Magnetic and Mössbauer studies of fucan-coated magnetite nanoparticles for application on antitumoral activity

Fucan-coated magnetite (Fe₃O₄) nanoparticles were synthesized by the co-precipitation method and studied by Mössbauer spectroscopy and magnetic measurements. The sizes of the nanoparticles were 8–9 nm. Magnetization measurements and Mössbauer spectroscopy at 300 K revealed superparamagnetic behavior. The magnetic moment of the Fe₃O₄ is partly screened by the Fucan coating aggregation. When the magnetite nanoparticles are capped with oleic acid or fucan, reduced particle-particle interaction is observed by Mössbauer and TEM studies. The antitumoral activity of the fucan-coated nanoparticles were tested in Sarcoma 180, showing an effective reduction of the tumor size.     

Ferrimagnetic to Paramagnetic Transition in Magnetite: Mössbauer versus Monte Carlo

Powder magnetite was analyzed in situ via Mössbauer with temperatures ranging from 170 K up to 900 K. Hyperfine fields of the tetrahedral and octahedral sites of magnetite as well as the corresponding average field were followed as a function of temperature in order to elucidate the critical behavior of magnetite at around the Curie temperature. Results evidence a progressive collapse of the Mössbauer spectra onto a singlet-type line at a critical temperature of around 870 K characterized by a critical exponent β = 0.28(2) for the hyperfine field. In order to describe such temperature dependence of the hyperfine field, a Monte Carlo-Metropolis simulation based on a stoichiometric magnetite and an Ising model with nearest magnetic neighbor interactions was also carried out. In the model, we have taken into account antiferromagnetic and ferromagnetic interactions depending on the involved ions. A discussion about the critical behavior of magnetite and a comparison between the hyperfine field obtained via Mössbauer and the magnetization obtained via Monte Carlo is finally presented.     

Magnetic composites from minerals: study of the iron phases in clay and diatomite using Mössbauer spectroscopy, magnetic measurements and XRD

Magnetic particles as matrix for enzyme immobilization have been used and due to the enzymatic derivative can be easily removed from the reaction mixture by a magnetic field. This work presents a study about the synthesis and characterization of iron phases into magnetic montmorillonite clay (mMMT) and magnetic diatomaceous earth (mDE) by ⁵⁷Fe Mössbauer spectroscopy (MS), magnetic measurements and X-ray diffraction (XRD). Also these magnetic materials were assessed as matrices for the immobilization of invertase via covalent binding. Mössbauer spectra of the magnetic composites performed at 4.2 K showed a mixture of magnetite and maghemite about equal proportion in the mMMT, and a pure magnetite phase in the sample mDE. These results were verified using XRD. The residual specific activity of the immobilized invertase on mMMT and mDE were 83 % and 92.5 %, respectively. Thus, both magnetic composites showed to be promising matrices for covalent immobilization of invertase.     

Synthesis of magnetic nanoparticles: effects of polyelectrolyte concentration and pH

This study refers to the effect of sodium polyacrylate concentration (1 to 5 mass %) and pH (10 to 12) on the synthesis of magnetic nanoparticles (magnetite?Cmaghemite) and their characterization by Mössbauer spectroscopy. The magnetic particles were obtained by coprecipitation method using iron chloride (II) and iron chloride (III) as precursor reagents and sodium polyacrylate as stabilizing agent. All samples showed Mössbauer broad resonance lines in typical doublet and sextets patterns of magnetite or maghemite with corresponding wide particle size distributions. The stability of magnetic particles was carried out by measuring particle sizes with dynamic light scattering (DLS). The z-average values for magnetic particles were in the range 24 to 590 nm and no significant change in size was observed on aging by leaving this material in air for 20 days. X-ray diffraction patterns showed characteristic peaks of the spinel structure and have an increase in their broadening as the pH decreases, effect that is dominated by the decrease in crystallite sizes. The nanoparticles showed to be magnetic at pH 12 and at room temperature.     

Mössbauer spectroscopy study of iron oxide nanoparticles obtained by spray pyrolysis

Mössbauer spectroscopy was used in this study to investigate magnetite nanoparticles, obtained by spray pyrolysis and thermal treatment under H₂ reduction atmosphere. Room temperature XRD data indicate the formation of magnetite phase and a second phase (metallic iron) which amount increases as the time of reduction under H₂ is increased. While room temperature Mössbauer data confirm the formation of the cubic phase of magnetite and the occurrence of metallic iron phase, the more complex features of 77 K-Mössbauer spectra suggest the occurrence of electronic localization favored by the different crystalline phase of magnetite at low temperatures which transition to the lower symmetry structure should occur at T ～120 K (Verwey transition).     

