Size-dependent magnetic properties of iron oxide nanoparticles

Uniform iron oxide nanoparticles in the size range from 10 to 24 nm and polydisperse 14 nm iron oxide particles were prepared by thermal decomposition of Fe(III) carboxylates in the presence of oleic acid and co-precipitation of Fe(II) and Fe(III) chlorides by ammonium hydroxide followed by oxidation, respectively. While the first method produced hydrophobic oleic acid coated particles, the second one formed hydrophilic, but uncoated, nanoparticles. To make the iron oxide particles water dispersible and colloidally stable, their surface was modified with poly(ethylene glycol) and sucrose, respectively. Size and size distribution of the nanoparticles was determined by transmission electron microscopy, dynamic light scattering and X-ray diffraction. Surface of the PEG-functionalized and sucrose-modified iron oxide particles was characterized by Fourier transform infrared (FT-IR) and Raman spectroscopy and thermogravimetric analysis (TGA). Magnetic properties were measured by means of vibration sample magnetometry and specific absorption rate in alternating magnetic fields was determined calorimetrically. It was found, that larger ferrimagnetic particles showed higher heating performance than smaller superparamagnetic ones. In the transition range between superparamagnetism and ferrimagnetism, samples with a broader size distribution provided higher heating power than narrow size distributed particles of comparable mean size. Here presented particles showed promising properties for a possible application in magnetic hyperthermia.     

Magnetic, resonance and transport properties of nanopowder of La0.7Sr0.3MnO3 manganites

X-ray powder diffraction, magnetization, transport and magnetic resonance measurements of nanosize La_0.7Sr_0.3MnO₃ (LCMO) manganites have been performed. The nanosize manganites were synthesized with a co-precipitation method at different (600, 700, 800 and 1000 °C) temperatures. The crystal structure of the nanopowders obtained was determined to be perovskite-like with a rhombohedral distortion (the space group R3¯c). The average size of synthesized nanoparticles (from 17 to 88 nm) was estimated using the X-ray diffraction and low temperature adsorption of argon methods. All the nanosize manganites show ferromagnetic-like ordering. Both the Curie temperature and magnetization decrease with reducing the particle size. The decrease of magnetization is due to the disordered surface shell of particles. The disordered surface layer is a source of the surface anisotropy and is responsible for the increase of coercivity. Temperature dependences of the magnetic resonance spectra parameters have allowed obtaining information on dynamics of magnetic properties in the nanoparticle systems. The resistivity was established to become higher by reducing the particles’ size and increases to a great extent in nanoparticles with the smallest average size at low temperatures. The magnetic entropy was shown to be smaller for the small particles. Using the temperature dependence of magnetic entropy the relative cooling power of the nanosize samples studied was evaluated.     

Novel magnetic Fe onion-like fullerene micrometer-sized particles of narrow size distribution

Magnetic polydivinylbenzene (PDVB)/magnetite micrometer-sized particles of narrow size distribution were prepared by entrapping Fe(CO)₅ within the pores of uniform porous PDVB particles, followed by the thermal decomposition of the encapsulated Fe(CO)₅ at 300 °C in a sealed cell under inert atmosphere. Magnetic Fe onion-like fullerene micrometer-sized particles of narrow size distribution have been prepared by the thermal decomposition of the PDVB/magnetite magnetic microspheres at 1100 °C under inert atmosphere. The graphitic coating protects the elemental iron particles from oxidation and thereby preserves their very high magnetic moment for at least a year. Characterization of these unique magnetic carbon graphitic particles was also performed.     

