Non-equilibrium cation distribution and enhanced spin disorder in hollow CoFe2O4 nanoparticles

We present magnetic properties of hollow and solid CoFe(2)O(4) nanoparticles that were obtained by annealing of Co(33)Fe(67)/CoFe(2)O(4) (core/shell) nanoparticles. Hollow nanoparticles were polycrystalline whereas the solid nanoparticles were mostly single crystal. Electronic structure studies were performed by photoemission which revealed that particles with hollow morphology have a higher degree of inversion compared to solid nanoparticles and the bulk counterpart. Electronic structure and the magnetic measurements show that particles have uncompensated spins. Quantitative comparison of saturation magnetization (M(S )), assuming bulk Néel type spin structure with cationic distribution, calculated from quantitative XPS analysis, is presented. The thickness of uncompensated spins is calculated to be significantly large for particles with hollow morphology compared to solid nanoparticles. Both morphologies show a lack of saturation up to 7 T. Moreover magnetic irreversibility exists up to 7 T of cooling fields for the entire temperature range (10-300 K). These effects are due to the large bulk anisotropy constant of CoFe(2)O(4) which is the highest among the cubic spinel ferrites. The effect of the uncompensated spins for hollow nanoparticles was investigated by cooling the sample in large fields of up to 9 T. The magnitude of horizontal shift resulting from the unidirectional anisotropy was more than three times larger than that of solid nanoparticles. As an indication signature of uncompensated spin structure, 11% vertical shift for hollow nanoparticles is observed, whereas solid nanoparticles do not show a similar shift. Deconvolution of the hysteresis response recorded at 300 K reveals the presence of a significant paramagnetic component for particles with hollow morphology which further confirms enhanced spin disorder.     

Tuneable magnetic properties of hydrothermally synthesised core/shell CoFe2O4/NiFe2O4 and NiFe2O4/CoFe2O4 nanoparticles

The aim of this study was to prepare a novel targeting nano drug delivery system of 2-methoxyestradiol (2-ME) based on the folic acid-modified bovine serum albumin, in order to improve the clinical application disadvantages and antitumor effect of 2-ME. In this study, 2-methoxyestradiol-loaded albumin nanoparticles (2-ME-BSANPs) were prepared by desolvation method, and then the activated folic acid was conjugated to 2-ME-BSANPs by covalent attachment (2-ME-FA-BSANPs). The size and zeta potential of 2-ME-FA-BSANPs were about 208.8 ± 5.1 nm and ?32.70 ± 1.01 mV, respectively. 2-ME loading efficiency and loading amount of the nanoparticles were 80.49 ± 3.80 and 10.25 ± 1.59 %, respectively. SEM images indicated that 2-ME-FA-BSANPs were of a round shape, similar uniform size, and smooth surface. Studies on drug release indicated that 2-ME-FA-BSANPs had the properties of sustained and controlled release, which provided them with the ability to fight continually against cancer cells. Internalization analysis demonstrated that 2-ME-FA-BSANPs-targeting drug delivery system could get efficiently transferred into the cells through the folic acid-mediated endocytosis, leading to higher apoptosis and affording higher antitumor efficacy against SMMC-7721 cells in vitro compared with 2-ME alone. Furthermore, the cell-cycle arrest of 2-ME-FA-BSANPs on the SMMC-7721 cells occurred at G2/M phase, and 2-ME-FA-BSANPs did not change the inhibition of the tumor mechanisms of 2-ME. Based on these results, it was concluded that albumin nanoparticles could be the promising nano carrier for 2-ME, and 2-ME-FA-BSANPs-targeting drug delivery system may be promising candidate for providing high treatment efficacy with minimal side effects in future cancer therapy.     

Size-dependent magnetic properties of CoFe2O4 nanoparticles prepared in polyol

Highly crystalline CoFe(2)O(4) nanoparticles with different diameters ranging from 2.4 to 6.1 nm have been synthesized by forced hydrolysis in polyol. The size can be controlled through adjusting the nominal water/metal molar ratio. X-ray diffraction, transmission electron microscopy, x-ray absorption spectroscopy and (57)Fe M?ssbauer spectrometry were employed to investigate the structure and the microstructure of the particles produced. Magnetic measurements performed on these particles show that they are superparamagnetic with a size-dependent blocking temperature. At 5 K, high saturation magnetization (~85 emu g(-1)) approaching that of the bulk was found for the larger particles, whereas a very large coercivity (14.5 kOe) is observed for the 3.5 nm sized particles.     

CoFe2O4纳米颗粒的结构、磁性以及离子迁移

聚乙烯醇(PVA)溶胶凝胶法制备出CoFe2O4纳米微粉,用X 射线衍射研究了铁氧体纳米颗粒的结构.测量了CoFe2O4纳米颗粒80-873 K的变温穆斯堡尔谱,发现纳米颗粒的磁转变温度范围为793-813 K,比块体材料的磁性转变温度要低.CoFe2O4纳米颗粒的德拜温度θA=674 K,θB=243 K,比块体材料要小.CoFe2O4纳米颗粒超精细场Hf随温度的变化符合T3/2+T5/2定理.当温度较高时,平均同质异能移IS随温度的升高而减小,并呈线性关系.     