Mössbauer study of Cu1−xZnxFe2O4 catalytic materials

In the present work, we have synthesized and characterized magnetic nanoparticles of maghemite γ-Fe₂O₃ to study their structural and magnetic properties. For the preparation, magnetite precursor, were oxidized by adjusting the pH = 3.5 at about 80 °C in an acid medium, The mean size of the maghemite particles calculated from the X-ray diffractogram was around 5.7 nm. Mössbauer spectroscopy measurements at room temperature show their superparamagnetic behavior. Furhermore, Mössbauer measurements were carried out at 77 K and 4.2 K in order to find the typical hyperfine fields of the maghemite. Magnetite phase was not found. FC and ZFC magnetization curves measured at 500 Oe indicate a blocking temperature of 105.3 K. The magnetization measurements also show almost zero coercivity at RT. TEM images show nanoparticles with diameter smaller than 10 nm, which are in good agreement with the X-ray pattern and the fitting of the magnetization data.     

Magnetite nanoparticles as-prepared and dispersed in Copaiba oil: study using magnetic measurements and Mössbauer spectroscopy

Study of magnetite nanoparticles, as-prepared and dispersed in Copaiba oil as magnetic fluid, by means of magnetic measurement and Mössbauer spectroscopy at various temperatures demonstrated differences in the saturation magnetization and Mössbauer hyperfine parameters which were related to the interactions of Copaiba oil polar molecules with iron cations on magnetite nanoparticle’s surface.     

Mössbauer study of a Fe3O4/PMMA nanocomposite synthesized by sonochemistry

Magnetite nanoparticles of 10 nm average size were synthesized by ultrasonic waves from the chemical reaction and precipitation of ferrous and ferric iron chloride (FeCl₃ · 6H₂O y FeCl₂ · 4H₂O) in a basic medium. The formation and the incorporation of the magnetite in PMMA were followed by XRD and Mössbauer Spectroscopy. These magnetite nanoparticles were subsequently incorporated into the polymer by ultrasonic waves in order to obtain the final sample of 5 % weight Fe₃O₄ into the polymethylmethacrylate (PMMA). Both samples Fe₃O₄ nanoparticles and 5 % Fe₃O₄/PMMA nanocomposite, were studied by Mössbauer spectroscopy in the temperature range of 300 K–77 K. In the case of room temperature, the Mössbauer spectrum of the Fe₃O₄ nanoparticles sample was fitted with two magnetic histograms, one corresponding to the tetrahedral sites (Fe^3?+?) and the other to the octahedral sites (Fe^3?+? and Fe^2?+?), while the 5 % Fe₃O₄/PMMA sample was fitted with two histograms as before and a singlet subspectrum related to a superparamagnetic behavior, caused by the dispersion of the nanoparticles into the polymer. The 77 K Mössabuer spectra for both samples were fitted with five magnetic subspectra similar to the bulk magnetite and for the 5 % Fe₃O₄/PMMA sample it was needed to add also a superparamagnetic singlet. Additionally, a study of the Verwey transition has been done and it was observed a different behavior compared with that of bulk magnetite.     

Mechanochemical and magnetomechanical synthesis of hematite nanoparticles

Samples of hematite were exposed to mechanochemical activation by high energy ball milling for 0–27 h. The milling-induced changes to the structural and magnetic properties of hematite were characterized by X-ray diffraction (XRD) and Mössbauer spectroscopy. The particle size was found to decrease from 80 to 16.5 nm after 8 h of ball milling time, followed by a small increase to 19.8 nm at the end of the milling period. An overall expansion of the crystalline lattice parameters a and c with the milling time was deduced. The magnetic hyperfine field decreased with the ball milling time, from 51.46 down to 50.68 T after 27 h of grinding. Magnetite and traces of iron were observed at the longest milling time employed. The recoilless fraction (f ) was measured simultaneously using a dual Mössbauer absorber consisting of hematite and a stainless steel etalon. The f factor first decreased with the milling time due to occurrence of nanoparticles in the system, had a maximum at 12 h due to agglomerations of nanoparticles and exhibited a second maximum at 27 h, due to the appearance of magnetite in the system. More samples of hematite were subjected to magnetomechanical activation by magnetic ball milling for 52 and 134 h. A phase mixture of hematite and magnetite was observed.     

Surface oxidation control of nanosized magnetite and Mössbauer measurements

Selected highly homogeneous powders of Fe₃O₄ with different particle size on the nanometer scale (10?±?2 and 3?±?2 nm) obtained by soft-chemical methods were studied by Mössbauer spectroscopy. The study shows clearly the powerful possibilities of Mössbauer spectroscopy to analyze the surface oxidation of nanostructured powders of magnetite. On the other hand, it is shown that for very small superparamagnetic particles the spectrum of magnetite might be quite similar to that of maghemite, making it difficult to distinguish between both phases.     

