Mössbauer investigations of Fe and Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> magnetic nanoparticles for hyperthermia applications

Magnetic nanoparticles of magnetite Fe₃O₄ and Fe synthesized by physical vapor deposition with a fast highly effective method using a solar energy have been studied. Targets have been prepared from tablets pressed from Fe₃O₄ or Fe powders. Relationships between the structure of nanoparticles and their magnetic properties have been investigated in order to understand principles of the control of the parameters of magnetic nanoparticles. Mössbauer investigations have revealed that the nanoparticles synthesized from tablets of both pure iron and Fe₃O₄ consist of two phases: pure iron and iron oxides (γ-Fe₂O₃ and Fe₃O₄). The high iron oxidability suggests that the synthesized nanoparticles have a core/shell structure, where the core is pure iron and the shell is an oxidized iron layer. Magnetite nanoparticles synthesized at a pressure of 80 Torr have the best parameters for hyperthermia due to their core/shell structure and core-to-shell volume ratio.     

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.     

Particle speciation during PEG–Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> hybrid nanoparticle self-assembly on Si(Ti)O<Subscript>2</Subscript>

The kinetics of assembly of polyethylene glycol (PEG)-coated superparamagnetic Fe₃O₄ nanoparticles in aqueous suspension on planar Si(Ti)O₂ surfaces have been determined using high-resolution optical waveguide lightmode spectroscopy (OWLS). Analysis of the results revealed that the initially uniform population was spontaneously transformed into two types of particles with significantly different adsorption behaviour.     

Mössbauer studies of stoichiometry of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>: characterization of nanoparticles for biomedical applications

The iron oxide Fe₃O₄, the mineral magnetite sometimes called ferrosoferric oxide, is notoriousy non-stoichiometric even in bulk form so its formula may be written Fe_3?δO₄. In nanoparticle form, where it has applications in medicine and information technology, it is even more susceptible to oxidation. In this paper we report synthesis and studies of superparamagnetic Fe₃O₄ nanoparticles with controlled diameters of 5.3, 10.6 and 11.9 nm. In room temperature spectra, departures from stoichiometry δ of up to 0.02 were estimated from the relative amounts of Fe ³⁺/ Fe ²⁺ and from their isomer shifts. This cannot be used for very small particles of diameter 10.6 nm and less as they are superparamagnetic at room temperature and do not show hyperfine splitting owing to fast relaxation. Such particles have promise for use in enhancing MRI signals. The magnetic spectrum is restored by the application of a relatively small magnetic field (10 kG). As the temperature is lowered the relaxation slows down and 6-line magnetic hyperfine patterns appear below a blocking temperature T_B. The values of T_B obtained are lower than those of many other researchers reported in the literature, suggesting that our particles are less affected by magnetic interactions between them. At low temperatures all the spectra are similar and closely resemble that of bulk Fe₃O₄ confirming that departures from stoichiometry are small.     

Sol–gel electrophoretic deposition and optical properties of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowire arrays

Ordered Fe₂O₃ nanowire arrays embedded in anodic alumina membranes have been fabricated by Sol–gel electrophoretic deposition. After annealing at 600 °C, the Fe₂O₃ nanowire arrays were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED) and X-ray diffraction (XRD). SEM and TEM images show that these nanowires are dense, continuous and arranged roughly parallel to one another. XRD and SAED analysis together indicate that these Fe₂O₃ nanowires crystallize with a polycrystalline corundum structure. The optical absorption band edge of Fe₂O₃ nanowire arrays exhibits a blue shift with respect of that of the bulk Fe₂O₃ owing to the quantum size effect. PACS 78.67.Lt; 81.05.Je; 81.07.Vb     

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.     

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.     

