Microwave-hydrothermal synthesis of γ-Fe2O3 nanoparticles and their magnetic properties

Nanosized γ-Fe₂O₃ is synthesized by the microwave-hydrothermal method. Powder X-ray diffraction and transmission electron microscopic studies showed that the average particle size is 10 nm. Magnetic studies reveal that the γ-Fe₂O₃ nanoparticles are superparamagnetic at room temperature, with a superparamagnetic blocking temperature of 200 K. The magnetic characteristics of the nanoparticles indicate their strongly interacting nature.     

Structural and magnetic properties of Mn nanoparticles prepared by arc-discharge

Mn nanoparticles are prepared by arc discharge technique. MnO, α-Mn, β-Mn, and γ-Mn are detected by X-ray diffraction, while the presence of Mn₃O₄ and MnO₂ is revealed by X-ray photoelectron spectroscopy. Transmission electron microscopy observations show that most of the Mn nanoparticles have irregular shapes, rough surfaces and a shell/core structure, with sizes ranging from several nanometers to 80 nm. The magnetic properties of the Mn nanoparticles are investigated between 2 and 350 K at magnetic fields up to 5 T. A magnetic transition occurring near 43 K is attributed to the formation of the ferrimagnetic Mn₃O₄. The coercivity of the Mn nanoparticles, arising mainly from Mn₃O₄, decreases linearly with increasing temperature below 40 K. Below the blocking temperature T_B ≈ 34 K, the hysteresis loops exhibit large coercivity (up to 500 kA/m), owing to finite size effects, and irreversibility in the loops is found up to 4 T, and magnetization is not saturated up to 5 T. The relationship between structure and the magnetic properties are discussed.     

Synthesis and characterizations of manganese ferrites for hyperthermia applications

In the last few years, magnetic nanoparticles have turned out to offer great potential in biomedical applications. This study was focused on Mn_xFe_1−xFe₂O₄ ferrite particles series with x ranging between 0 and 1. Manganese ferrites nanoparticles were prepared by co-precipitation method that allows a good control of their shape and size. The X-ray analysis indicated a crystallite size of the particles in the nanometers domain increasing with the Mn cation substitution level. Average grain size of the nanoparticles calculated from transmission electron microscopy images of the samples was ranging between 10.5 and 19.0 nm suggesting that the majority of the nanoparticles are monodomain. The hydrodynamic diameter of the water dispersed nanoparticles measured by dynamic light scattering was ranging between 60 and 105 nm proving the tendency of agglomeration. Vibrating sample magnetometer measurement confirmed the superparamagnetic behavior of the powders. The magnetic properties were analyzed considering the proposed cation distribution and Yafet–Kittel angles, while the specific absorption rate (SAR) measurement at 1.95 MHz frequency confirmed the influence of substitution level on magnetic properties and thermal transfer rate. From our results the highest value for specific absorption rate was 148.4 W g⁻¹ for Mn₂Fe₂O₄ at an AC field of 4500 A m⁻¹.     

Magnetodielectric and dielectric properties of orthorhombic HoMnO3 thin films

Sandwich-structural multilayer films Au/HoMnO₃/YBa₂Cu₃O_7 − δ were prepared epitaxially on SrTiO₃ (001) single crystal substrates by using pulsed laser deposition technique. The HoMnO₃ films crystallized in a metastable orthorhombic structure and the Au and YBa₂Cu₃O_7 − δ were used as electrodes to investigate the dielectric and magnetodielectric properties of HoMnO₃ films. The impedance and electric modulus spectroscopic plots were used to discern the intrinsic characteristics of HoMnO₃ films or unwanted interface effects. The low-temperature (~ 2 K) dependence of the dielectric constant of HoMnO₃ films as function of frequency shows anomalies around 43 K and 22 K, which is corresponding to the Néel temperature and lock-in transition of Mn³⁺ moments, respectively. The magnetodielectric effects of HoMnO₃ films were investigated at 100 kHz under a 2T applied magnetic field, and the dielectric constant was tuned resulting in a decrease of 3%. The results indicate the strong coupling between the dielectric properties and magnetic orders in orthorhombic HoMnO₃ films.     

