Preparation and application of core–shell Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/polythiophene nanoparticles

The Fe₃O₄/polythiophene nanoparticles, possessing core–shell structure, were prepared by two-step method. In the first step, the Fe₃O₄ particles were synthesized via co-precipitation of FeCl₃ and FeSO₄, using the NH₃·H₂O and N₂H₄·H₂O as precipitant system. In the second step, the thiophene adsorbed and polymerized on the surface of the Fe₃O₄ in the solvent of chloroform. Raman, FTIR, EDS, XRD, TEM, Zeta potential measurement and TG-SDTA were employed to characterize the composition and structure of the products. The results showed that the Fe₃O₄/polythiophene nanoparticles were successfully synthesized with good dispersion and stable core–shell structure, provided with average particle size of approximately 20 nm, in which the diameter of Fe₃O₄ core was approximately 14 nm and the thickness of polythiophene shell was approximately 3–4 nm. Then, the nanoparticles were added into alkyd varnish to prepare a composite coating. The neutral salt spray test, paraffin control test and mechanical test were carried out to identify the properties of the composite coating. It was found that the composite coating had good performances of anticorrosion and paraffin controlling when the mass fraction of the nanoparticles was 0.8–1 wt% in alkyd varnish. As a multifunctional material, the Fe₃O₄/polythiophene nanoparticles can be used in the internal coating of pipeline and have great potential application in crude oil pipeline transportation.     

High-yield fabrication of W<Subscript>18</Subscript>O<Subscript>49</Subscript>@TiO<Subscript>2</Subscript> core–shell nanoparticles: microstructures and optical-thermal properties

In the present study, high-yield W₁₈O₄₉@TiO₂ core–shell nanoparticles were prepared by modified plasma arc gas condensation without any catalysts or substrates. All the as-prepared samples were characterized by FEG-SEM, XRD, FEG-STEM, and HAADF analytic techniques. The results of the structural analysis show that the as-prepared nanoparticles presenting a core–shell morphology with an average diameter of 43.5 ± 8.0 nm were composed of non-stoichiometric tungsten oxide (W₁₈O₄₉ phase) as the core (20–40 nm) and rutile-phase TiO₂ as the shell with non-uniform thickness (10–20 nm). For the optical properties of the as-prepared W₁₈O₄₉@TiO₂ core–shell nanoparticles, Raman spectroscopy and photoluminescence (PL) spectra were used. Compared with pure TiO₂ and W₁₈O₄₉ nanocrystals, the experimental results reveal that the defects in the lattice between the core and shell layers induced the board and shifted peaks in Raman spectra. Also, W₁₈O₄₉@TiO₂ core–shell nanoparticles exhibited green emission at 483 nm wavelength observed in PL spectrum. Thermal gravimetric analyzer (TGA) results indicate that the TiO₂ shell served a stable layer and prevented further oxidation from the atmosphere of the W₁₈O₄₉ core, thereby improving the thermal stability of W₁₈O₄₉ nanoparticles.     

Size-controllable synthesis of functional heterostructured TiO<Subscript>2</Subscript>–WO<Subscript>3</Subscript> core–shell nanoparticles

Mono and bicomponent TiO₂ and WO₃ nanoparticles were synthesized inside Vycor^® glass pores, by cycles of impregnation of the glass with the respective oxide precursor followed by its thermal decomposition. The impregnation-decomposition cycle (IDC) methodology promoted a linear mass increase of the glass matrix, and allowed tuning the nanoparticle size. X-ray diffraction and Raman spectroscopy data allowed identifying the formation of TiO₂ as anatase phase, while WO₃ is a mixture of the γ-WO₃ (monoclinic) and δ-WO₃ (triclinic) phases. High resolution transmission electron microscopy images revealed that for 3, 5, and 7 IDC, the TiO₂ nanoparticles obtained presented average diameters of 3.4, 4.3, and 5.1 nm, and the WO₃ nanoparticles have 2.9, 4.6, and 5.7 nm sizes. These TiO₂ and WO₃ monocomponent nanoparticles were submitted to IDC with the other oxide precursor, resulting in bicomponent nanoparticles. The broadening and shift of the Raman bands related to titanium and tungsten oxides suggest the formation of hetero-structure core–shell nanoparticles with tunable core sizes and shell thicknesses.     

