Processing, properties and some novel applications of magnetic nanoparticles

Magnetic nanoparticles have been prepared by various soft chemical methods including self-assembly. The bare or surface-modified particles find applications in areas such as hyperthermia treatment of cancer and magnetic field-assisted radioactive chemical separation. We present here some of the salient features of processing of nanostructured magnetic materials of different sizes and shapes, their properties and some possible applications. The materials studied included metals, metal-ceramic composites, and ferrites.     

Zero-field and in-field Mössbauer spectroscopy as a tool for structural and magnetic characterization of maghemite (γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>) nanoparticles

Nowadays, nanoparticles of maghemite (γ-Fe₂O₃) represent one of the most useful materials in modern advanced nanotechnological applications due to their superior magnetic properties. For their characterization,⁵⁷Fe zero-field and in-field Mössbauer spectroscopy have proved themselves to be very powerful and effective tools which are crucial for an investigation of the local surrounding of iron atoms and observation of dynamic effects. The structural and magnetic characteristics of maghemite and its nanoparticles are thus discussed with regard to their zero-field and in-field Mössbauer spectra recorded at various temperatures and applied external magnetic fields. In addition, a special attention is also devoted to remarkable physical phenomena (superparamagnetism, spin canting) occurring largely in maghemite nanosized particles.     

Synthesis and characterizations of water-based ferrofluids of substituted ferrites [Fe1−xBxFe2O4, B=Mn,Co (x=0–1)] for biomedical applications

Nanomagnetic particles have great potential in the biomedical applications like MRI contrast enhancement, magnetic separation, targeting delivery and hyperthermia. In this paper, we have explored the possibility of biomedical applications of [Fe_1−xB_xFe₂O₄, B=Mn, Co] ferrite. Superparamagnetic particles of substituted ferrites [Fe_1−xB_xFe₂O₄, B=Mn, Co (x=0–1)] and their fatty acid coated water base ferrofluids have been successfully prepared by co-precipitation technique using NH4OH/TMAH (Tetramethylammonium hydroxide) as base. In vitro cytocompatibility study of different magnetic fluids was done using HeLa (human cervical carcinoma) cell lines. Co²⁺-substituted ferrite systems (e.g. CoFe₂O₄) is more toxic than Mn²⁺-substituted ferrite systems (e.g. MnFe₂O₄, Fe_0.6Mn_0.4Fe₂O₄). The later is as cytocompatible as Fe₃O₄. Thus, Fe_1−xMn_xFe₂O₄ could be useful in biomedical applications like MRI contrast agent and hyperthermia treatment of cancer.     

Effect of Magnetic Pulse Processing on the Structure and Magnetic Properties of Ferrites

The effect a pulsed magnetic field has on the crystal structure and macroscopic magnetic parameters of hexagonal ferrites BaFe₁₂O₁₉ and SrFe₁₂O₁₉ are studied. It is shown that changes in the physical properties of ferrites are due to the ordering of cation vacancies on the boundaries of hexagonal and spinel blocks that minimize local distortion of the oxygen polyhedrons. Violation of the collinear ordering of the magnetic moments of iron ions in the nonequivalent positions of SrFe₁₂O₁₉ ferrite is observed, due to the selective localization of such vacancies (and thus violations of the magnetic relationships in Fe–O–Fe).     

Studies on the activation energy from the ac conductivity measurements of rubber ferrite composites containing manganese zinc ferrite

Manganese zinc ferrites (MZF) have resistivities between 0.01 and 10 Ω m. Making composite materials of ferrites with either natural rubber or plastics will modify the electrical properties of ferrites. The moldability and flexibility of these composites find wide use in industrial and other scientific applications. Mixed ferrites belonging to the series Mn_(1−x)Zn_xFe₂O₄ were synthesized for different ‘x’ values in steps of 0.2, and incorporated in natural rubber matrix (RFC). From the dielectric measurements of the ceramic manganese zinc ferrite and rubber ferrite composites, ac conductivity and activation energy were evaluated. A program was developed with the aid of the LabVIEW package to automate the measurements. The ac conductivity of RFC was then correlated with that of the magnetic filler and matrix by a mixture equation which helps to tailor properties of these composites.     

A.C. and D.C. conductivity of NiZn ferrite nanoparticles in wet and dry conditions

Promising future applications of ferrite nanoparticles in medicine, drug delivery, sensors and ferrofluids are expected to be in wet or humid environments. Therefore nanostructured powders of ferrites having the chemical compositions.Ni_xZn _(1−x)Fe₂O₄ with (x=0.0, 0.25, 0.5, 0.75, and 1) were pressed immediately after preparation - by the co-precipitation method - without any drying to simulate a humid environment. The nanoparticles were characterized by X-ray diffraction analysis (XRD) to be sure of the formation of the ferrite in nanoscale. The infrared (IR) spectroscopy of the samples ensures the existence of water as well as the characteristic absorption bands of ferrites. The ac and dc conductivity of the samples had been investigated immediately after preparation (the as-prepared samples). Then, the samples were dried at 200 °C for about 12 h and reinvestigated. The behavior of conductivity differs significantly in the two cases showing a noticeable effect due to humidity. Also, the magnetic induction of the as-prepared samples was investigated by using the vibrating sample magnetometer (VSM). The samples show superparamagnetic behavior.     