Facilely dispersible magnetic nanoparticles prepared by a surface-initiated atom transfer radical polymerization

Facilely dispersible magnetic nanoparticles (Fe₃O₄) prepared by a surface-initiated atom transfer radical polymerization (ATRP) of poly (ethylene glycol) methyl ether monomethacrylate (PEGMA) are reported. The initiator of 2-bromoisobutyrate (BIB) for ATRP was immobilized onto the surface of Fe₃O₄ nanoparticles by the reaction between 2-bromoisobutyryl bromide (BIBB) and the hydroxyl group on the nanoparticles. The results indicated that the poly(poly(ethylene glycol) monomethacrylate) (PPEGMA) was successfully grafted onto the surface of the magnetic nanoparticles. The core-shell nanoparticles with particle size of ≈ 20 nm in water (about 20 mg/mL) are facilely dispersible and can be easily captured by a magnet with magnetic field of 2000 G.     

Low-temperature synthesis,structural and magnetic properties of self-dopant LaMnO3+δ nanoparticles from a metal-organic polymeric precursor

Self-dopant LaMnO_3+δ nanoparticles have been successfully synthesized by metal citrate complex method based on Pechini-type reaction route, at low temperature (773 K). Powder X-ray diffraction and transmission electron microscope revealed pure and nanostructured phase of LaMnO_3+δ (δ = 0.125) with an average grain size of ∼72 nm (773 K) and ∼80 nm (1173 K). DC-magnetization measurements under an applied magnetic field of H = ±60 kOe showed an increase in the magnetization with the increase of calcination temperature. Ferromagnetic nature shown by non-stoichiometric LaMnO_3+δ was verified by well-defined hysteresis loop with large remanent magnetization (M_r) and coercive field (H_c). Surface areas of LaMnO_3+δ nanoparticles were found to be 157.4 and 153 m² g⁻¹ for the samples annealed at 773 K and 1173 K, respectively.     

Magnetic properties of Ni(II)–Mn(III) LDHs

The synthesis of Ni_1−xMn_x(OH)₂(CO₃)_x/2·nH₂O Layered Double Hydroxides (LDHs) for x = 0.2, 0.25 and 0.33, their characterisation by electron microscopy, X-ray diffraction and their magnetic properties are reported in this study. When x increases, the crystallinity of the nanoparticles is improved. The low temperature magnetic behaviour of these compounds is characteristic of the competition between in plane ferromagnetic and interlayer antiferromagnetic interactions. The ferromagnetism is due to in plane Ni cations interaction and decreases when manganese content increases (Tc decreases from 26 to 15 K when x increases from 0.2 to 0.33). It was found that the substitution of Ni by Mn ions favours the in plane antiferromagnetic order. This study demonstrates that magnetic interactions occur in LDH with non magnetic interlayer anions.     

Hydrothermal fabrication of various morphological α-Fe2O3 nanoparticles modified by surfactants

Two kinds of various morphological α-Fe₂O₃ nanoparticles modified by anionic surfactant (sodium dodecylsulfonate, SDS) and cationic surfactant (hexadecyipyridinium chloride, HPC), respectively, have been synthesized via hydrothermal method, using simple inorganic salt (NH₄)₃Fe(C₂O₄)₃ and alkali NaOH as starting precursors. Meanwhile, α-Fe₂O₃ nanoparticles without surfactant are also fabricated under the same conditions for comparison. The resultant products were characterized by means of Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron micrograph (TEM) combined with electron diffraction (ED) and magnetization measurements. It is interesting that the obtained α-Fe₂O₃ nanoparticles without surfactant are polyhedral with average particle size of 90 ± 35 nm; while the obtained α-Fe₂O₃ nanoparticles modified by SDS are ellipsoidal with mean particle size of major axis: ca. 420 nm; minor axis: ca. 205 nm and those modified by HPC are spherical with mean particle size of ca. 185 nm observed from TEM. In addition, magnetic hysteresis measurements reveal that the α-Fe₂O₃ nanoparticles modified by two surfactants show enhancement in coercivity (H_c) and the remanent magnetization (M_r) compared with those of the obtained α-Fe₂O₃ nanoparticles without surfactant at room temperature. The experimental results suggest that the surfactants not only significantly influence the size and shape of the particles, but also their magnetic properties.     