Controlled flame synthesis of αFe<Subscript>2</Subscript>O<Subscript>3</Subscript> and Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles: effect of flame configuration,flame temperature,and additive loading

Superparamagnetic iron oxide nanoparticles are used in diverse applications, including optical magnetic recording, catalysts, gas sensors, targeted drug delivery, magnetic resonance imaging, and hyperthermic malignant cell therapy. Combustion synthesis of nanoparticles has significant advantages, including improved nanoparticle property control and commercial production rate capability with minimal post-processing. In the current study, superparamagnetic iron oxide nanoparticles were produced by flame synthesis using a coflow flame. The effect of flame configuration (diffusion and inverse diffusion), flame temperature, and additive loading on the final iron oxide nanoparticle morphology, elemental composition, and particle size were analyzed by transmission electron microscopy (TEM), high-resolution TEM (HR-TEM), energy dispersive spectroscopy (EDS), and Raman spectroscopy. The synthesized nanoparticles were primarily composed of two well known forms of iron oxide, namely hematite αFe₂O₃ and magnetite Fe₃O₄. We found that the synthesized nanoparticles were smaller (6–12 nm) for an inverse diffusion flame as compared to a diffusion flame configuration (50–60 nm) when CH₄, O₂, Ar, and N₂ gas flow rates were kept constant. In order to investigate the effect of flame temperature, CH₄, O₂, Ar gas flow rates were kept constant, and N₂ gas was added as a coolant to the system. TEM analysis of iron oxide nanoparticles synthesized using an inverse diffusion flame configuration with N₂ cooling demonstrated that particles no larger than 50–60 nm in diameter can be grown, indicating that nanoparticles did not coalesce in the cooler flame. Raman spectroscopy showed that these nanoparticles were primarily magnetite, as opposed to the primarily hematite nanoparticles produced in the hot flame configuration. In order to understand the effect of additive loading on iron oxide nanoparticle morphology, an Ar stream carrying titanium-tetra-isopropoxide (TTIP) was flowed through the outer annulus along with the CH₄ in the inverse diffusion flame configuration. When particles were synthesized in the presence of the TTIP additive, larger monodispersed individual particles (50–90 nm) were synthesized as observed by TEM. In this article, we show that iron oxide nanoparticles of varied morphology, composition, and size can be synthesized and controlled by varying flame configuration, flame temperature, and additive loading.     

Features of the structure and properties of β-FeSi<Subscript>2</Subscript> nanofilms and a β-FeSi<Subscript>2</Subscript>/Si interface

The electronic, geometric, and magnetic structure of nanofilms of the β phase of iron disilicide FeSi₂ with the (001), (100), and (010) surfaces have been simulated through density functional calculations. A substantial reconstruction of the (001) surface terminated with silicon atoms has been observed, which was accompanied by an increase in the surface symmetry and appearance of “squares” of silicon atoms. Analysis of the electron density of states (DOS) and spin DOS projected on the contributions of layers of atoms (LSDOS) indicates that all plates have metallic properties. The main contribution near the Fermi level comes from the surface iron layers and it decreases rapidly with an increase in the distance from the surface of the plate. Analysis of the calculated effective magnetic moments of atoms shows that the surface layers in the plates have a significant magnetic moment, in particular, iron layers on the (001) surface (1.89 μ_B/atom). The moments of atoms decrease rapidly with an increase in their distance from the surface. The electron and geometric regions of a (001)Si/FeSi₂ interface have been studied. Analysis of the LSDOS shows that the surface conducting state mainly determined by the contribution from the near-surface silicide layers is implemented in this region. The possibility of the formation of the perfect and sharp Si/FeSi₂ interface has been demonstrated.     

