The modulation of coupling in the relaxation behavior of light transmitted through binary ferrofluids

With an external magnetic field, a relaxation process is observed when the light transmit through binary ferrofluids composed of ferrimagnetic CoFe₂O₄ and paramagnetic p-NiFe₂O₄ nanoparticles similar to ferrofluids consisting only of CoFe₂O₄. Since only the ferrimagnetic nanoparticles are able to form field-induced chainlike structures for such binary ferrofluids by magnetic interaction between the particles, so the relaxation behavior of the transmitted light is caused mainly by the ferrimagnetic system. In the binary ferrofluids, the paramagnetic nanoparticles, regarded as magnetically polarized gas molecules, are restrained to occupy the space between the ferrimagnetic chains and distribute following the CoFe₂O₄ particle chains covering and diverging, producing a modulation effect on the relaxation behavior of the transmitted light. The modulation effect can be characterized by range and time parameters that describe the relationship of the relaxation behavior of the transmitted light to the properties of the binary ferrofluids and single CoFe₂O₄ ferrofluids.     

Ferrite-based magnetic nanofluids used in hyperthermia applications

Magnetic ferrofluids (magnetic nanofluids) have received special attention due to their various biomedical applications such as drug delivery and hyperthermia treatment for cancer. The biological applications impose some special requirements. For example, the well-known iron oxide ferrofluids become undesirable because their iron atoms are poorly distinguishable from those of hemoglobin. A conceivable solution is to use mixed-ferrites (MFe₂O₄ where M=Co, Mn, Ni, Zn) to have a range of magnetic properties. These ferrites have attracted special attention because they save time, and because of their low inherent toxicity, ease of synthesis, physical and chemical stabilities and suitable magnetic properties. Based on the importance of ferrite particles in ferrofluids for hyperthermia treatment, this paper gives a summary on the physical concepts of ferrofluids, hyperthermia principal, magnetic properties and synthesis methods of nanosized ferrites.     

A magnetic field-dependent modulation effect tends to stabilize light transmission through binary ferrofluids

In binary ferrofluids composed of ferromagnetic γ?Fe₂O₃/Ni₂O₃ composite nanoparticles (A particles) and noncrystalline Fe₂O₃ nanoparticles (B particles), the A particles alone will form chain-like aggregates upon application of a magnetic field. Due to both the long-range ‘magnetic convergent force’ (F_C) and the short-range ‘magnetic divergent force’ (F_D), the A-particle chains immersed in the B-particle ‘sea’ will move in a manner similar to the process of vibrational damping. The apparent damping of the ferrofluids will vary from weak to overdamping according to the motion of the chains, so that the intensity of light transmitted through a ferrofluid film along the direction of the field would tend to stabilize after a period of rapid decrements and increments. In binary ferrofluids, the B-particle system can produce a modulation effect on both the damping and the driving force, further stabilizing the behavior of the transmitted light. At low fields (e.g., 500 Gs, 900 Gs) only the modulation of the viscosity drag force (F_v) is considerable, so that overdamping increases linearly with B-particle volume fraction (Ф_B), and the variation in the transmitted light is much slower during the process tending towards stability as Ф_B increases. However, at high fields (e.g., 1300 Gs) the polarization of the B-particle ‘sea’ is enhanced, so that F_D is modulated as well as F_v (i.e., both the practical damping and driving forces are modulated simultaneously). Thus, the apparent overdamping of the binary ferrofluids system will vary non-linearly as Ф_B increases, and the transmitted light will tend to stabilize faster for ferrofluids with high Φ_B than for those with low Ф_B at an applied magnetic field of 1300 Gs.     

Relaxation process and ferromagnetic resonance investigation of ferrofluids with Mn–Zn and Mn–Fe mixed ferrite particles

The magnetic relaxation processes in two ferrofluids with Mn_0.4Zn_0.6Fe₂O₄ (sample F1) and Mn_0.6Fe_0.4Fe₂O₄ (sample F2) mixed ferrite particles, dispersed in n-decan and kerosene, respectively, are investigated through the determination of components χ′ and χ′′ of the complex magnetic susceptibility in the range of (2–30) MHz. The values of the saturation magnetization of the two ferrofluids are M_∞=5.28 kA/m for sample F1 and M_∞=10.99 kA/m for sample F2. A maximum of the imaginary component χ′′ was observed for both samples at frequencies of tens MHz. This maximum was assigned to relaxation processes of Néel type.The effective anisotropy constant K of the particles from the studied samples was evaluated, using both static and dynamic measurements and the values were found to be K₁=6.12×10³ J m⁻³ for the ferrofluid F1, and K₂=5.60×10³ J m⁻³ for the ferrofluid F2. From ferromagnetic resonance measurements, and based on the theoretical values computed for the Lande factor (g), the effective anisotropy constants for the mixed ferrite particles in the studied ferrofluids and the anisotropy field values were determined using a new method. The values obtained in this way for the anisotropy constants K₁ and K₂ are compared to the ones determined from magnetic relaxation measurements.     