Synthesis, characterization and in vitro cytotoxicity of self-regulating magnetic implant material for hyperthermia application

Gd-substituted zinc ferrite nanoparticles with low Curie temperatures (T_c) were synthesized by a chemical co-precipitation method. The magnetic properties and heat generation characteristics of these magnetic nanoparticles were investigated. The T_c of ZnGd_xFe_2 − xO₄ nanoparticles increased with increasing Gd³⁺ substitution, and was ~ 318 K at x = 0.02, which was a suitable Curie temperature for thermal seeds implanted in human body. The study on heat generation ability under external alternating magnetic field showed that the temperatures of these nanoparticles could be safely controlled around T_c without the temperature probe and controller. Furthermore, in vitro cytotoxicity of the ferrite nanoparticles was assessed using MTT assay. The results demonstrated that exposure to the bare ferrite nanoparticles for 48 h resulted in concentration-dependent toxicity. Cell growth inhabitation was observed when 4.0 mg/ml of bare ferrite nanoparticles was used. In contrast, PEG-capped nanoparticles had no significant effect on cell viability at any of the concentrations tested.     

Structural and magnetic properties of pristine and Fe-doped NiO nanoparticles synthesized by the co-precipitation method

Ni_1?xFe_xO (x = 0 and 0.03) nanoparticles are synthesized by a chemical route. XRD and TEM measurements confirm phase purity and crystallinity of the nanoparticles. Fe substitution in NiO reduces considerably the average particle size of the nanoparticles. The pristine NiO sample with size 14 nm and Fe-substituted sample having size 7 nm show room temperature ferromagnetism. The pristine NiO having 31 nm size and Fe-substituted sample with size 25 nm are found to be antiferromagnetic. The M–H and M–T behavior of the pristine and Fe-doped samples are explained with a core–shell model with an antiferromagnetic core and a ferromagnetic shell. The disordered spins at the shell give rise to a spin-glass like frozen state below 10 K. The obtained room temperature ferromagnetism in the pristine and Fe-doped NiO has been attributed to particle size effect.     

Carrier induced magnetism in dilute Fe doped Ge1−xSbx thin films

Thin films of Fe_0.01Ge_1−xSb_x (x = 0.01, 0.05, 0.10) alloys were prepared by thermal evaporation technique. Characterization of these thin films was done using High Resolution X-Ray Diffraction (HRXRD), Two Probe Resistivity measurement, Atomic Force Microscopy (AFM) and Magnetic Force Microscopy (MFM) respectively. The resistivity results show that activation energy increases with increase in Sb concentration. The low temperature conduction is explained by Variable Range-Hopping mechanism, which fits very well for the whole temperature range. The Arrhenius plot reveals semiconducting behavior. The AFM images of alloys show almost uniform particle size distribution with average particle size varying from 35 to 60 nm with increase in Sb concentration. The MFM images corresponding to the AFM images show the films exhibiting ferromagnetic interactions at room temperature. The average magnetic domain sizes were observed to increase from 43 to 68 nm with increase in Sb concentration from x = 0.01 to x = 0.10.     

Critical behaviour and magnetocaloric effect of nano crystalline La0.67Ca0.33Mn1−xFexO3 (x = 0.05, 0.2) synthesized by nebulized spray pyrolysis

The structure, critical exponents and magnetocaloric effect (MCE) of Nebulized Spray Pyrolysis (NSP) synthesized nano crystalline La_0.67Ca_0.33Mn_1−xFe_xO₃ (x = 0.05, 0.2) were investigated. The Reitveld refinement of XRD patterns show that the samples adopt an orthorhombic structure with Pnma space group. TEM inspection reveals that the average particle size is about 15 nm and 42 nm for NSP synthesized LCMFe_0.05 and LCMFe_0.2 samples respectively. The temperature and field dependent magnetization studies reveal the superparamagnetic state of La_0.67Ca_0.33Mn_0.95Fe_0.05O₃ and spin-glass-like state of La_0.67Ca_0.33Mn_0.8Fe_0.2O₃. The critical behaviour at the transition region studied using modified Arrott plot provides a second order nature of phase transition for both samples. The magnetocaloric studies show the maximum value of magnetic entropy change (ΔS_max) is in the range 2.3 J kg⁻¹ K⁻¹ at 158 K for LCMFe_0.05 and 0.3 J kg⁻¹ K at 92 K for LCMFe_0.2 respectively at 5 T field. The field dependence of the magnetic entropy changes are also analysed, which show a power law dependence (ΔS_M ∞ Hⁿ, n = 0.72 (2)) at transition temperature, T_C = 162 K for LCMFe_0.05 and n = 1.11(3) at 92 K for LCMFe_0.2.     

