Magnetic properties of disordered ferrite and ilmenite-hematite thin films

We have synthesized thin films of disordered zinc ferrite (ZnFe₂O₄) and ilmenite-hematite (FeTiO₃-Fe₂O₃) solid solution, the former and the latter of which are interesting from the viewpoints of magnetooptics and spintronics, respectively, by utilizing sputtering and pulsed laser deposition methods, and have explored their magnetic, magnetooptical, and electrical properties. Although ZnFe₂O₄ possesses a normal spinel structure as its stable phase, some of the Fe³⁺ ions occupy the tetrahedral as well as the octahedral sites in ZnFe₂O₄ of which the sputtered thin film is composed. Consequently, the as-deposited thin film manifests large magnetization even at room temperature although the magnetic phase transition temperature of the stable phase of ZnFe₂O₄ is as low as 10 K. Also, the thin film exhibits a cluster spin glass transition at a temperature as high as 325 K. Furthermore, the ZnFe₂O₄ thin films exhibit large Faraday effects at a wavelength of 400 nm or so. The ilmenite-hematite solid solution is one of the ferrimagnetic semiconductors. Most of the compositions possess Curie temperatures higher than room temperature, and the type of carrier can be tuned only by changing the composition. We have succeeded in synthesizing solid-solution thin films of various compositions grown epitaxially on sapphire substrates with a (0 0 0 1) plane, and have shown that the thin films are ferrimagnetic semiconductors.     

Magnetic properties of polycrystalline films of CoCr2O4 and CoFe0.5Cr1.5O4 multiferroics

This paper reports on the first study of the magnetic properties of polycrystalline films of CoCr₂O₄ and CoFe_0.5Cr_1.5O₄ multiferroics. The study covered, in particular, magnetization reversal curves and temperature dependences of the magnetization at temperatures ranging from 4.2 to 300 K in magnetic fields of up to 10 kOe. It has been shown that the Curie temperature and the pattern of the temperature dependence of the magnetization depend on the cation composition of the multiferroic. The temperature dependence of the magnetization of polycrystalline CoCr₂O₄ films has revealed an anomaly in the temperature range 10–70 K.     

Magnetization anomalies of nanosize zinc ferrite particles prepared using electrodeposition

Nanosize zinc ferrite particles have been prepared for the first time using electrodeposition. Zinc and iron are deposited on the cathode from a common bath containing the salts of zinc and iron. The deposited materials were forced to undergo electrochemical oxidation in a strong alkaline solution (1 M KOH) to convert them into oxides. Crystallization in ZnFe₂O₄ structure was obtained by heating the deposited material at appropriate temperature. X-ray diffraction pattern confirmed that the procedure leads to the formation of pure phase of ZnFe₂O₄. The magnetization value for the smallest size ZnFe₂O₄ is much smaller than that for the ZnFe₂O₄ made by most of the other methods although it shows a nice hysteresis shape. The magnetization shows very little variation with size in the range studied.     

Magnetic relaxation in spinel Mo-ferrite and Ti substituted Mo-ferrite

A compensation temperature of 138 K was observed in the temperature-dependent magnetization curves of MoFe₂O₄. Relatively slow magnetization relaxation characterized the transitions between different spin states (compensated and uncompensated). Large magnetic after effect was found in time-dependent magnetization curves after heating or cooling from different characteristic temperatures for different spin states. The magnetic relaxation was nearly independent on magnetic field, supporting the presence of spin states and no involvement of domain structure. For the Ti substituted Mo_0.6Ti_0.4Fe₂O₄ sample, there were a compensation at ∼ 100 K and a maximum of magnetization at ∼ 175 K. Similar results of anomalous magnetic relaxation was observed in Ti substituted Mo-ferrite (Mo_0.6Ti_0.4Fe₂O₄). If the Mo_0.6Ti_0.4Fe₂O₄ sample was heated from 100 K to 235 K, the time-dependent magnetization curve could be considered as a combination of two magnetic relaxation processes. However, if the sample was heated from 100 K to 295 K, the time- dependent magnetization curve became complex. Received 30 October 2001 and Received in final form 21 January 2002     