Synthesis of copper-nickel nanoparticles prepared by mechanical milling for use in magnetic hyperthermia

Mechanical alloying of a mixture of copper and nickel powders has been applied for the preparation of copper-nickel alloy particles in the nanometer range. The particles were designed to be used for controlled magnetic hyperthermia applications. The milling conditions were optimized using the desired alloy composition. Utilizing a ball-to-powder mass ratio of 20, we could obtain a nanocrystalline Cu_27.5Ni_72.5 (at%) alloy with a crystallite size of around 10 nm and a Curie temperature of 45 °C.Thermal demagnetization in the vicinity of the Curie temperature of the nanoparticles was determined by thermomagnetic measurements using an adapted TGA-SDTA apparatus. The size and morphology of the particles were determined by XRD measurements and TEM analyses. The magnetic properties were also examined with a VSM. The magnetic heating effects were measured for the powdered material.     

Investigations on magnetic particles prepared by cyclic growth

Magnetic iron oxide nanoparticles are promising tools for medical applications like hyperthermia or magnetic drug targeting. The relevant properties in these applications strongly depend on particle size and size distribution. In order to investigate the influence of mean size as well as size distribution, iron oxide powders from particles by a cyclic method based on “conventional” precipitation from Fe-salt solution were prepared. Increasing mean particle size with increasing number of cycles is confirmed by XRD. Magnetic parameters of the saturation hysteresis loop, hysteresis losses calculated from minor loops and switching field distributions are shown. A fractionation experiment on a fluid sample of particles prepared by 3 cycles was carried out in order to improve the hysteresis losses.     

An investigation on the behavior of fine-grained magnetite particles as a function of size and surface modification

By using a KNO₃-aging ferrous hydroxide gel method, Fe₃O₄ particles with sizes ranging from 35 to 1500 nm were synthesized. The particles were covered with a silica coating to form Fe₃O₄-SiO₂ core-shell structures by using the improved conventional Stöber polycondensation method. The thickness of the SiO₂ covering on magnetite particles surface varies from 10 to 20 nm. The morphology, size and composition of the particles were determined by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The particles with and without coating with SiO₂ were pressed into slices with an oil press at 10 MPa. Subsequently, the coercive forces H_C of the particles were measured by VSM at room temperature, and the critical size for a single domain was estimated. The shape of the particles is basically spherical when the size is smaller than 800 nm, while it is hexagonal for larger particles. The H_C of Fe₃O₄-SiO₂ core-shell structure was larger than that of the uncoated Fe₃O₄ particles by 20%, which was explained to be due to the reduction of inter-particle magnetostatic interaction, supported by an agreement with the packing factor. The dependence of H_C on magnetic particle size could be explained and fitted by the Heewell-Knozam stacking density equation and object-oriented micromagnetic computing framework (OOMMF) micromagnetic software. the results agree well with the experimental data.     

Magnetite ferrofluid with high specific absorption rate for application in hyperthermia

A magnetite ferrofluid coated by dextran with a high specific absorption rate (SAR) of 75 W/g in an AC field of 55 kHz and 200 Oe was prepared by the gel crystallization method with ultrasonic treatment. For comparison, uncoated magnetite particles with a mean diameter of 50 nm were also fabricated. Several possible mechanisms such as Brownian, Neel and diffusion relaxation processes on heating effects and their influence on SAR are discussed. Several factors which can increase the value of SAR were discussed, including dextran coating, ultrasonic treatment, proper particle size and the presence of defects and disorder in the particles.     

Magnetic resonance in iron oxide nanoparticles: Quantum features and effect of size

In order to better understand the transition from quantum to classical behavior in spin system, electron magnetic resonance (EMR) is studied in suspensions of superparamagnetic magnetite nanoparticles with an average diameter of ∼9 nm and analyzed in comparison with the results obtained in the maghemite particles of smaller size (∼5 nm). It is shown that both types of particles demonstrate common EMR behavior, including special features such as the temperature-dependent narrow spectral component and multiple-quantum transitions. These features are common for small quantum systems and not expected in classical case. The relative intensity of these signals rapidly decreases with cooling or increase of particle size, marking gradual transition to the classical ferromagnetic resonance (FMR) behavior.     