Preparation and characterization of PNIPAAm-b-PLA/Fe3O4 thermo-responsive and magnetic composite micelles

Novel magnetic micelles with the flowerlike morphology were prepared with Fe₃O₄ nanoparticles and poly(N-isopropylacrylamide)-block-polylactide (PNIPAAm-b-PLA) copolymers by a dialysis method. The diameter of flowerlike micelles was about 1 μm. The core and shell of the micelles were hydrophilic, while the other area of the micelles was hydrophobic. The lower critical solution temperature (LCST) of PNIPAAm-b-PLA was about 38 °C. The magnetic intensity of Fe₃O₄ nanoparticles decreased after they were encapsulated into PNIPAAm-b-PLA micelles. Thermo-responsive and magnetic properties of the micelles would provide useful applications in the target drug delivery and release system.     

A facile route to synthesis of superparamagnetic Fe3O4–PDVB nanoworms

Fe₃O₄–polydivinylbenzene (PDVB) nanoworms were firstly synthesized by precipitation polymerization of divinylbenzene in the presence of oleic acid coated iron oxide nanoparticles. The nanoworms had superparamagnetic properties at room temperature, but ferromagnetism at 5 K. Thermogravimetric analysis curves indicated that in comparison with magnetic nanoparticles, the weight percent of iron oxide in nanoworms was slightly declined due to the formation of Fe₃O₄–PDVB nanocomposites. The superparamagnetic nanoworms could be well dispersed in ethanol, and were capable of easy separation by an external magnetic field. Overall, this provided a valuable methodology for preparation of elongated magnetic nanoparticles with high surface-to-volume ratio, which had potential applications in drug delivery/targeting, magnetic resonance imaging, and nanoprobes for diagnosis and disease treatment.     

Elastic coupling and anelastic relaxation associated with multiple phase transitions in para-chloroanilinium tetrachlorocuprate, [p-ClC6H4NH3]2CuCl4

The perovskite-like salt [p-ClC₆H₄NH₃]₂CuCl₄1 exhibits a wealth of magnetic and structural phase transitions which have been probed by variable temperature single crystal X-ray diffraction, SQUID magnetometry, resonant ultrasound spectroscopy (RUS), EPR spectroscopy, DSC measurements and DFT calculations. Single crystal X-ray diffraction studies between room temperature and 3 K reveal a rich tapestry of structural changes; at 298 K the structure conforms to a monoclinic setting but undergoes a first order phase transition upon cooling below ∼275 K to a higher symmetry orthorhombic cell. This is facilitated by a transition to an intermediate phase at ∼277 K. Whilst the intermediate phase has a limited stability window (∼2 K) and has not been structurally determined, the two discrete phase transitions at 275.5 K and 277 K have been clearly detected by differential scanning calorimetry, EPR spectroscopy and RUS studies. On further cooling a dynamic relaxation process is observed in RUS measurements, evidenced by a Debye-like peak in the dissipation at ∼140 K. Residual electron density maps from single crystal X-ray diffraction studies reveal that this may be associated with a freezing out of the NH₃?Cl hydrogen-bonding between cation and anion frameworks upon cooling. The activation barrier for this order/disorder process was estimated to be at least 27 kJ mol⁻¹ from the RUS data. Variable temperature dc SQUID data reveal that 1 is a 2D ferromagnet with antiferromagnetic interactions between layers below 9 K. Analysis of the temperature dependence of the magnetic susceptibility for T > 40 K reveals that 1 exhibits Curie–Weiss behaviour with θ = +22.8 K indicative of dominant ferromagnetic interactions. Good agreement is observed between the strength of the ferromagnetic interaction extracted from the Weiss constant (J/k = +22.8 K) and that calculated by DFT (J/k = +25 to +28 K) and from EPR studies (J/k = +17 K). The presence of short range ferromagnetic interactions is reflected in a marked temperature dependence of the g-factors determined from EPR spectroscopy below 20 K and possibly a small elastic anomaly in the RUS data. RUS studies indicate a very small elastic anomaly associated with the transition to long range order, implying weak or no magnetoelastic effect. At fields above ∼15 G a spin flip transition is induced and 1 displays metamagnetic behaviour, with a saturation magnetization of 0.96 μ_B.     

