more compatible with the Langmuir isotherm and the maximum adsorption capacity was reached for Congo red.
(Co + Al)-doped ZnO films have been synthesized by the RF magnetron sputtering. Films of this composition have first been obtained in mixed atmosphere of Ar + H-2. High hydrogen concentration of 20-50% has been used together with high enough substrate temperature of 450 degrees C. The used technological conditions affected the morphology, chemical composition, optical, electric, and magnetic properties of the films to an even more than in the case of Co-doped ZnO films synthesized under the same conditions and studied earlier. The films exhibit ferromagnetic behavior at room temperature with much greater magnetization and magneto-optical activity compared to the Co-doped films. At the same time, the hydrogenated films show an increase in electric conductivity in comparison with samples synthesized in the atmosphere of Ar + O-2. The magnetic nature of the hydrogenated films has been associated with the defect-related mechanism.
Protective SiO2 coating deposited to iron microparticles is highly demanded both for the chemical and magnetic performance of the latter. Hydrolysis of tetraethoxysilane is the crucial method for SiO2 deposition from a solution. The capabilities of this technique have not been thoroughly studied yet. Here, two factors were tested to affect the chemical composition and the thickness of the SiO2 shell. It was found that an increase in the hydrolysis reaction time thickened the SiO2 shell from 100 to 200 nm. Moreover, a decrease in the acidity of the reaction mixture not only thickened the shell but also varied the chemical composition from SiO3.0 to SiO8.6. The thickness and composition of the dielectric layer were studied by scanning electron microscopy and energy-dispersive X-ray analysis. Microwave permeability and permittivity of the SiO2-coated iron particles mixed with a paraffin wax matrix were measured by the coaxial line technique. An increase in thickness of the silica layer decreased the real quasi-static permittivity. The changes observed were shown to agree with the Maxwell Garnett effective medium theory. The new method developed to fine-tune the chemical properties of the protective SiO2 shell may be helpful for new magnetic biosensor designs as it allows for biocompatibility adjustment.
An approach to a design of tunable frequency‐selective surfaces (FSSs) for radio frequency (RF) domain based on vanadium dioxide (VO2) thin films is proposed. As an example, a thermally tunable annular slot FSS with integrated VO2 switchable elements for C‐band of the RF domain is described. Switching is based on abrupt change of conductivity of the VO2 film, initiated by heating from room temperature to a temperature of the metal–insulator phase transition of 44 °C. A tuning mechanism of the FSS allows continuous change of frequency response from room temperature state, where the FSS acts as a band‐pass filter, to high‐temperature state, where the FSS works as a reflector. In the process of tuning, a reflection coefficient at a central frequency of the filter can be increased from −26.4 dB up to −2.2 dB. The proposed approach can be used for the design of tunable FSS for applications that allow thermal control of the frequency response.
An approach to a design of tunable frequency-selective surfaces (FSSs) for radio frequency (RF) domain based on vanadium dioxide (VO2) thin films is proposed. As an example, a thermally tunable annular slot FSS with integrated VO(2)switchable elements for C-band of the RF domain is described. Switching is based on abrupt change of conductivity of the VO(2)film, initiated by heating from room temperature to a temperature of the metal-insulator phase transition of 44 degrees C. A tuning mechanism of the FSS allows continuous change of frequency response from room temperature state, where the FSS acts as a band-pass filter, to high-temperature state, where the FSS works as a reflector. In the process of tuning, a reflection coefficient at a central frequency of the filter can be increased from -26.4 dB up to -2.2 dB. The proposed approach can be used for the design of tunable FSS for applications that allow thermal control of the frequency response.
The effect of Ti substitution on the microwave and magnetostatic properties of nanostructured hexagonal BaFe12−xTixO19 ferrite composites is studied. The microwave permeability is measured in the frequency range of 0.1–22 GHz by a coaxial technique. An analysis of the magnetostatic data is made by the law of approach to saturation. The ferrimagnetic resonance frequencies calculated from the magnetostatic data are consistent with those obtained from the microwave measurements. The natural ferrimagnetic resonance frequencies are located in the frequency range of 15 to 22 GHz, depending on the substitution level x. An increase in the amount of substitution elements results in a low-frequency shift of the ferrimagnetic resonance frequency for samples with x < 1. With x rising from 1 to 2.5, the resonance frequency increases. The results of the study demonstrate that the tailored optimization of the nano-structure of a functional material is a robust tool to fine-tune its microwave magnetic properties. The ferrites under study are promising materials to be applied as functional coatings intended to control electromagnetic interference in microwave devices.