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.     

Study of polydiethylsiloxane-based ferrofluid with excellent frost resistance property

The polydiethylsiloxane-based ferrofluid was prepared by dispersing finely divided magnetic Fe₃O₄ particles which are modified with oleoyl sarcosine and lauroyl sarcosine. The optimized experiment parameters including molar ratio of surfactant to Fe₃O₄ (1:5), temperature (80 °C), stirring rate (300 RPM), the surfactant content of lauroyl sarcosine (0 to 33 mol%) and the modification time (25 min) were obtained by the orthogonal test. The magnetic liquid was characterized by a transmission electron microscope (TEM), infrared (IR) spectrometer, X-ray diffractometer (XRD), thermogravimetry (TG), vibrating sample magnetometer (VSM) and differential scanning calorimetry (DSC). It is indicated that the surfactant is mainly bonded to the surface of Fe₃O₄ nanoparticles through covalent bond between carboxylate (COO⁻) and Fe atom. The modified magnetic particles are equally dispersed into the carrier and remain stable below −12 °C over 4 months. The ferrofluids exhibit excellent frost resistance property and distinctly reduced temperature coefficient of viscosity compared with polydimethylsiloxane-based ferrofluids and hydrocarbon-based ferrofluids, respectively. The saturation magnetization could reach up to 27.7 emu/g.     

Relaxation behavior measuring of transmitted light through ferrofluids film

In this paper, relaxation behavior of transmitted light through thin ferrofluid film under an applied magnetic field is measured. The results show that the intensity of transmitted light through a ferrofluid film increases quickly as soon as an external magnetic field is applied then weakens with time. If uniformity of the field is poor, the transmission of light continuously decreases in a measured duration. Otherwise, the transmission of light will tend increasingly towards a stable value after it decreases to a minimum value while the gradient of the field is low. The relaxation time would increase to an order of some hundreds seconds magnitude and is dependent on the strength of magnetic field and viscosity of the ferrofluids. The field-induced relaxation behaviors of transmitted light through ferrofluids correspond to anisotropic microstructure of the ferrofluids under applied magnetic field. PACS 75.50.Mm; 78.20.Ls     

Mössbauer spectroscopic characterization of manganese and cobalt ferrite ferrofluids

Aqueous ferrofluids based on Mn and Co ferrites have been synthesized by a novel method. Mössbauer spectra of dried samples (average particle diameter ≈ 10 nm) were measured in the 77–340 K temperature range. CoFe₂O₄ spectra show no superparamagnetic (SP) relaxation, in accordance with the high magnetic anisotropy of this compound. MnFe₂O₄ spectra exhibit SP relaxation, from which an effectiveK=(8±3)×10⁴ J/m³ is estimated. This value represents a 20× enhancement over intrinsic magnetocrystalline anisotropy.     

Simple theory of superparamagnetism and spin-tunneling in Mössbauer spectroscopy

The magnetic relaxation of isolated small (< 100 Å) monodomain magnetic particles is due to superparamagnetic relaxation (predominant at high temperatures) and eventually quantum tunneling of the magnetic moment (at low temperatures). The superparamagnetic relaxation process can be formally described by an (multiple phonon absorption and emission) Orbach process with an anisotropy Hamiltonian due to crystalline or form anisotropy \widehat_Ion = S² _z and a usual dynamical spin-Hamiltonian for the spin--phonon interaction. From this Mössbauer spectra can be calculated using ab-initio or stochastic methods. Phonon-assisted tunneling and its influence on Mössbauer spectra are discussed.     

Influence of solvent on the superparamagnetic relaxation of nanocrystalline Fe3O4 in ferrofluids

Mössbauer spectra for 5 nm Fe₃O₄ nanocrystallites coated with different surfactants were measured and show a significant influence on superparamagnetic relaxation with and without the solvent in ferrofluids.     