Synthesis and characterization of uncoated and gold-coated magnetite nanoparticles

We report on the synthesis and characterization of uncoated and gold coated magnetite nanoparticles. Structural characterizations, carried out using X-ray diffraction, confirm the formation of magnetite phase with a mean size of ~7 and ~8 nm for the uncoated and gold covered magnetite nanoparticles, respectively. The value of the gold coated Fe₃O₄ nanoparticles is consistent with the mean physical size determined from transmission electron microscopy images. Mössbauer spectra at room temperature are consistent with the thermal relaxation of magnetic moments mediated by particle-particle interactions. The 77 K Mössbauer spectra are modeled with four sextets. Those sextets are assigned to the signal of iron ions occupying the tetrahedral and octahedral sites in the core and shell parts of the particle. The room-temperature saturation magnetization value determined for the uncoated Fe₃O₄ nanoparticles is roughly ~60 emu/g and suggests the occurrence of surface effects such as magnetic disorder or the partial surface oxidation. These surface effects are reduced in the gold-coated Fe₃O₄ nanoparticles. Zero-field–cooled and field-cooled curves of both samples show irreversibilities which are consistent with a superparamagnetic behavior of interacting nanoparticles.     

Mössbauer and mineral magnetic studies on archaeological potteries from Adhichanallur, Tamilnadu, India

Megalithic potteries collected from Adhichanallur, Tamilnadu, India (Lat. 8°44′ N; Long. 77°42′ E) have been subjected to various spectroscopic and rock magnetic studies. The type of clay, their origin, level of structural deformation due to firing, firing temperature and atmospheric condition followed during making the potteries are analyzed. The potteries were subjected to Mössbauer and X-ray diffraction studies to analyze the iron phases in them. It is found that the samples were made of local clay (red clay), fired above 600°C under open atmospheric and/or reduced atmospheric conditions and air has been allowed during cooling. The Mössbauer spectra reveal the presence of Fe^3?+?, Fe^2?+? and iron oxides of hematite and magnetite. The firing temperature and firing conditions established from Mössbauer studies are similar to the observation made from FT-IR studies. The magnetic mineral types, the mass fractions and the domain states of the constituent magnetic grains were elucidated from a range of rock magnetic measurements including variation of susceptibility with low field, frequency and temperature, hysteresis parameters and isothermal remanence acquisition data. The magnetic mineralogy of most pottery samples was dominated by magnetite/(titano) magnetite, while magnetic grain size spectrum varies from very fine (super paramagnetic) to fine (stable single domain, pseudo single domain). The reversible thermo magnetic behavior reflects no mineralogical transformations during reheating and all the samples show same Curie temperature 580°C due to magnetite. From the above information it is demonstrated that these samples are suitable for determining the reliable ancient geomagnetic field intensity values existed during that period.     

Temperature dependence of the hyperfine parameters of the iron bearing phases in the Mössbauer spectra collected by the Mars Exploration Rover Spirit

This contribution focuses on the Mössbauer spectra acquired by the Mars Exploration Rover Spirit which carried a MIMOS II Mössbauer spectrometer. Only those spectra which present a reasonable statistical quality were selected to for this study. Twenty five Mössbauer spectra have been considered. Common phases identified from the temperature dependent hyperfine parameters are olivine, pyroxene, hematite and magnetite. It is believed that the applied analysis method has provided accurate values for the various hyperfine data averaged over single 10 K temperature intervals in the range 210–260 K. The obtained results, to some extent forced to evolve consistently over the various ΔT intervals considered for a given soil/rock target, are in many cases different from previously published data. Possible reasons for these differences will be discussed.     

Evidence of magnetic broadening in Mössbauer spectra of superconducting FeTe 0.8 S 0.2

Magnetic properties of the FeTe_0.8S_0.2 superconductor were studied by Mössbauer spectroscopy. Low-velocity Mössbauer spectra that were recorded in the temperature range from 5.7 K up to 300 K show a paramagnetic doublet with a broadening at temperatures below 77 K. The broadening can be explained by the appearance of a distribution of hyperfine magnetic fields due to the magnetic ordering of a part of the sample. The magnetically ordered fraction starts to decrease at temperatures below 20 K indicating a possible competition with the onsetting superconductive state.     