Particles size effects of single domain CoFe2O4 on suspensions stability

Single domain magnetic CoFe₂O₄ nanoparticles with spinel structure were prepared by the coprecipitation method. Particles with size of 16, 20, 40 and 60 nm were synthesized by sintering the precursor at 500, 600, 800 and 900 °C, respectively. The magnetic hysteresis measurement of CoFe₂O₄ particles showed that particles were single domain particles with similar saturation magnetization (∼300 emu/cm³) at room temperature. The zeta potential study of suspensions (CoFe₂O₄-acetylacetone system) with various particle sizes showed the suspension systems had similar zeta potential values (∼40 mV). The effects of magnetic particle size on the suspension stability characterized by electrophoretic deposition yields and sediment volumes were studied. The suspension stability decreased with an increase in particle size and a flocculation threshold of particle radius a was found at 30 nm. A suspension stability theory approaching to the phenomenon was established. The theory based on the DLVO theory was developed by introducing an extra magnetic interaction force. Dormann model was adopted, in which the magnetic interactions of two spherical nanoparticles were investigated in terms of dipole-dipole interactions. Compared to DLVO, suspension's physical parameters not only zeta potential ζ and the Debye length 1/κ, but also particles' radius a brought about stable to flocculation transition in the theory.     

A microfluidic spiral for size-dependent fractionation of magnetic microspheres

Magnetic microspheres (MMS) are useful tools for a variety of medical and pharmaceutical applications. Typically, commercially manufactured MMS exhibit broad size distributions. This polydispersity is problematic for many applications. Since the direct synthesis of monodisperse MMS is often fraught with technical challenges, there is considerable interest in and need associated with the development of techniques for size-dependent fractionation of MMS. In this study we demonstrated continuous size-dependent fractionation of sub-micron scale particles driven by secondary (Dean effect) flows in curved microfluidic channels. Our goal was to demonstrate that such techniques can be applied to MMS containing superparamagnetic nanoparticles. To achieve this goal, we developed and tested a microfluidic chip for continuous MMS fractionation. Our data address two key areas. First, the densities of MMS are typically in the range 1.5–2.5 g/cm³, and thus they tend be non-neutrally buoyant. Our data demonstrate that efficient size-dependent fractionation of MMS entrained in water (density 1 g/cm³) is possible and is not significantly influenced by the density mismatch. In this context we show that a mixture comprising two different monodisperse MMS components can be separated into its constituent parts with 100% and 88% success for the larger and smaller particles, respectively. Similarly, we show that a suspension of polydisperse MMS can be separated into streams containing particles with different mean diameters. Second, our data demonstrate that efficient size-dependent fractionation of MMS is not impeded by magnetic interactions between particles, even under application of homogeneous magnetic fields as large as 35 kA/m. The chip is thus suitable for the separation of different particle fractions in a continuous process and the size fractions can be chosen simply by adjusting the flow velocity of the carrier fluid. These facts open the door to size dependent fractionation of MMS.     

Characterisation of advanced metal particle recording media pigments

Advanced metal particle (MP) pigments used in high density digital storage applications on flexible substrates have been characterised using a wide range of techniques. We have examined the chemical composition of the particles and find that the core consists of an iron–cobalt alloy in a structure BCC, analogous to that of α-Fe. Surface layers on the particle used to provide oxidation resistance, have been found to contain some form of oxides of Co, Al and Y as well as iron oxide which we find to be in a spinel form. From Mössbauer spectroscopy we have determined the proportion of the iron atoms in the oxide layer and find that by controlling the percentage of Y in the surface, a much thinner oxide layer results with a corresponding increase in the overall saturation magnetisation. From high resolution TEM images we have determined the particle size of each sample and compared those values with those obtained from X-ray line broadening. We find that in each case the X-ray ‘size' is about a quarter of the physical size excluding the oxide layer. This indicates the polycrystalline character of the particles and the crystallite size is in broad agreement with the activation volume of magnetisation reversal determined from an analysis of magnetic viscosity in the materials. These results are indicative of incoherent magnetisation reversal in the particles which may account for the lower than expected coercivity values in such pigments.     