Magnetic and optical response of tuning the magnetocrystalline anisotropy in Fe3O4 nanoparticle ferrofluids by Co doping

Co_xFe_3−xO₄ (0?x?0.10) nanoparticles coated with tetramethyl ammonium hydroxide as a surfactant were synthesized by a co-precipitation technique. The Fe:Co ratio was tuned up to x=0.10 by controlling the Co²⁺ concentration during synthesis. The mean particle size, determined by transmission electron microscopy, ranged between 15±4 and 18±4 nm. The superparamagnetic blocking temperature and the magnetocrystalline anisotropy constant of the ferrofluids, determined using ac and dc magnetic measurements, scale approximately linearly with cobalt concentration. We also find distinct differences in the optical response of different samples under an applied magnetic field. We attribute changes in field-induced optical relaxation for the x=0 and 0.05 samples to differences in the anisotropic microstructure under an applied magnetic field.     

A study of modified Fe3O4 nanoparticles for the synthesis of ionic ferrofluids

XRD and XPS analyses revealed that a Fe(NO₃)₃·9H₂O layer formed outside γ-Fe₂O₃ particles when Fe₃O₄ nanoparticles were treated with ferric nitrate. The particle density differed for untreated and treated particles and was not uniform for the latter. The specific saturation magnetization of both treated and untreated particles was used to estimate the thickness of the Fe(NO₃)₃·9H₂O layer and the average density of the treated particles. The density of the treated particles was used to calculate the density of ferrofluids of different particle volume fractions. These values are in agreement with measured results. Therefore, the particle volume fraction can be designed to synthesize acid ionic ferrofluids based on Fe₃O₄ nanoparticles using Massart's method.     

Study of surface morphology of ferrofluid deposited etched ion tracks in dielectric layers

An AFM study is reported on swift heavy irradiated Si/SiO₂ substrates which have been etched by aqueous hydrofluoric acid solution leading to ion tracks in which ferrofluids have been deposited leading to tunable electronic materials with pores in oxide on silicon (TEMPOS) structure. Two ferrofluids with different carrier fluids (aqueous and non-aqueous) have been deposited in the tracks. Atomic force microscopy has been used to study the empty as well as filled tracks. Since the ferrofluids contain iron oxide particles, there is a possibility of agglomeration of these particles inside and outside the tracks. Surface area and pore volume of the tracks have been measured by Brunauer-Emmett-Teller (BET) method. The track properties (empty and filled) as observed by AFM have been correlated with BET measurements.     

Structure of Co-Zn ferrite ferrofluid: A small angle neutron scattering analysis

A hydrothermal synthesis route is used to synthesize nanomagnetic particles of Co_0.3Zn_0.7Fe₂O₄ ferrite ferrofluids with particle diameter ranging from 5.5–9 nm. XRD analysis shows the formation of a single phase spinel structure. EDX results confirm the stoichiometric composition of the cations. Small angle neutron scattering technique is used to determine the size and size distribution of Co_0.3Zn_0.7Fe₂O₄ ferrofluid. The sizes thus obtained are in the range of 5.4 to 8.4 nm. These results are in agreement with magnetic measurements.      

Anisotropy and relaxation processes of uniaxially oriented CoFe2O4 nanoparticles dispersed in PDMS

When a uniaxial magnetic field is applied to a non-magnetic dispersive medium filled with magnetic nanoparticles, they auto-assemble into thin needles parallel to the field direction, due to the strong dipolar interaction among them. We have prepared in this way magnetically oriented nanocomposites of nanometer-size CoFe₂O₄ particles in a polydimethylsiloxane polymer matrix, with 10% w/w of magnetic particles. We present the characteristic magnetic relaxation curves measured after the application of a magnetic field forming an angle α with respect to the needle direction. We show that the magnetic viscosity (calculated from the logarithmic relaxation curves) as a function of α presents a minimum at α=0, indicating slower relaxation processes associated with this configuration of fields. The results seems to point out that the local magnetic anisotropy of the nanoparticles is oriented along the needles, resulting in the macroscopic magnetic anisotropy observed in our measurements.     

Synthesis and characterization of magnetite particles covered with α-trietoxysilil-polydimethylsiloxane

New silicon magnetite ferrofluids were prepared by dispersing siloxane-coated magnetite particles in polydimethylsiloxane with low or high molecular weights. Ferrofluids are stable colloidal dispersions of ultra fine covered magnetite particles, which may be selected for a specific application. We demonstrated new methods of stabilizing the magnetic particles by reacting the hydroxyl groups on the surface of magnetite particles with terminal ethoxy groups of polydimethylsiloxane, followed by their dispersion in silicon fluids. The new silicon ferrofluids were tested from the morphology, magnetic properties/losses, and rheological properties point of view.     