Dynamic magnetization of <Emphasis Type="Bold">γ</Emphasis>- nanoparticles isolated in an amorphous matrix

We have studied the magnetization of a system of γ-Fe₂O₃ (0.68 vol.%) nanoparticles isolated in an SiO₂ amorphous matrix placed in an alternating magnetic field with a frequency of 640 Hz and in the temperature range of (77-300) K. Compared to temperatures closer to 300 K (where the system has a superparamagnetic behaviour), at lower temperatures, the magnetization has a dynamic hysteresis loop due to the magnetization's phase shift between the field and the magnetization. The delay of the magnetization (attributed to the Néel relaxation processes) increases with the decrease of temperature. It has been shown that the relaxation time resulting from the Néel theory is determined by an effective anisotropy constant ( K ) that takes into account the magnetocrystalline anisotropy, as well as the shape, surface and strain anisotropies. In the following we will show that the surface and strain anisotropy components have the most significant influence. When the temperature decreases from 300 to 77 K, the relative increase of the saturation magnetization of the nanoparticles is much higher than that of the (spontaneous) saturation magnetization of bulk γ-Fe₂O₃. This increase is due to the increase of the mean magnetic diameter of the particles attached to the core of aligned spins, from 10.16 nm to 11.70 nm, as a result of the modification of the superexchange interaction in the surface layer. Received 25 April 2002 / Received in final form 11 August 2002 Published online 14 February 2003 RID="a" ID="a"e-mail: ccaizer@physics.uvt.ro     

Synthesis and characterization of magnetic diphase ZnFe(2)O(4) /γ-Fe(2)O(3) electrospun fibers

Magnetic nanofibers of ZnFe₂O₄/γ-Fe₂O₃ composite were synthesized by electrospinning from a sol-gel solution containing a molar ratio (Fe/Zn) of 3. The effects of the calcination temperature on phase composition, particle size and magnetic properties have been investigated. Zinc ferrite fibers were obtained by calcinating the electrospun fibers in air from 300 to 800 °C and characterized by thermogravimetric analyses, Fourier transformed infrared spectroscopy, X-ray photoemission spectroscopy, X-ray diffraction, vibration sample magnetometry and magnetic force microscopy. The resulting fibers, with diameters ranging from 90 to 150 nm, were ferrimagnetic with high saturation magnetization as compared to bulk. An increase in the calcination temperature resulted in an increase in particle size and saturation magnetization. The observed increase in saturation magnetization was most likely due to the formation and growth of ZnFe₂O₄/γ-Fe₂O₃ diphase crystals. The highest saturation magnetization (45 emu/g) was obtained for fibers calcined at 800 °C.     

Magnetic properties of nanostructured MnZn ferrite

Mn_0.5Zn_0.5Fe₂O₄ nanoparticles (10-30 nm) have been prepared via mechanochemical processing, using a mixture of two single-phase ferrites, MnFe₂O₄ and ZnFe₂O₄. SQUID measurements (field-cooled magnetization curves and hysteresis loops) were performed to follow the mechanically induced evolution of the MnFe₂O₄/ZnFe₂O₄ mixture submitted to the high-energy milling process. The resulting single MnZn nanoferrite phase was characterized by SQUID (M-H curve), Faraday balance (M-T curve) and transmission electron microscopy. The magnetic characteristics of the mechanosynthesized material were compared with those of bulk Mn_0.5Zn_0.5Fe₂O₄. It was found that the saturation magnetization of nanostructured Mn_0.5Zn_0.5Fe₂O₄ (87.2 emu/g) is lower than that of the bulk Mn_0.5Zn_0.5Fe₂O₄, but, the Néel temperature of the sample (583 K) is higher than that of the bulk Mn_0.5Zn_0.5Fe₂O₄.     