Luminescence properties of Nd<Superscript>3+</Superscript>-doped Y<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles in organic media

Nd³⁺-doped yttrium oxide nanoparticles (Y₂O₃:Nd) with cubic phase were obtained successfully by a glycine-nitrate solution combustion method. The results of Fourier transform infrared spectra (FTIR) showed that the –OH groups residing on the nanoparticles surfaces were reduced effectively by modifying with capping agent. The modified Y₂O₃:Nd nanoparticles displayed good monodispersity and excellent luminescence in N,N-dimethylformamide (DMF) solvent. Some optical parameters were calculated by Judd–Ofelt analysis based on absorption and fluorescence spectra. A relative large stimulated emission cross section, 1.7×10⁻²⁰ cm², of the ⁴F_3/2→⁴I_11/2 transition was calculated. Theses results show that the modified Y₂O₃:Nd nanoparticles display good luminescence behavior in organic media.     

Terahertz spectroscopy of central and soft phonon modes in LuFe<Subscript>2</Subscript>O<Subscript>4</Subscript>

The terahertz dielectric response of LuFe₂O₄ is investigated by terahertz time-domain spectroscopy over a temperature range of 6–290 K. It is revealed that besides the central mode associated with the charge-ordered state, a soft TO₁ mode at below ∼240 K is identified indicating the existence of displacing ferroelectricity, in addition to the charge-ordering-induced ferroelectricity at below 320 K. The anomaly of the soft mode at ∼180 K reflects the magnetoelectric correlation between the soft TO₁ mode and the spin/charge fluctuations revealed recently. Finally, the magnetic property at below ∼240 K is discussed.     

The Influence of the V<Subscript>2</Subscript>O<Subscript>5</Subscript> · GeO<Subscript>2</Subscript> Glass Phase on the Properties of AgI Nanolayers

Using X-ray phase analysis and impedance monitoring, it was shown that for a nanolayered structure, softened glass (V₂O₅ · GeO₂) can take an imprint from AgI lattice and retain it while being cooled to temperatures below Tg.     

Crossing of the πd<Subscript>5/2</Subscript> and πg<Subscript>7/2</Subscript> orbitals in the <Subscript>51</Subscript>Sb isotopes

Self-consistent calculations using the D1S Gogny force have been performed in order to study the mechanism involved in the crossing of the πd _5/2 and πg _7/2 orbitals in the Sb isotopes. This inversion is well predicted by the HFB + blocking calculations with spherical symmetry performed for the odd-A Sb isotopes. In addition, several HFB and HF calculations have been performed for even-even nuclei of the five neighbouring isotopic chains (Z = 46 to 54, from the proton dripline to N = 82). The results obtained for the binding energies of the two proton orbitals indicate that the radii of the systems play an important role in the crossing, even though some particular πν interactions also give a contribution. The spin-orbit interaction, which is known to be concentrated mainly at the nuclear surface, is proposed to be the main responsible of the crossing.     

Coercivity of homogenized ensembles of anisotropic γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles

The influence of interaction between anisotropic γ-Fe₂O₃ nanoparticles on their coercive force H _c is studied. In samples where the degree of homogenization of anisotropic γ-Fe₂O₃ nanoparticles is high owing to mechanical, ultrasonic, and magnetic dispersion with subsequent filtering of resulting suspensions, H _c is almost independent of volume concentration η of the particles when η varies between 4 × 10⁻⁴ and 10⁻¹. In samples homogenized only mechanically, the H _c versus logη dependence is linear.     