Size effects in monodomain magnetite based ferrofluids

Ferrofluids based on two types of hybrid particles Fe₃O₄/β-cyclodextrin were prepared: Using monodomain (below 60 nm) magnetite nanoparticles with (A) non-superparamagnetic (non-SPM) behaviour and (B) with superparamagnetic (SPM) behaviour. We found a strong dependence of the hybrid particles’ magnetic properties on their size and homogeneity. In both types of ferrofluids we observed hyperthermia upon applying an ac electromagnetic field with frequency 40 kHz and amplitude 30 kA/m. The maximal ΔТ upon irradiation with duration of about 12 min for the non-SPM particles was 12 °C, while for the SPM ones it was 3.5 °C.     

Synthesis of aqueous ferrofluids of ZnxFe3−xO4 nanoparticles by citric acid assisted hydrothermal-reduction route for magnetic hyperthermia applications

Superparamagnetic and monodispersed aqueous ferrofluids of Zn substituted magnetite nanoparticles (Zn_xFe_3−xO₄, x=0, 0.25, 0.3, 0.37 and 0.4) were synthesized via hydrothermal-reduction route in the presence of citric acid, which is a facile, low energy and environmental friendly method. The synthesized nanoparticles were characterized by X ray diffraction (XRD) analysis, Fourier transform infrared (FTIR) spectroscopy, scanning and transmission electron microscopy (SEM and TEM) and the dynamic light scattering (DLS) method. The results showed that a certain amount of citric acid was required to obtain single phase Zn substituted magnetite nanoparticles. Citric acid acted as a modulator and reducing agent in the formation of spinel structure and controlled nanoparticle size and crystallinity. Mean particle sizes of the prepared nanoparticles were around 10 nm. The results that are obtained from XRD, magnetic and power loss measurements showed that the crystallinity, saturation magnetization (M_S) and loss power of the synthesized ferrofluids were all influenced by the substitution of Zn in the structure of magnetite. The Zn substituted magnetite nanoparticles obtained by this route showed a good stability in aqueous medium (pH 7) and hydrodynamic sizes below 100 nm and polydispersity indexes below 0.2. The calculated intrinsic loss power (ILP) for the sample x=0.3 (e.g. 2.36 nH m²/kg) was comparable to ILP of commercial ferrofluids with similar hydrodynamic sizes.     

Glass like magnetic alternating field susceptibility behavior of structurally frozen ferrofluids

Four ferrofluids, distinct in size distribution and aggregate structure, were investigated. The relaxation time ,related to the temperature of susceptibility maximum, was fitted to a Vogel-Fulcher law. A mean ordering temperature, T₀, was calculated using magnetic particle parameters derived from the structure. It is assumed that at T₀ the particle moments of particle clusters correlate, leading to a spin glass-like transition. Hence, then dynamic slows down considerably, as indicated by a strong broadening of relaxation-time distribution. T₀ roughly agrees with the energy of competing interaction between particle moments, as calculated from the structure of particle aggregates. Differences between particle arrangements clearly influence the dispersion and absorption, particularly within the cluster phase. Received 15 July 1998     

The quasi-magnetic-hysteresis behavior of polydisperse ferrofluids with small coupling constant

The magnetization behaviors of ferrofluids based on γ-Fe₂O₃/Ni₂O₃ composite nanoparticles of size about 11 nm have been investigated. The dipole coupling constant λ of these particles is so small (0.43) that they cannot form aggregates through magnetic interaction alone. Experimental results have shown that for a polydisperse ferrofluid with a particle volume fraction of ?_V=2.4%, the magnetization curve exhibits quasi-magnetic-hysteresis behavior, i.e., the demagnetization curve lies above the magnetization curve in a high field. However, for a more dilute γ-Fe₂O₃/Ni₂O₃ ferrofluid with ?_V=0.94%, the magnetization curve does not show such behavior. According to the bidisperse model for polydisperse ferrofluids, these magnetization behaviors may be attributed to field-induced effects of self-assembled pre-existing chain-like aggregates. For such pre-existing chain-like aggregates, the orientation of the moments inside the particles is not co-linear, so that during the magnetization and demagnetization processes, their apparent magnetizations at the high-field limit are different. As a consequence, the magnetization curve of the ferrofluid with ?_V=2.4% displays quasi-magnetic-hysteresis.