Magnetic susceptibility and magnetic-field behavior of CuB2O4 copper metaborate

An experimental study is reported regarding the temperature dependence of the magnetic susceptibility of a CuB₂O₄ tetragonal single crystal within the 4.2–200-K range. It has been established that the magnetic susceptibility exhibits anomalies at 21 and 10 K and depends strongly on crystal orientation in the magnetic field. A study has been carried out of the field dependences of the magnetization of CuB₂O₄ at various temperatures and crystal orientations. It is shown that for T>21 K, the crystal is in a paramagnetic state determined by Cu²⁺ copper ions with an effective magnetic moment of 1.77 μ_B. Within the 10–21 K interval, the field dependence of the magnetization is typical of a weak ferromagnet with magnetic moments of the two antiferromagnetically coupled sublattices lying in the tetragonal plane of the crystal. The spontaneous weakly-ferromagnetic moment is 0.56 emu/g at 10 K. The canting angle of the sublattice magnetic moments, determined by the Dzyaloshinski-Moriya interaction, is 0.49°. It is believed that below 10 K, the CuB₂O₄ crystal retains its easy-plane magnetic structure, but with a zero spontaneous magnetic moment.     

Mössbauer characterization of LixFe3O4

Mössbauer spectra of lithium intercalated Fe₃O₄, have been recorded at 300 K and 4.2 K. It has been observed that lithium can be incorporated and/or extruded at room temperature. The coexistence of lithiated and unlithiated particles after exposure of the sample to air, is interpreted in terms of the Li⁺-ion mobility. The results are compared with those obtained from X-Ray diffraction data and magnetization measurements.     

Magnetic properties of ZnFe2O4 nanoparticles produced by a low-temperature solid-state reaction method

ZnFe₂O₄ nanoparticles with average grain size ranging from 40 to 60 nm behaving superparamagnetic at room temperature have been produced using a low-temperature solid-state reaction (LTSSR) method without ball-milling process. Abnormal magnetic properties such as S-shape hysteresis loops and non-zero magnetic moments were observed. ZnFe₂O₄ nanoparticles were also synthesized using a NaOH coprecipitation method and a PVA sol-gel method to study the relationship between the preparation processes and the magnetic properties. Spin-glass behavior was observed in the low temperature solid-state reaction produced Zn ferrite in the zero-field cooled (ZFC) measurement. Our work proves that the various preparation methods will to some extent determine the properties of magnetic nanoparticles.     

Study of ferrofluids by Mössbauer spectroscopy

The parameters of the log‐normal size distribution of a MnFe₂O₄ ferrofluid powder sample have been determined by X‐ray diffraction. The mean blocking temperature was determined from the maximum of _Xi . Mössbauer spectra at 4.2–300 K are interpreted by a new simple theory of superparamagnetism and taking a reduction of the internal magnetic field for small particles, a size dependence of the anisotropy constant, the size distribution and collective excitations into account.     

Site preference of Fe in nanoparticles of ZnFe2O4

Nanoparticles of ZnFe₂O_4, prepared by both high-energy ball milling and sol–gel methods, have been investigated by X-ray diffraction and Mössbauer spectroscopy. These results are compared with those for the bulk material. Mössbauer measurements which cover the temperature range 4.2 K to room temperature were acquired in zero field and an applied magnetic field of 5 T. The results show that the Neel temperature T_N of bulk ZnFe₂O₄ is about 9 K, whereas for the nanoparticle it is much higher; furthermore the transition temperature for particles of the same size depends on the preparation technique. The likely origin for this increase of T_N in the nanoparticles, namely the redistribution of Fe and Zn cations on the A and B sites, is proposed and discussed.     