Synthesis and characterization of “mulberry”-like Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/multiwalled carbon nanotube nanocomposites

Nanocomposites composed of multi-wall carbon nanotubes (MWNTs) and Fe₃O₄ nanoparticles were fabricated using solvothermal method. Transmission and scanning electron microscopy, energy dispersive spectroscopy, and X-ray powder diffraction measurements confirmed that these mulberry-like Fe₃O₄ microparticles which were combined with the MWNTs in a random pattern are constructed with tiny nanocrystallites (12 nm in average diameter). The magnetic properties of the Fe₃O₄/MWNTs nanocomposites were measured using a vibrating sample magnetometer. Results showed that the Fe₃O₄/MWNTs nanocomposites exhibited superparamagnetism at room temperature and possessed a lower saturation magnetization (around 27.6 emu/g) than that of the pure Fe₃O₄ nanoparticles (around 33.7 emu/g). The Fe₃O₄/MWNTs nanocomposites have potential applications in engineering and medicine.     

Magnetic Pd nanocatalyst Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@Pd for C–C bond formation and hydrogenation reactions

Small core-shell Fe₃O₄@Pd superparamagnetic nanoparticles (MNPs) were obtained with good control in size and shape distribution by metal-complex thermal decomposition in organic media. The role of the stabilizer in the synthesis of MNPs was studied, employing oleylamine (OA), triphenylphosphine (TPP) and triphenylamine (TPA). The results revealed that, among the stabilizer investigated, the presence of oleylamine in the reaction media is crucial in order to obtain an uniform shell of Pd(0) in Fe₃O₄@Pd MNPs of 7?±?1 nm. The synthesized core-shell MNPs were tested in Pd-catalyzed Heck-Mizoroki and Suzuki-Miyaura coupling reactions and p-chloronitrobenzene hydrogenation. High conversion, good reaction yields, and good TOF values were achieved in the three reaction systems with this nanocatalyst. The core-shell nanoparticle was easily recovered by a simple magnetic separation using a neodymium commercial magnet, which allowed performing up to four cycles of reuse.

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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.     

Synthesis,structure, and optical and photocatalytic properties of quasi-one-dimensional ZnO doped with Со<Subscript>3</Subscript>O<Subscript>4</Subscript> and carbon

One-dimensional nanocomposites Zn_1–x Co _x O_1–y С _у :nCo₃O₄ and solid solutions Zn_1–x Co _x O_1–y С _у , which are promising photocatalysts for the oxidation of toxic organic compounds in visible light, are obtained via the thermolysis of Zn_1–x Co _x (HCOO)(OCH₂CH₂O)_1/2 (0.1 ≤ x ≤ 0.5) precursor in a controlled gaseous atmosphere.     

Synthesis and magnetic properties of CdS/α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> hierarchical nanostructures

CdS/α-Fe₂O₃ hierarchical nanostructures, where the CdS nanorods grow irregularly on the side surface of α-Fe₂O₃ nanorods, were synthesized via a three-step process. The diameters and lengths of CdS nanorods can be tuned by changing the ethylenediamine (EDA) and Cd ion concentrations. The magnetic investigations by superconducting quantum interference device indicate that the hierarchical nanostructures have an Morin transition at lower temperature (230 K) than that of the single bulk α-Fe₂O₃ materials (263 K). Importantly, the hierarchical nanostructures exhibit weakly ferromagnetic characteristics at 300 K. A sharp peak assigned to the surface trap induced emission are observed in room temperature PL spectra. Combining with the optoelectronic properties of CdS, the CdS/α-Fe₂O₃ hierarchical nanostructures may be used as multi-functional materials for optoelectronic and magnetic devices. Supported by the National Natural Science Foundation of China (Grant Nos. 50772025 and 50872159), the Ministry of Science and Technology of China (Grant No. 2008DFR20420), the China Postdoctoral Science Foundation (Grant Nos. 20060400042 and 200801044), the Natural Science Foundation of Heilongjiang Province, China (Grant No. F200828), the Specialized Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20070217002), and the Innovation Foundation of Harbin City (Grant No. RC2006QN017016)     

XRD,impedance, and Mössbauer spectroscopy study of the Li<Subscript>3</Subscript>Fe<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> + Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> composite for Li ion batteries

The synthesis procedure of the Li₃Fe₂(PO₄)₃?+?Fe₂O₃ composite is presented. The monoclinic (A type) and hematite phases were detected by X-ray diffraction after the synthesis of the composite. The structural α–β (at a temperature of 460 K) and β–γ (at a temperature of 523 K) phase transitions in the composite were indicated by the anomalies of the electrical conductivity, dielectric permittivity, and changes of activation energies of conductivity. Two phase transitions have been detected in the Li₃Fe₂(PO₄)₃?+?Fe₂O₃ composite by ⁵⁷Fe Mössbauer spectroscopy: the phase transition in Li₃Fe₂(PO₄)₃ from the paramagnetic to antiferromagnetic phase at temperature T _N?=?29.5 K and the Morin phase transition in Fe₂O₃ at temperature T _M?=?235 K.     