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.     

A facile method to synthesize magnetic polymer nanospheres with multifunctional groups

Magnetic poly(styrene methyl methacrylate)/Fe₃O₄ nanospheres with ester groups were prepared by a modified one-step mini-emulsion polymerization in the presence of Fe₃O₄ ferrofluids. The effects of monomer dose, surfactant content, ferrofluid concentration and initiator content on the particle characteristics such as the size, morphology and magnetic properties were investigated by Fourier-transform infrared spectroscopy, transmission electron microscopy, thermogravimetric analysis and vibrating sample magnetometer. The results indicated that magnetic nanospheres were superparamagnetic with high saturation magnetization of 51.0 emu/g and corresponding magnetite content of 61.5 wt%. Subsequently, magnetic nanospheres with carboxyl and amino groups were also obtained by hydrolysis and ammonolysis reaction. These magnetic nanospheres with multifunctional groups have biomedical applications.     

Gummic acid stabilized γ-Fe2O3 aqueous suspensions for biomedical applications

Biomedical applications of magnetic nanoparticles depend critically on their preparation as aqueous colloidal suspensions, or ferrofluids, with long term stability under physiological conditions. Dispersion of the magnetic nanoparticles is generally achieved by the use of protein cages, polysaccharide, polypeptide and charged macromolecular coatings, which minimize interparticle magnetic interactions, particle agglomeration and precipitation. The synthesis and characterization of gummic-acid stabilized maghemite ferrofluids is reported. X-ray diffraction, transmission electron microscope and dynamic light scattering measurements give a γ-Fe₂O₃ magnetic core diameter of 8 nm and a nanocomposite particle hydrodynamic diameter of 50 nm. Mössbauer and magnetization measurements indicate the presence of isolated, sterically stabilized superparamagnetic nanoparticles resistant to aging, and thus, promising agents for the production of novel magneto-pharmaceuticals.     

Influence of V2O5 on the densification and the magnetic properties of Ni—Zn ferrite

The effects of V₂O₅ addition on the densification and the magnetic properties of the Ni—Zn ferrites have been studied. The maximum density was observed at a V₂O₅ content of 0.2 mo1% and 0.5 mo1% in iron excess and deficient ferrites respectively. The minimum loss factor occured at a V₂O₅ content of 0.4 mo1% irrespective of sintering temperature in both iron excess and iron deficient compositions. The variation of Curie temperature with the amount of V₂O₅ (? 1 mo1%) added suggests that V₂O₅ goes into solid solution in the Ni—Zn ferrites, though the lattice parameter does not change appreciably with such addition.     

Magnetic nanoparticle-induced hyperthermia treatment under magnetic resonance imaging

Super paramagnetic iron oxide Fe₃O₄ nanoparticles prepared via photochemical reaction in pure form were used for inducing hyperthermia to treat subcutaneous Ehrlich carcinoma implanted in female mice. Our results indicate that the mean temperature profiles at the rectum, periphery of the tumor surface and at the center of the tumor during hyperthermia treatment increased gradually. The maximum temperature achieved in the tumor center was 47±1°C after 20 min with radiofrequency exposures at 25 kW. The acquired magnetic resonance images identified apoptotic cells in the center of the tumor which were exposed to magnetic resonance hyperthermia (MRH). Apoptotic cells presented as dark signal intensity in the T₁-weighted images which were further confirmed by pathological examinations. Also, the results revealed that the tumor size in the all mice exposed to MRH is still as the same as before the treatment, but the rate of tumor growth was very slow by comparing with the growth rate of the control group.     

Synthesis and functionalization of magnetite nanoparticles with different amino-functional alkoxysilanes

Superparamagnetic iron oxide (SPIO) nanoparticles show great promise for many biotechnological applications. This paper addresses the synthesis and characterization of SPIO nanoparticles grafted with three different alkoxysilanes: 3-aminopropyl-triethoxysilane (APTES), 3-aminopropyl-ethyl-diethoxysilane (APDES) and 3-aminopropyl-diethy-ethoxysilane (APES). SPIO nanoparticles with an average particle diameter of 10 nm were prepared by chemical sonoprecipitation. As confirmed by Fourier transform infrared (FTIR) spectroscopy, silylation of these nanoparticles occurs through a two-step process. Decreasing the number of alkoxide groups reduced the concentration of free amino groups on the SPIO surface ([SPIO-NH₂]—APTES>APDES>APES). This phenomenon results from steric contributions and the formation of H-bonded amines provided by the ethyl groups present in the APDES and APES molecules. A simulation of SPIO nanoparticles in a saline physiologic solution shows that the ethyl groups impart larger steric stability onto the ferrofluids, which reduces aggregation. The magnetization (M) versus magnetic field (H) curves show that the synthesized iron oxide nanoparticles display superparamagnetic behavior. The zero-field cooling (ZFC) and field cooling (FC) curves show that the changes in the blocking temperature depend on the alkoxysilane-functionalized particle surface.     