Neutron Diffraction Investigation of the DyFe11Ti Magnetic Structure and Its Spin Reorientations

In this article, we report on the magnetic structure of DyFe₁₁Ti and its thermal evolution as probed by neutron powder diffraction. A thermodiffraction technique was used to follow the temperature dependence of the magnetic moments, as well as their orientation. The Dy and Fe moments were coupled to each other in an antiparallel manner to form a ferrimagnet, where the easy magnetization direction at 2 K was the [110] axis in the basal (a, b) plane. This magnetic structure underwent two successive spin reorientation phenomena with increasing temperature. A large Dy magnetic moment of 9.7 Bohr magneton (μ_B) was obtained at low temperatures, and the magnitude decreased rapidly to 7.5μ_B at 200 K. The largest Fe magnetic moment was observed on the Fe 8i position. A ThMn₁₂-type crystal structure was preserved in the studied temperature range, despite the large changes of the magnetic structure. A sharp tilt was observed at the first-order spin reorientation, T_SR1; the angle between the easy magnetization axis and the crystal c axis was reduced from 90° at 2 K to about 20° at 200 K (where c is the easy axis above 200 K); and the Dy and Fe magnetic moments maintained an antiparallel coupling.     

Preparation of La1−xSrxMnO3 nanoparticles by sonication-assisted coprecipitation

La_1−xSr_xMnO₃ (x=0.3) (LSM) nanoparticles were prepared by a sonication-assisted coprecipitation method. The coprecipitation reaction is carried out with ultrasound radiation. Lower sintering temperatures are required for the sonication-assisted product. Fully crystallized LSM with an average particle size 24 nm is obtained after the as-prepared mixture is annealed at 900 °C for 2 h. Magnetic properties indicate that the transition temperature from the paramagnetic to ferromagnetic state of the sample is quite sharp and occurs at 366 K for samples annealed for 2 h at 900 and 1100 °C.     

The synthesis and characterization of electrical and magnetic nanocomposite: PEDOT/PSS–Fe3O4

The poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate)–Fe₃O₄ (PEDOT/PSS–Fe₃O₄) nanoparticles have been prepared by using polystyrene sulfonic sodium (NaPSS) as a dispersant and dopant. The characterization of nanocomposites was investigated by transmission electron microscope, X-ray diffraction, UV spectroscopy, electrochemical study, four-probe, thermogravimetric analysis and magnetic property measurement system. XRD revealed the presence of spinel phase of Fe₃O₄ and the average size was calculated to be about 12 nm. The conductivity of nanocomposites at room temperature is excellent and it depends on the Fe₃O₄ content. The thermal stability of composites is outstanding. Higher saturation magnetization of 6.47 emu g⁻¹ (20 wt.% Fe₃O₄) was observed at 300 K.     

Solvothermal synthesis and characterization of size-controlled monodisperse Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles

Monodisperse Fe₃O₄ nanoparticles with narrow size distribution could be successfully synthesized in large quantities by a facile solvothermal synthetic method in the presence of oleic acid and oleylamine. Well-defined assembly of uniform nanoparticles with average sizes of 8 nm can be obtained without a further size-selection process. The sizes of final products could be readily tuned from 5 to 12 nm by adjusting the experimental parameters such as reaction time, temperature, and surfactants. The phase structures, morphologies, and magnetic properties of the as-prepared products were investigated in detail by X-ray diffraction, transmission electron microscopy, selected area electron diffraction, high-resolution transmission electron microscopy, and magnetometry with a superconducting quantum interference device. The magnetic study reveals that the as-synthesized nanoparticles are ferromagnetic at 2 K while they are superparamagnetic at 300 K.     

Structure and surface morphology of Mn-implanted TiO2

A study of structure and surface morphology together with magnetic properties of Mn-implanted rutile-type TiO₂ single crystals is performed. Homogenous thin films of about 100 nm with different Mn_xTi_1 − xO₂ (x = 0.03; 0.05 and 0.07) chemical formula were obtained. The Mn ion implanted surface exhibited a dense microstructure with a nano grain size. The dependence of c/a axial ratio on manganese content suggests that Mn³⁺ species substituted tetragonal Ti⁴⁺. The annealing at 873 K caused changes in surface structure, morphology and roughness. A migration of manganese ions into the rutile single crystal takes place and in certain conditions Ti₂O phase occurs. Mn-implanted samples exhibit room temperature ferromagnetism and a Curie temperature of 680 K. Electron spin resonance analysis evidenced that manganese is incorporated by substitution as magnetically isolated Mn⁴⁺, Mn³⁺ and Mn²⁺ species. At 0.07% contents the Mn³⁺ species may enter in interstitial sites contributing to extinction of substitutional magnetic moment.