AC and DC properties of M-type SrCo<Subscript>x</Subscript>Ti<Subscript>x</Subscript>Fe<Subscript>(12−2x)</Subscript>O<Subscript>19</Subscript> hexagonal ferrite

Microwave characterization of SrCo _x Ti _x Fe_(12?2x)O₁₉ (x = 0.0, 0.2, 0.3, 0.5, 0.6, 0.7, 1.0) ferrites has been studied as a function of frequency, substitution and thickness, and static electrical current density-electric field characteristics have been investigated as a function of substitution. Microwave characteristics have been measured using power meter in the rectangular slotted waveguide and current density is measured using electrometer. The microwave absorption is evaluated using the standard available model. The results depict ?11.57 dB reflection loss at 10.38 GHz in composition x = 0.6. The electrical current density decreases at lower substitution and increases at higher substitution. The substitution of Co²⁺ and Ti⁴⁺ ions causes enhancement of electromagnetic and static electrical properties.     

Synthesis and characterization of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>–Ba<Subscript>0.9</Subscript>Sr<Subscript>0.1</Subscript>TiO<Subscript>3</Subscript> magnetoelectric composites with dielectric and magnetic properties

Composite structures consisting of (001)-oriented SrTiO₃ (STO)/La_0.7Sr_0.3MnO₃ (LSMO) films of 30 nm thickness, grown on an (001) Pb(Mg_1/3Nb_2/3)TiO₃– 28 mol.% PbTiO₃ piezoelectric relaxor-ferroelectric single-crystalline wafer were investigated by means of Wide-Angle X-ray Diffraction (WAXRD) in situ under influence of a d.c. electric field with strength E up to ±18 kV/cm. The WAXRD measurements of the films and substrate reflection profiles resulted in a determination of the strain s in the films and the substrate separately. The strained state of the STO/LSMO films is effectively controlled by a huge converse piezoelectric effect of the PMN-PT substrate. The coefficients of coupling between electric-field-induced out-of-plane strain in the films and in the substrate for the composite system STO/LSMO/PMN-PT are obtained.     

Phase formation in the BaCO<Subscript>3</Subscript>–PbO–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> system

Features of the formation of lead-ferroniobate compounds in the xBaCO₃–(1 – x)PbO–Fe₂O₃–Nb₂O₅ system by solid-phase synthesis are investigated. For perovskite-type lead-ferroniobate solid solution, a single-phase concentration region is revealed at 1233 K. The crystalline structures of the synthesized compounds are refined using Rietveld analysis and the Pm3?m and R3m space groups. Ceramic samples of lead ferroniobate are studied by scanning electron microscopy.     

Domain state–dependent magnetic formation of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles analyzed via magnetic resonance

Magnetic properties, arising from surface exchange and interparticle interactions of the Fe₃O₄ (magnetite) nanoparticles, were investigated in the temperature range of 5–300 and 120–300 K using vibrating sample magnetometer technique and electron spin resonance spectroscopy, respectively. The research was based on to figure out the origin of intraparticle interactions and the change of interparticle interactions in wide size range Fe₃O₄ nanoparticles. The analyses were done for samples having almost same particle size distributions. The average particle sizes were changed in between 30 ± 2 and 34 ± 2 nm. The observed magnetization values were demonstrated the mixture of single-domain size particles, exhibiting both single-domain (SD) and superparamagnetic (SPM) states. The symmetry of resonance curves changed according to the ratio of SD and SPM-stated particles in mixture under located temperature. The changes of anisotropy up to domain state were understood by freezing magnetic moment in glycerol matrix from room temperature to 120 K under 5-kG field. The shift of H _R values to higher magnetic fields and the more symmetric resonance spectrum proved the effect of anisotropy and interparticle interactions fields on magnetic behave. In addition, the origin of intra-interaction was exposed from Fe³⁺ centers and exchange coupling in between Fe²⁺, Fe³⁺, and O⁻, and Fe³⁺ centers found from g factor (g).     