Synthesis of magnetic core–shell Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>–Au nanoparticle for biomolecule immobilization and detection

The production of monodispersed magnetic nanoparticles with appropriate surface modification has attracted increasing attention in biomedical applications including drug delivery, separation, and purification of biomolecules from the matrices. In the present study, we report rapid and room temperature reaction synthesis of gold-coated iron nanoparticles in aqueous solution using the borohydride reduction of HAuCl₄ under sonication for the first time. The resulting nanoparticles were characterized with transmission electron microscopy (TEM), electron spectroscopy for chemical analysis (ESCA), ultraviolet visible spectroscopy (UV–Vis), and X-ray diffraction (XRD). Surface charges and magnetic properties of the nanoparticles were also examined. The pattern of Fe₃O₄ nanoparticles is face centered cubic with an average diameter of 9.5 nm and the initial reduction of gold on the surface of Fe₃O₄ particles exhibits uniform Fe₃O₄–Au nanoparticles with an average diameter of 12.5 nm. The saturation magnetization values for the uncoated and gold-coated Fe₃O₄ nanoparticles were found to be 30 and 4.5 emu/g, respectively, at 300 K. The progression of binding events between boronic acid terminated ligand shell and fructose based on the covalent bonding interaction was measured by absorbance spectral changes. Immunomagnetic separation was also performed at different E. coli concentration to evaluate capturing efficiency of resulting nanoparticles. Immunomagnetic separation percentages were varied in a range of 52.1 and 21.9% depend on the initial bacteria counts.     

The role of structural and nonstructural water in oxyfluoride K<Subscript>2</Subscript>WO<Subscript>2</Subscript>F<Subscript>4</Subscript> · H<Subscript>2</Subscript>O

X-ray structural and polarization optical investigations have been performed, and birefringence and rotation angles of the optical indicatrix φ _b and φ _c of the K₂WO₂F₄ · H₂O crystal have been measured in the temperature range of 100–600 K. The structure and symmetry of compounds at room temperature have been refined. It has been established that the layered crystal K₂WO₂F₄ · H₂O can exist in two states (A and B) depending on the atmospheric humidity and undergoes the sequence of reversible and irreversible phase transformations G ₃ ↔ G ₂ → G ₁ → G ₀. The sequences of changes in the phase symmetry P [`1]\bar 1 ↔ C2/m → P4/nmm for samples A and m ↔ C2/m → P4/nmm for samples B have been found. The second-order proper ferroelastic phase transition (P [`1]\bar 1 ↔ C2/m) at T ₀₃ = 270–290 K (G ₃ ↔ G ₂) is accompanied by twinning and appearance of the shift deformation x ₆. The crystal system of the substance for the B crystals remains invariable after the second-order phase transition G ₃ ↔ G ₂. The irreversible first-order phase transition G ₂ → G ₁ occurs in a temperature range T ₀₂ ≈ 350–380 K; it is accompanied by the loss of the crystallization water, which then is reduced easily from the atmosphere for a day. The substance decomposes at T ₀₁ ≈ 510 K (G ₁ → G ₀). The distinction between the A and B crystals has been explained by the presence or absence of free water in interlayer spacings.     

Size effect in spin-crossover systems investigated by FORC measurements,for surfacted [Fe(NH<Subscript>2</Subscript>-trz)<Subscript>3</Subscript>](Br)<Subscript>2</Subscript>·3H<Subscript>2</Subscript>O nanoparticles: reversible contributions and critical size

We investigated the thermal transition of coated nano-particles of the title compound, on a set of samples of average diameter ⟨d⟩ ~ 30, 50, 70, 110 nm, with rather broad size distributions. As expected, the width of the major hysteresis loop was an increasing function of ⟨d⟩. We recorded first-order reversal curves (FORC), the initial parts of which displayed a finite slope, revealing the presence of reversible contributions expected from particles smaller than the critical size d _C associated with the collapse of the hysteresis loop. Kinetic effects were also evidenced thanks to isothermal stages. Reversibility of the FORC curves at the vicinity of the reversal temperature was controlled. Thanks to the reversibility property we could determine the reversible contributions to the total response of all samples and derive the corresponding d _C values. Consistent results were obtained by accounting for an anhysteretic contribution from the large particles, leading to an accurate determination d _C  ~ 45−50 nm, much better than the width of the size distributions.     