Glass additive influence on the sintering behavior, microstructure and microwave magnetic properties of Cu-Bi-Zn co-doped Co2Z ferrites

The Bi₂O₃-B₂O₃-ZnO-SiO₂ (BB35SZ) glass effects on the sintering behavior and microwave magnetic properties of Cu-Bi-Zn co-doped Co₂Z ferrites were investigated to develop low-temperature-fired ferrites. The glass wetting characteristics on the Co₂Z ferrite surface, X-ray diffractometer, scanning electron microscopy and a dilatometer were used to examine the BB35SZ glass effect on Co₂Z ferrite densification and the chemical reaction between the glass and Co₂Z ferrites. The results indicate that BB35SZ glass can be used as a sintering aid to reduce the densification temperature of Co₂Z ferrites from 1300 to 900 °C. 3(Ba_0.9Bi_0.1O)·2(Co_0.8Cu_0.2O)·12(Fe_1.975Zn_0.025O₃) ferrite with 2 wt% BB35SZ glass can be densified below 900 °C, exhibiting an initial permeability of 3.4. This process provides a promising candidate for multilayer chip magnetic devices for microwave applications.     

Simulating magnetic nanoparticle behavior in low-field MRI under transverse rotating fields and imposed fluid flow

In the presence of alternating-sinusoidal or rotating magnetic fields, magnetic nanoparticles will act to realign their magnetic moment with the applied magnetic field. The realignment is characterized by the nanoparticle's time constant, τ. As the magnetic field frequency is increased, the nanoparticle's magnetic moment lags the applied magnetic field at a constant angle for a given frequency, Ω, in rad s⁻¹. Associated with this misalignment is a power dissipation that increases the bulk magnetic fluid's temperature which has been utilized as a method of magnetic nanoparticle hyperthermia, particularly suited for cancer in low-perfusion tissue (e.g., breast) where temperature increases of between 4 and 7 °C above the ambient in vivo temperature cause tumor hyperthermia. This work examines the rise in the magnetic fluid's temperature in the MRI environment which is characterized by a large DC field, B₀. Theoretical analysis and simulation is used to predict the effect of both alternating-sinusoidal and rotating magnetic fields transverse to B₀. Results are presented for the expected temperature increase in small tumors ( radius) over an appropriate range of magnetic fluid concentrations (0.002-0.01 solid volume fraction) and nanoparticle radii (1-10 nm). The results indicate that significant heating can take place, even in low-field MRI systems where magnetic fluid saturation is not significant, with careful the goal of this work is to examine, by means of analysis and simulation, the concept of interactive fluid magnetization using the dynamic behavior of superparamagnetic iron oxide nanoparticle suspensions in the MRI environment. In addition to the usual magnetic fields associated with MRI, a rotating magnetic field is applied transverse to the main B₀ field of the MRI. Additional or modified magnetic fields have been previously proposed for hyperthermia and targeted drug delivery within MRI. Analytical predictions and numerical simulations of the transverse rotating magnetic field in the presence of B₀ are investigated to demonstrate the effect of Ω, the rotating field frequency, and the magnetic field amplitude on the fluid suspension magnetization. The transverse magnetization due to the rotating transverse field shows strong dependence on the characteristic time constant of the fluid suspension, τ. The analysis shows that as the rotating field frequency increases so that Ωτ approaches unity, the transverse fluid magnetization vector is significantly non-aligned with the applied rotating field and the magnetization's magnitude is a strong function of the field frequency. In this frequency range, the fluid's transverse magnetization is controlled by the applied field which is determined by the operator. The phenomenon, which is due to the physical rotation of the magnetic nanoparticles in the suspension, is demonstrated analytically when the nanoparticles are present in high concentrations (1-3% solid volume fractions) more typical of hyperthermia rather than in clinical imaging applications, and in low MRI field strengths (such as open MRI systems), where the magnetic nanoparticles are not magnetically saturated. The effect of imposed Poiseuille flow in a planar channel geometry and changing nanoparticle concentration is examined. The work represents the first known attempt to analyze the dynamic behavior of magnetic nanoparticles in the MRI environment including the effects of the magnetic nanoparticle spin-velocity. It is shown that the magnitude of the transverse magnetization is a strong function of the rotating transverse field frequency. Interactive fluid magnetization effects are predicted due to non-uniform fluid magnetization in planar Poiseuille flow with high nanoparticle concentrations.     