Magnetization of sol-gel prepared zinc ferrite nanoparticles: Effects of inversion and particle size

Nanoparticles of ZnFe₂O₄ have been prepared by using sol-gel method in two different mediums (acidic and basic) in order to observe the influence of the medium on the magnetic properties of the obtained nanoparticles. X-ray diffraction and Mössbauer studies of these samples show the presence of single-phase spinel structure. The average size of the particles as determined by X-ray diffraction increases with the annealing temperature from 18 to 52 nm. With the increase in particle size, magnetization decreases while the magnetization blocking temperature increases. Magnetization studies show that the samples prepared in basic medium have more ferrimagnetic nature as compared to those prepared in acidic medium. We understand this increase in magnetization as reflective of the increased degree of inversion (transfer of Fe³⁺ ions from octahedral to tetrahedral sites) in the particles of smaller size unit cells. From lattice parameter calculations on different particles it is determined that inversion is more favorable in the particles prepared in a basic medium than in the acidic medium due to the smaller cell size in the former.     

High magnetic field properties of mixed terbium-yttrium ferrite garnets

Magnetization measurements in d.c. magnetic fields up to 180 kOe have been performed on polycrystalline specimens and on single crystals of mixed terbium-yttrium iron garnets: Tb _x Y_3–x Fe₅O₁₂ in the 4.2–300 K temperature range. On polycrystals (x=2.5; 2; 1; 0.37) the concentration dependence of both compensation point and spontaneous magnetization has been determined. In the single crystals (x=2; 1; 0.37) a strong magnetic anisotropy has been observed with a change of the easy direction of magnetization from [111] to [100] whenx decreases; abrupt field-induced transitions have been observed at low temperatures when the external field is applied along the [100] direction.     

Novel behavior in the M–H and field cooled (FC) curves of the MnFe2O4 nanoparticles synthesized by the coprecipitation method

MnFe₂O₄ nanoparticles were prepared by a coprecipitation chemical method. The average size of the obtained nanoparticles was about 30 nm. The hysteresis measured at T=300 K clearly shows ferromagnetic order at room temperature while that measured at T=450 K shows superparamagnetic behavior. The difference in the magnetization curves in the field increasing cycle and field decreasing cycle at higher temperatures (450 K or higher) is very unusual. In this case, a hysteresis in magnetization in higher magnetic fields with an opening up of the magnetization curve was observed. In this work, the effect of temperature and time of application of the applied field on the magnetization behavior was studied.     

Magnetization and Mössbauer studies of 57Fe doped SrCoO3

⁵⁷Fe (1%) doped SrCoO₃ obtained by high-pressure method, has been investigated by magnetization and Mössbauer spectroscopy studies (MS) in the temperature range 4.2 K to 300 K. The ferromagnetic ordering temperature T _C obtained is 272(2) K. Isothermal magnetization curves have been measured at various temperatures, from which the saturation moments (M _sat) have been deduced. The ⁵⁷Fe MS spectra display standard six-line patterns with an isomer shift typical of Fe^3?+? and a very small quadrupole splitting (QS = 0.14(1) mm/s above T _C). The magnetic hyperfine field at 4.2 K is 276(1) kOe. The temperature dependencies of the iron hyperfine field and M _sat (1.83 µ _B at 5 K) are almost identical. This shows that the Fe^3?+? is replacing Co^4?+?, both of the same electronic configuration. They also interact similarly, namely the Fe–Co exchange is almost identical to the Co–Co exchange.     

Magnetoresistive properties of Zn1−xCoxFe2O4 ferrites

The magnetic and magnetoresistive properties of spinel-type Zn_1−xCo_xFe₂O₄ (x=0, 0.2 and 0.4) ferrites are extensively investigated in this study. A large negative magnetoresistance (MR) effect is observed in Zn_1−xCo_xFe₂O₄ ferrites of spinel structure. These materials are either ferrimagnetic or paramagnetic at room temperature, and show a spin-(cluster) glass transition at low temperatures, depending on the chemical compositions. The MR curves as a function of magnetic fields, MR(H), are parabolic at all temperatures for paramagnetic polycrystalline ZnFe₂O₄. The MR for ZnFe₂O₄ at 110 K in the presence of 9 T applied magnetic field is 30%. On the other hand, MR(H) are linear for x=0.2 and 0.4 ferrimagnetic Zn_1−xCo_xFe₂O₄ samples up to 9 T. The MR effect is independent of the sintering temperatures, and can be explained with the help of the spin-dependent scattering and the Yafet–Kittel angle of Zn_1−xCo_xFe₂O₄ mixed ferrites.     