Electron diffraction study of various lattice defects in a Bi<Subscript>4</Subscript>Ge<Subscript>3</Subscript>O<Subscript>12</Subscript> crystal

Lattice defects in a scintillation detector made of Bi₄Ge₃O₁₂ (BGO) could severely impact detector efficiency via non-radiative transfer of electron excitation, thus making thorough investigations of these defects highly important. Here we present a combined experimental and theoretical study of two- and three-dimensional defects in a Czochralski-grown BGO crystal. Upon examination by transmission electron microscopy the selected-area electron diffraction (SAED) patterns in two neighboring parts of the specimen reveal different kinds of two- and three-dimensional defects. Three sub-grains misoriented at 2.47° with reference to each other and probable presence of stacking faults lying in {011} planes were observed in the first examined local area. The SAED image taken from an area in the close neighborhood is much more complicated and is explained in terms of the superposition of reflections from: (i) a partially textured GeO₂ second-phase inclusion; (ii) the basic lattice of BGO and (iii) a superlattice-like structure based on the BGO lattice. The atomic structure of such a superlattice-like structure was theoretically modeled and the corresponding simulated SAED patterns were found to be in good agreement with the experimentally observed one.     

Magnetic and magnetoresistive properties of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sr<Subscript>2</Subscript>FeMoO<Subscript>6–δ</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoheterostructures

A method has been developed for fabricating nanoporous matrices based on anodic aluminum oxide for the deposition of ferromagnetic nanoparticles in them. The modes of deposition of strontium ferromolybdate thin films prepared by the ion-plasma method have been worked out, and the magnetic and magnetoresistive properties, structure, and composition of the films have been investigated. It has been revealed that the microstructure and properties of the strontium ferromolybdate films deposited by ionplasma sputtering depend on the deposition rate and the temperature of the substrate. Based on the measurement of the electrical resistivity of nanoheterostructures in a magnetic field, it has been found that the magnetoresistance reaches 14% at T = 15 K and B = 8 T, which is due to the manifestation of tunneling magnetoresistance.     

The absorption spectrum of D<Subscript>2</Subscript>O in the region of 0.97 μm: the 3ν<Subscript>1</Subscript> + ν<Subscript>3</Subscript> vibrational–rotational band

The vibrational–rotational absorption spectrum of D₂O in the range from 10 120 to 10 450 cm^–1 is recorded on a Fourier transform spectrometer with a resolution of 0.05 cm^–1. The measurements were performed using a multipass White cell with an optical path length of 24 m. A light-emitting diode with brightness higher than that of other devices was used as a radiation source. The signal-to-noise ratio was about 10⁴. The spectrum is interpreted as consisting of lines of more than 400 transitions. The spectral characteristics of lines (centers, intensities, and half widths) are determined by fitting the Voigt profile parameters to experimental data by the least-squares method. The intensities of lines and the experimental rotational energy levels of the (301) vibrational state of the D₂ ¹⁶O molecule with high rotational quantum numbers are determined for the first time.     

Effect of annealing temperature on microstructures and optical properties of Ba<Subscript>0.9</Subscript>Sr<Subscript>0.1</Subscript>TiO<Subscript>3</Subscript> films

Evolution of microstructure and optical property with annealing temperature has been examined for Ba_0.9Sr_0.1TiO₃ films derived from one single precursor solution containing polyethylene glycol polymer. The films sintered below 750°C exhibit a uniform phase structure across the cross-sections and an ordinary optical thin film feature, while the Ba_0.9Sr_0.1TiO₃ films crystallized at 750°C or higher temperature render a lamellar texture consisting of dense and porous Ba_0.9Sr_0.1TiO₃ layers and a good performance as a one-dimensional photonic crystal. The discrepancy in cross-sectional morphology and reflectance property observed in these Ba_0.9Sr_0.1TiO₃ films has been preliminarily explained.     