Polyol synthesis and magnetic study of Mn3O4 nanocrystals of tunable size

Nanosized manganese oxide particles were prepared by the so-called polyol process. The average diameter of the particles was controlled by the growth time. X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photon spectroscopy (XPS) show that the particles are well crystallized, pure, stoichiometric Mn₃O₄ single crystals of uniform size ranging from about 5 to 12 nm. The variation of their dc-magnetization, M, as a function of the magnetic field, H, and temperature, T, clearly corresponds to ferromagnetic ordering at low temperature, with a Curie temperature slightly higher than 40 K. The evidence for superparamagnetism in these particles, due to their very small size, has been discussed in the light of their M(H) and M(T) for zero-field-cooled (ZFC) and field-cooled (FC) plots.     

Ferromagnetic properties of glucose coated Cu2O nanoparticles

Magnetic properties of glucose coated cuprous oxide nanoparticles of different sizes have been studied. Unlike bulk Cu₂O, which shows diamagnetic behavior, the nanoparticles show superparamagnetic behavior. A superparamagnetic blocking temperature of 21 K is observed for 5 nm particles. A magnetic hysteresis loop with a coercivity of 406 Oe is observed for these particles at 5 K. The magnetization and the coercivity increase with decreasing particle size. The superparamagnetic behavior, along with the increase in magnetization and coercivity with decreasing particle size, is due to the enhanced surface contributions to the magnetism.     

Pulsed electrodeposition and magnetism of two-dimensional assembly of controlled-size Co particles on Si substrates

We present an extremely simple and inexpensive way to obtain controlled-size and density Co metallic particles on Si(1 1 1) using electrodeposition. When unpatterned substrates are used, the particle density and size can be controlled by adjusting the pulse frequency and the total deposition time. Randomly arranged cobalt particles with diameters of few tens of nanometres are obtained for short deposition times. Continuing the deposition, the particle size and density can be increased until coalescence. Magnetic force microscopy images show magnetically coupled/uncoupled particles depending on the size and distance between them. For small decoupled particles, no in-plane uniaxial anisotropy is found, in agreement with transmission electron microscopy observations which show randomly oriented single crystal particles. As the particle coalescence increases, the in-plane anisotropy evaluated from magnetization loops increases as well. When deposited on focused ion beam patterned substrates, well organized nanoparticles with adjustable magnetic anisotropy are obtained. Ferromagnetic resonance measurements performed on these samples reveal that the magnetic anisotropy originates mainly from the particle shape.     

Synthesis and magnetic properties of the size-controlled Mn-Zn ferrite nanoparticles by oxidation method

Size-controlled Mn_0.67Zn_0.33Fe₂O₄ nanoparticles in the wide range from 80 to 20 nm have been synthesized, for the first time, using the oxidation method. It has been demonstrated that the particle size can be tailor-made by varying the concentration of the oxidant. The magnetization of the 80 nm particles was 49 A m² kg⁻¹ compared to 34 A m² kg⁻¹ for the 20 nm particles. The Curie temperatures for all the samples are found to be within 630±5 K suggesting that there is no size-dependent cation distribution. The critical particle size for the superparamagnetic limit is found to be about 25 nm. The effective magnetic anisotropy constant is experimentally determined to be 7.78 kJ m⁻³ for the 25 nm particles, which is about an order of magnitude higher than that of the bulk ferrite.     

Manipulation of magnetic carriers for drug delivery using pulsed-current high Tc superconductors

An innovative method of manipulating magnetic carriers is proposed, and its feasibility for drug delivery and therapy is demonstrated experimentally. The proposed method employs pulsed-field solenoid coils with high-critical- temperature (T_c) superconductor inserts. Pulsed current is used to magnetize and de-magnetize the superconductor insert. The proposed method was demonstrated to be able to (1) move magnetic particles, ranging in size from a few millimeters to 10 μm, with strong enough forces over a substantial distance, (2) hold the particles at a designated position as long as needed, and (3) reverse the processes and retrieve the particles. We further demonstrated that magnetic particles can be manipulated in a stationary environment, in water flow, and in simulated blood (water/glycerol mixture) flow.     