A comprehensive overview on the structure and comparison of magnetic properties of nanocrystalline synthesized by a thermal treatment method

This study reports the simple synthesis of MFe₂O₄ (where M=Zn, Mn and Co) nanostructures by a thermal treatment method, followed by calcination at various temperatures from 723 to 873 K. Poly(vinyl pyrrolidon) (PVP) was used as a capping agent to stabilize the particles and prevent them from agglomeration. The pyrolytic behaviors of the polymeric precursor were analyzed by use of simultaneous thermo-gravimetry analyses (TGA) and derivative thermo-gravimetry (DTG) analyses. The characterization studies were conducted by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Fourier transform infrared spectroscopy (FT-IR) confirmed the presence of metal oxide bands for all the calcined samples. Magnetic properties were demonstrated by a vibrating sample magnetometer (VSM), which displayed that the calcined samples exhibited different types of magnetic behavior. The present study also substantiated that magnetic properties of ferrite nanoparticles prepared by the thermal treatment method, from viewing microstructures of them, can be explained as the results of the two important factors: cation distribution and impurity phase of α-Fe₂O₃. These two factors are subcategory of the preparation method which is related to macrostructure of ferrite. Electron paramagnetic resonance (EPR) spectroscopy showed the existence of unpaired electrons ZnFe₂O₄ and MnFe₂O₄ nanoparticles while it did not exhibit resonance signal for CoFe₂O₄ nanoparticles.     

Characterization of partially inverse spinel ZnFe2O4 with high saturation magnetization synthesized via soft mechanochemically assisted route

ZnFe₂O₄ was prepared by a soft mechanochemical route from two starting combinations of powders: (1) Zn(OH)₂/α-Fe₂O₃ and (2) Zn(OH)₂/Fe(OH)₃ mixed in a planetary ball mill. The mechanochemical treatment provoked reaction leading to the formation of the ZnFe₂O₄ spinel phase that was monitored by XRD, TEM, IR and Raman spectroscopy. The spinel phase was first observed after 4 h of milling and its formation was completed after 18 h in both the cases of starting precursors. The synthesized ZnFe₂O₄ has a nanocrystalline structure with a crystallite size of about 20.3 and 17.6 nm, for the cases (1) and (2), respectively. In the far-infrared reflectivity spectra are seen four active modes. Raman spectra suggest an existence of mixed spinel structure in the obtained nanosamples. In order to confirm phase formation and cation arrangement, Mössbauer measurements were done. Estimated degree of inversion is about 0.58 for both starting mixtures. The magnetic properties of the prepared ZnFe₂O₄ powders were also studied. The results show that the samples have a typical superparamagnetic-like behavior at room temperature. Higher values of magnetization in the case of samples obtained with starting mixture (2) suggest somewhat higher degree of cation inversion.     

Cation distribution in natural ferrites

Mössbauer spectra of jacobsite have been recorded at temperatures of 4.2, 125, 180, 240 and 300 K and with an external magnetic field of 60 kOe applied parallel to the incident radiation at 4.2 K. The results show the presence of two different magnetic hyperfine interactions associated with the iron nuclei. Spectra of samples in external magnetic fields indicate the same sign for the magnetic hyperfine interactions, implying that both iron ions occupy only the octahedral sublattice. These results are compared with data from synthetic stoichiometry manganese ferrite, and a model of cation distribution, assuming the existence of vacancies, is proposed. According to this model, the mineral jacobsite is rich in manganese compared with stoichiometric MnFe₂O₄ ferrite.