Characterization and applications of as-grown β-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles prepared by hydrothermal method

The production of low-dimensional nanoparticles (NPs) with appropriate surface modification has attracted increasing attention in biological, biochemical, and environmental applications including chemical sensing, photocatalytic degradation, separation, and purification of toxic molecules from the matrices. In this study, iron oxide NPs have been prepared by hydrothermal method using ferric chloride and urea in aqueous medium under alkaline condition (pH 9 ~ 10). As-grown low-dimensional NPs have been characterized by UV–vis spectroscopy, FT-IR, X-ray diffraction, Field emission scanning electron microscopy, Raman spectroscopy, High-resolution Transmission electron microscopy, and Electron Diffraction System. The uniformity of the NPs size was measured by the scanning electron microscopy, while the single phase of the nanocrystalline β-Fe₂O₃ was characterized using powder X-ray diffraction technique. As-grown NPs were extensively applied for the photocatalytic degradation of acridine orange (AO) and electrochemical sensing of ammonia in liquid phase. Almost 50% photo-catalytic degradation with AO was observed in the presence of UV sources (250 W) with NPs. β-Fe₂O₃ NP-coated gold electrodes (GE, surface area 0.0216 cm²) have enhanced ammonia-sensing performances in their electrical response (I–V characterization) for detecting ammonia in liquid phase. The performances of chemical sensor were investigated, and the results exhibited that the sensitivity, stability, and reproducibility of the sensor improved significantly using β-Fe₂O₃ NPs on GE surface. The sensitivity was approximately 0.5305 ± 0.02 μAcm⁻²mM⁻¹, with a detection limit of 21.8 ± 0.1 μM, based on a signal/noise ratio of 3 with short response time.     

O<Subscript>2</Subscript> photodesorption from AuO<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> and Au<Subscript>2</Subscript>O<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack>

Using time-resolved photoelectron spectroscopy, the decay channels of AuO₂⁻ and Au₂O₂⁻ following photoexcitation with 3.1-eV photons have been studied. For AuO₂⁻, a state with a rather long lifetime of 30 ps has been identified. Its decay path could not be determined but photodesorption can be excluded. For Au₂O₂⁻, the spectra indicate O₂ desorption after 3.1-eV photoexcitation on a time scale of 1 ps. While comparing these results on Au _n O₂⁻ with analogous data on Ag _n O₂⁻ clusters, a discernible pattern emerges: for dissociatively bound O₂(AuO₂⁻, Ag₃O₂⁻), there are long-living excited states which do not decay by oxygen desorption, while for molecular chemisorption (Au₂O₂⁻, Ag₂O₂⁻, Ag₄O₂⁻, Ag₈O₂⁻), the 3.1-eV photoexcitation triggers fast O₂ desorption with a high quantum yield.     

Atomistic simulation of sodium–gadolinium molybdate of stoichiometric (Na<Subscript>1/2</Subscript>Gd<Subscript>1/2</Subscript>MoO<Subscript>4</Subscript>) and cation-deficient (Na<Subscript>2/7</Subscript>Gd<Subscript>4/7</Subscript>MoO<Subscript>4</Subscript>) compositions

Crystals of sodium–gadolinium molybdates of two compositions: stoichiometric (Na_1/2Gd_1/2MoO₄) and cation-deficient (Na_2/7Gd_4/7MoO₄) composition in which 1/7 of the corresponding cation positions are not occupied are simulated by the method of interatomic potentials. For cation-deficient crystals, two kinds of cation position distribution are considered: the statistical distribution of sodium, gadolinium, and unoccupied cation positions in the I4₁/a structure and their partial ordering in the I space group. As a result of the simulation, structural characteristics of sodium–gadolinium molybdates agreeing well with the known experimental data are obtained. In addition, a number of important elastic and thermodynamic properties of these compounds are predicted. The results obtained in the partial-occupancy approximation and by constructing a 7 × 2 × 2 supercell are compared. The local structure of sodium–gadolinium molybdates are analyzed in detail. The influence of the deviation from the stoichiometry as well as cation ordering on the properties of these crystals is discussed.