Evidence for direct observation by Mössbauer spectroscopy of surface tin atoms in platinum–tin particles

The diamond-bearing gravels found along South Africa's West Coast are being beneficiated by means of dense medium separation (DMS) to reclaim the alluvial diamonds. Granular ferrosilicon (Fe–Si) is used as the DMS material and at the end of each operation the Fe–Si is reclaimed from the process stream using a magnetic separator and is then recycled but losses of Fe–Si due to attrition, adhesion to the separation products, density changes and changes to the magnetic properties can occur. The gravel obtained from the mining operation is washed and screened before heavy mineral separation. The concentrate, tailings and Fe–Si samples were investigated by means of SEM and Mössbauer spectroscopy to determine where changes to the Fe–Si, or contamination could occur. The composition of the Fe–Si was determined to be Fe (76.1 at.%), Si (20.3 at.%), Mn (1.5 at.%), Al (1.5 at.%) and Cr (0.6 at.%) resulting in a more or less ordered DO₃ phase with a calculated composition of Fe₃Si for this Fe–Si, consistent with the Mössbauer results where two sextets with hyperfine magnetic fields of 18.6 T and 28.4 T were observed. After DMS, magnetite and ilmenite, the minerals found in the gravel, were still present in the concentrate. In the tailings virtually no magnetite or ilmenite was found and only a doublet, identified as an oxihydroxide, due to the abrasion of the Fe–Si, was found. After magnetic separation, to wash and clean the Fe–Si for re-use, it was found that magnetite and ilmenite were still present in the Fe–Si, which results in a change in density of the Fe–Si, resulting in a higher density and loss of valuable diamonds.     

Magnetic and Mössbauer spectroscopic studies of NiZn ferrite nanoparticles synthesized by a combustion method

The properties of nanocrystalline Ni_0.5Zn_0.5Fe₂O₄ synthesized by an auto-combustion method have been investigated by magnetic measurements and Mössbauer spectroscopy. The as-synthesized single phase nanosized ferrite powder is annealed at different temperatures in the range 673–1,273 K to obtain nanoparticles of different sizes. The powders are characterized by powder X-ray diffraction, vibrating sample magnetometer, transmission electron microscopy and Mössbauer spectroscopy. The as-synthesized powder with average particle size of ~9 nm is superparamagnetic. Magnetic transition temperature increases up to 665 K for the nanosized powder as compared to the transition temperature of 548 K for the bulk ferrite. This has been confirmed as due to the abnormal cation distribution, as evidenced from room temperature Mössbauer spectroscopic studies.     

Separation of Contributions of the Magnetic Relaxation and Diffusion of Nanoparticles in Ferrofluids by Analyzing the Hyperfine Structure of Mössbauer Spectra

The theory and method for analysis of Mössbauer spectra of magnetic nanoparticles in a fluid have been developed by generalizing the model of the magnetic dynamics of a Néel ensemble of antiferromagnetic particles to the case of ferrimagnetic iron oxides. The resulting model describing the “superposition” of the magnetic dynamics and translational motion of nanoparticles in ferrofluids has been tested in application to the simultaneous analysis of Mössbauer spectra of “dry” magnetite nanoparticles and the same particles in glycerol.     

Hyperfine interaction characterization of iron minerals in Brazilian monazite sands

The Mössbauer spectra both at 300 K and 84 K of the naturally occuring monazite sands from the beaches of Marataizes (40°49′ 11.4″ LW and 21°02′ 26.7″ LS) indicate a paramagnetic phase of nearly 21% absorption and three other phases, including magnetic phases, of nearly 4% absorption each. Chemical analysis, X-ray diffraction and X-ray fluorescence alongwith Mössbauer spectra confirm these to be ilmenite, hematite, magnetite and orthopyroxene (chain silicate) minerals. Presence of a number of other non-iron minerals was also detected.     

Structural characterization and magnetic properties of NiMg3x/2Cr0.9Fe1.1 − x O4

Magnesium-substituted nickel–chrome ferrites have been studied using X-ray diffraction and Mössbauer spectroscopy. A single cubic spinel phase was obtained in the range 0.0?≤?x?≤?0.4. The lattice parameter was found to decrease with the increase of Mg concentration. The Mössbauer spectra measured at 295 and 78 K of all samples showed magnetic patterns interpreted in term of the tetrahedral and octahedral sites occupancies. The magnetic hyperfine field of both sites decrease with the increase of the Mg concentration. The magnetic properties as a function of the Mg concentration have been explained on the basis of the cation distribution among the two crystallographic sites driven from the Mössbauer measurements.     

237Np and 57Fe Mössbauer study of NpFeGa5

⁵⁷Fe and ²³⁷Np Mössbauer ōmeasurements have been performed for NpFeGa₅, which is one of the so-called neptunium 1-1-5 compounds. The ⁵⁷Fe Mössbauer spectra below T _N = 118 K show the magnetically ordered state. The magnitude of the hyperfine magnetic field at the ⁵⁷Fe nucleus is determined to be 1.98 ± 0.05 T at 10 K. From the ²³⁷Np Mössbauer spectrum at 10 K, the hyperfine magnetic field at the ²³⁷Np nucleus is 203 T and the hyperfine coupling constant is determined to be 237 T/μ_B using the Np atomic magnetic moment of 0.86 μ_B determined by the neutron diffraction study.