BaCO3 mediated modifications in structural and magnetic properties of natural nanoferrites

Preparing M-type barium hexaferrite and improving the magnetic response of natural ferrites by incorporating barium carbonate (BaCO₃) is ever-demanding. Series of barium carbonate doped ferrites with composition (100−x)Fe₃O₄·xBaCO₃ (x=0, 10, 20, 30 wt%) are prepared through solid state reaction method and sintered gradually at temperatures of 800 and 1000 °C. Nanoparticles of natural ferrite and commercial BaCO₃ are used as raw materials. Impacts of BaCO3 on structural and magnetic properties of these synthesized ferrites are inspected. The obtained ferrites are characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD) and vibrating sample magnetometer (VSM) at room temperature. Uniform barium hexaferrite particles in terms of both morphology and size are not achieved. The average crystallite size of BaFe₁₂O₁₉ is observed to be within 30–600 nm. The sintering process results phase transformation from Fe₃O₄ (magnetite) to α-Fe₂O₃ (hematite) and the formation of hexagonal barium ferrite crystals. The occurrence of barium crystal is found to enhance with the increase of BaCO₃ concentrations up to 20 wt% and suddenly drop at 30 wt%. Saturation and remanent magnetization of the doped ferrites are significantly augmented up to 16.37 and 8.92 emu g⁻¹, respectively compared to their pure counterpart. Furthermore, the coercivity field is slightly decreased as BaCO₃ concentrations are increased. BaCO₃ mediated improvements in the magnetic response of natural ferrites are demonstrated.     

Magnetic nanoparticles for application in cancer therapy

Magnetic particles play nowadays an important role in different technological areas with potential applications in fields such as electronics, energy and biomedicine. In this report we will focus on the hyperthermia properties of magnetite nanoparticles and the effect of several chemical/physical parameters on their heating properties. We will discuss about the need of searching new smaller magnetic systems in order to fulfill the required physical properties which allow treating tumoral tissues more efficiently by means of magnetically induced heat. Preliminary results will be shown about the effect of a biocompatible shell of core–shell magnetite NPs on the heating properties by application of a RF magnetic field.     

Saturation Magnetization and Law of Approach to Saturation for Self-formed Ionic Ferrofluids Based on MnFe2O2 Nanoparticles

测量了MnFe₂O₄纳米微粒及其磁性液体在室温下的磁化曲线.微粒的中值粒径为13.67 nm. 磁性液体的比饱和磁化强度小于理论值.在高场范围(5～10 kOe)下,磁性液体趋于饱和时,其体积分数越大,磁化曲线的斜率越大. 这种饱和磁化强度性质和趋饱和律分别源自于无场时的环状自组装团聚体和场致团聚体. 场致团聚体是耗散结构,以致于其趋饱和磁化律不同于顺磁理论所描述的趋饱和律. 磁性液体中的大微粒导致了表观磁滞现象.     

Synthesis and characterizations of microwave sintered ferrite powders and their composite films for practical applications

Phase pure single phase ferrite powders of (Ni_xR_1−x)_0.5Zn_0.5Fe₂O₄ (R=Mn, Co, Cu; x=0, 0.5) were manufactured using microwave sintering at 930 °C for 10 min in air atmosphere. The powders were characterized for their structure, microstructure, thermal, and magnetic properties. Selected powders were used as fillers to prepare their composite films using polymethyl methacrylate polymers as matrix. The composite films were prepared using the melt blending approach and were tested for their microstructure, thermal, and magnetic hysteresis loop as well as 3D magnetic field space mappings using an electromagnetic compatibility scanner. Among the studied ferrites, cobalt doped ferrites and their composites showed the best electromagnetic interference (EMI) shielding effectiveness value and have potential for practical EMI shielding applications.     

Synthesis of Fe3O4 magnetic fluid used for magnetic resonance imaging and hyperthermia

Fe₃O₄ magnetic nanoparticles were prepared by co-precipitation from FeSO₄·7H₂O and FeCl₃·6H₂O aqueous solutions using NaOH as precipitating reagent. The nanoparticles have an average size of 12 nm and exhibit superparamagnetism at room temperature. The nanoparticles were used to prepare a water-based magnetic fluid using oleic acid and Tween 80 as surfactants. The stability and magnetic properties of the magnetic fluid were characterized by Gouy magnetic balance. The experimental results imply that the hydrophilic block of Tween 80 can make the Fe₃O₄ nanoparticles suspending in water stable even after dilution and autoclaving. The magnetic fluid demonstrates excellent stability and fast magneto-temperature response, which can be used both in magnetic resonance imaging and magnetic fluid hyperthermia.