Iron oxide nanoparticles modified with oleic acid: Vibrational and phase determination

A simple path methodology to detect the phase composition of iron oxide nanoparticles modified with oleic acid based on vibrational spectroscopy is present here and applied on three different nanoparticles prepared by co-precipitation method. Firstly, the phase composition, magnetite, maghemite, and hematite, is determined using a reference intensity ratio methodology on X-ray diffraction pattern. Also, the size of each sample was calculated by Scherrer equation. Scanning, transmission electron microscopy, microanalysis and electron diffraction show a core magnetite particles size of around 10 nm for all particles. Based on lattice vibrations, we find a concentration of around 80% of magnetite and a hematite phase lower than 5%. Whereas, the magnetite composition from X-ray diffraction shows 76%. We also investigate the metal-organic interaction and disorder degree of organic molecule conformation by infrared and Raman spectroscopy analysis. Hematite lattice vibrations show more alterations as it interacts with the organic acid. Finally, magnetic measurements at room temperature of the modified particles, suggest a superparamagnetic behavior and high saturation magnetization.     

MFM probe control of magnetic vortex chirality in elliptical Co nanoparticles

Magnetic force microscopy (MFM) methods were applied to investigate the peculiarities of magnetization distribution in elliptical 400×600×27 nm Co particles. Reversible transitions between the uniform and vortex states under inhomogeneous magnetic field of MFM probe were observed. Possibility to control the chirality of a magnetic vortex in these particles by MFM probe manipulation was shown.     

The roles of hydrochloric acid and polyethylene glycol in magnetic fluids

Increasing interest has been drawn to the studies of magnetic fluids due to their multiple applications from industry to medicine. However, further exploration is still required for the techniques of preparing satisfying, convenient and stable magnetic fluids. We explored characteristics of magnetic liquids prepared by employing co-precipitation techniques of hydrochloric acid (HCl) and polyethylene glycol (PEG), and the functions of HCl and PEG in the magnetic liquid. According to the improved technique, after preparing Fe₃O₄ by a co-precipitation method, hydrochloric acid and PEG2000 react with magnetic particles at a certain temperature to generate the anticipated magnetic nanoparticles. The process could be under an air atmosphere rather than a N₂ atmosphere. Compared with traditional techniques, the magnetic nanoparticles prepared by this method have smaller size, better dispersion and stability, with the average hydrodynamic diameter adjustable between 8 and 50 nm. This study revealed that reduction of nanoparticles size is not mainly due to a [Cl⁻] coating over the magnetic nanoparticles, but that HCl reacts with Fe₃O₄ particles after being heated. Meanwhile, PEG can stabilize or coat Fe₃O₄ nanoparticles as a dispersing and stabilizing agent.     

Clustering of magnetic nanoparticles using a double hydrophilic block copolymer, poly(ethylene oxide)-b-poly(acrylic acid)

The use of a double hydrophilic block copolymer (DHBC), poly(ethylene oxide)-block-poly(acrylic acid) (PEO-b-PAA) to prepare magnetic nanoparticle (MNP) clusters was investigated. In this one-pot synthesis method, the DHBC controlled the particle growth and served as both stabilizer and clustering agent. Depending on the iron-to-polymer ratio, the synthesized particles can be in the form of colonies of small iron oxide particles or clusters of these particles with size larger than 100 nm. Compared to the previous reported result using random copolymers, the clusters prepared with DHBC were more compact and homogeneous. The yield of clusters increased when the amount of polymer added was limiting. Insufficient amounts of polymer resulted in the formation of bare patches on the magnetite surface, and the strong van der Waals attraction induced cluster formation.