The use of a coaxial air-filled line as a test fixture for measuring complex permittivity and permeability often shows odd resonance-like behavior of material parameters as functions of frequency. This effect is typically either ascribed to the half-wavelength resonance at the sample length, or erroneously misinterpreted as intrinsic resonance behavior of the material. However, as is shown in this paper, such behavior can be attributed to excitation of the higher-order modes on the surface of the sample resulting in resonance absorption of electromagnetic energy in the test fixture. Herein, analytical, numerical, and experimental results show that there can actually be a significant impact of higher-order modes in a coaxial line on the extracted constitutive material parameters of samples.
Measurement of the frequency dependence of the permeability under magnetic bias is proposed as a new method for studying the microwave magnetic properties of magnetic materials. The samples under study are either rolls of thin ferromagnetic films or the composites filled with sendust particles. It is shown that the permeability measured under external magnetic bias depends on sample thickness. The correct interpretation of the measured data is possible only when sample demagnetization is accounted for. The values of the anisotropy field and the saturation magnetization of thin nitrogen doped iron films and flake-shaped sendust particles are calculated considering demagnetization of the washer-shaped sample.
Iron powder particles were coated with a thin SiO2 shell for protection of corrosion. Dynamic magnetic behavior of the as-synthesized material was studied in comparison with uncoated metal in terms of frequency dispersion of the microwave permeability and permittivity. A uniform 100-nm SiO2 shell provides durable corrosion resistance to a 4.5-μm carbonyl iron powder. The shell was deposited through tetraethyl orthosilicate hydrolysis of technical grade chemicals. It was shown that the shell did not influence the magnetic properties of the iron powder. Electron microscopy, particle size analysis, and γ-resonance spectroscopy were applied in the study. The deposited SiO2 decreased the microwave permeability value and prevented percolation conductivity in a composite with a paraffin wax dielectric matrix.
A new method of studying microwave magnetic properties of metal particles and films is developed. The method is based on measurements with swept frequency under magnetic bias in a coaxial line. Application of the technique is illustrated by the data obtained for two types of samples, washer-shaped rolls of thin ferromagnetic films and composites filled with flake Sendust particles. The treatment of the measured data is performed with an account for sample demagnetization and anisotropy. The values of the anisotropy field and the saturation magnetization of thin iron films are calculated considering demagnetization of the sample. Because of the anisotropy of the composite samples, permeability depends slightly on the length of samples, and the saturation magnetization and the anisotropy field cannot be determined. (C) 2017 Elsevier B.V. All rights reserved.
The paper considers the application of mixing rules to the analysis of the microwave effective material parameters, the permittivity and permeability, of composites. It is suggested to perform the analysis in terms of the normalized inverse susceptibility defined as the volume fraction of inclusions divided by the effective dielectric or magnetic susceptibility of the composite. This allows the volume fraction dependence of the effective material parameters to be represented in a form that is convenient for the analysis, so that distinguishing features of the dependence become more pronounced and helpful for understanding the factors that affect the effective properties of the composite. The proposed approach is illustrated by the analysis of the measured data on the microwave material parameters of composites comprising Sendust powder with either spherical or platelet powder particles, and Permalloy powders with particles of the stone-like shape. The microwave material parameters are measured with paraffin-based composite samples in the 7/3-mm coaxial air-filled waveguide by the Nicolson‒Ross‒Weir technique. It is shown that for Sendust particles, the interaction between inclusions is low. For the composites comprising spherical particles, the Maxwell Garnet mixing rule is a good approximation of the volume fraction dependence of microwave permeability. For the platelet powder particles, the magnetic performance is governed by the Wiener mixing rule. For composites filled with Permalloy powder, the contribution of the interaction between inclusions to the effective permeability is essential. Therefore, the suggested approach allows the type of mixing rule suitable for description of material parameters of a given composite to be determined.