Elastic properties of TeO<Subscript>2</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–Ag<Subscript>2</Subscript>O glasses

A series of glasses [(TeO₂) _x (B₂O₃)_1−x ]_1−y [Ag₂O] _y with x = 70 and y = 10, 15, 20, 25 and 30 mol% were synthesised by rapid quenching. Longitudinal and shear ultrasonic velocity were measured at room temperature and at 5 MHz frequency. Elastic properties, Poisson's ratio, microhardness, softening temperature and Debye temperature have been calculated from the measured density and ultrasonic velocity at room temperature. The experimental results indicate that the elastic constants depend upon the composition of the glasses and the role of the Ag₂O inside the glass network is discussed. Estimated parameters based on Makishima–Mackenzie theory and bond compression model were calculated in order to analyse the experimental elastic moduli. Comparison between the experimental elastic moduli data obtained in the study and the calculated theoretically by the mentioned above models has been discussed.     

Optical and magneto-optical properties of Fe<Subscript>4−x</Subscript>Co<Subscript>x</Subscript> (x = 1–3)

We report a systematic study of the electronic, optical, and magneto-optical properties of the Fe_4−xCo_x (x = 1–3) compounds using the full-potential linearized augmented plane waves (FPLAPW) method within the local spin density approximation (LSDA). Pure Fe (x = 0) and Co (x = 4) have also been studied, the latter in hcp as well as bcc structure, to offer a better comparison. A good agreement is obtained between calculated optical conductivity spectra and experimental data. We note that the magneto-optical properties of these compounds are found to be more akin to those of bcc Co (which has MOKE very similar to that of bcc Fe) than to those of hcp Co. This shows strong impact of the environment on the MOKE of these compounds. With respect to the elemental values, the magnetic moments at Fe sites are found to be larger in general, while those at Co sites are almost the same. However, interestingly, despite their larger magnetic moment, the Kerr rotation remains comparable to that of bcc Fe for most of the energy range. The origin of Kerr spectra has been explained in terms of optical transitions.     

Structural and Mössbauer studies of nanocrystalline Mn<Superscript>4+</Superscript>-doped Li<Subscript>0.5</Subscript>Fe<Subscript>2.5</Subscript>O<Subscript>4</Subscript> particles prepared by mechanical milling

The structure and magnetic properties of spinel-related Mn⁴⁺-doped Li_0.5Fe_2.5O₄ nanocrystalline particles of the composition Li_0.5Fe_2.25Mn_0.1875O₄, prepared by milling a pristine sample for different times, were investigated. The average crystallite and particle size, respectively, decreased form ～40 nm to ～10 nm and ～2.5 μm to ～10 nm with increasing milling time from 0 h to 70 h. Rietveld refinement of the XRD data of the non-milled sample show the Mn⁴⁺ dopant ions to substitute for Fe³⁺ at the octahedral B-sites of the spinel-related structure. The Mössbauer spectra of the milled ferrites indicate that more particles turn superparamagnetic with increasing milling time. The Mössbauer data collected at 78 K suggest that while in the non-milled sample the Mn⁴⁺ ions substitute for Fe³⁺ at the octahedral B-sites, this is reversed as milling proceeds with doped Mn⁴⁺ ions, balancing Fe³⁺ vacancies and possibly Li⁺ ions progressively migrate to the tetrahedral A-sites. This is supported by the slight increase observed in the magnetization of the milled samples relative to that of the non-milled one. The magnetic data suggest that in addition to the increasing superparamagentic component of the milled particles, thermal spin reversal and/or spin canting effects are possible at the surface layers of the nanoparticles.