CoFe2O4和MnFe2O4纳米复合介质的制备及其磁性研究

采用热分解法制备了分散程度高且平均晶粒尺寸为20 nm的CoFe₂O₄和MnFe₂O₄复合介质.低温磁化曲线测量显示,制备的复合介质具有软-硬磁交换弹性耦合效应,且合成温度以及软磁和硬磁相的成分比例对磁交换弹性耦合的强度有很大的影响.变温磁测量显示,温度为20K时,复合纳米介质的表面自旋冻结效应导致饱和磁化强度显著增加.Henkel测量显示,对分散的CoFe₂O₄和MnFe₂O₄复合介质,磁偶极相互作用占主导作用.     

Spin canting in ferrite nanoparticles

Recently, an easily scalable process for the production of small (3 ?7 nm) monodisperse superparamagnetic ferrite nanoparticles MeFe₂O₄ (Me = Zn, Mn, Co) from iron metal and octanoic acid has been reported (Salih et al., Chem. Mater. 25 1430–1435 2013). Here we present a Mössbauer spectroscopic study of these ferrite nanoparticles in external magnetic fields of up to B = 5 T at liquid helium temperatures. Our analysis shows that all three systems show a comparable inversion degree and the cationic distribution for the tetrahedral A and the octahedral B sites has been determined to (Zn_0.19Fe_0.81) ^A [Zn_0.81Fe_1.19] ^B O₄, (Mn_0.15Fe_0.85) ^A [Mn_0.85Fe_1.15] ^B O₄ and (Co_0.27Fe_0.73) ^A [Co_0.73Fe_1.27] ^B O₄. Spin canting occurs presumably in the B-sites and spin canting angles of 33°, 51° and 59° have been determined for the zinc, the manganese, and the cobalt ferrite nanoparticles.     

Synthesis of CoFe2O4 nanoparticles embedded in a silica matrix by the citrate precursor technique

A metals–citrate–silica gel was prepared from metallic salts, citric acid and tetraethylorthosilicate by sol–gel method (citrate precursor technique) and it was further used to prepare magnetic nanocomposites. The gel was dried at 100 °C and then calcined at temperatures between 600 and 1000 °C to obtain powder samples. The nanocomposites were characterized by XRD, IR, VSM and TEM techniques. The diffraction patterns show the formation of a single magnetic phase identified as CoFe₂O₄. Magnetic nanoparticles with average size less than 50 nm were obtained which are well dispersed in the silica matrix. The combination of different metals concentrations and calcining temperatures allowed obtaining samples with magnetization ranging from 3.6 to 25.3 emu/g.     

Thermal conductivity of Zn doped CoFe2O4 ferrites

A series of samples of the type Co_1-xZn_xFe₂O₄ (x = 0.0, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8 and 1.0) was prepared as ceramics. The existence of a single phase was confirmed by x-ray studies. The thermal conductivity and specific heat were measured at temperatures ranging from 100°C to 200°C. The thermal conductivity had a minimum value at x = 0.4, caused by maximum scattering of thermal phonons which arose from the change of crystal size and excess of lattice vacancies. The phonon frequency was estimated to have an optimum value at x = 0.4, resulting from maximum porosity which disturbs the propagation of the thermal waves.     

Mechanical stability of ferrimagnetic CoFe2O4 flexible thin films

We fabricated high-quality ferrimagnetic CoFe₂O₄ (CFO) thin films on a mica substrate using a pulsed laser deposition technique. High-resolution X-ray diffraction and transmission electron microscopy revealed that the film grew epitaxially with the relationships of CFO <1-10> || Mica [010] and CFO [111] || Mica [001]. The films were highly flexible in terms of both inward and outward bending, and exhibited clear ferrimagnetic hysteresis with weak anisotropy in both the in-plane and out-of-plane directions. We observed that the magnetization of CFO films was robust against mechanical stimuli without microcracks. The remnant magnetization and coercive field were within 8% and 11% over a strain of ±0.54%. As the number of bending cycles increased, the magnetic easy axis became more closely aligned to the out-of-plane direction, without any noticeable change in domain size.     

Low temperature measurements by infrared spectroscopy in CoFe2O4 ceramic

This paper presents results of new far-infrared and middle-infrared measurements (wavenumber range of 4000?C100 cm^?1) of the CoFe₂O₄ ceramic in the temperature range from 300 K to 8 K. The band positions and their shapes remain constant across the wide temperature range. The quality of the sample was investigated by X-ray, EDS and EPMA studies. The CoFe₂O₄ retains the cubic structure (Fd - 3m) across the temperature range from 85 K to 360 K without any traces of distortion. Based on current knowledge the polycrystalline CoFe₂O₄ does not exhibit any phase transitions across the temperature range from 8 K to 300 K.     

Electrochemical characterization of core@shell CoFe2O4/Au composite

Quantum dots (QDs) have received considerable attention due to their unique optical and electrical properties. Although substantial research has focused on the potential applications and toxicological impacts of QDs, far less effort has been directed toward understanding their fate and transport in the environment. In this work, the effect of four coatings, polyethylene glycol functionalized polymer (PEGP), carboxyl derivatized polymer (COOHP), linoleic acid (LA), and polyacrylic acid-octylamine (PAA-OA), on the transport and retention of QDs in porous media were evaluated under environmentally relevant conditions. Aqueous QD suspensions (ca. 10 nM) were introduced into water-saturated columns packed with 40–50 mesh Ottawa sand at a pore-water velocity of 7.6 m/day. At an ionic strength (IS) of 3 mM and pH of 7, PEGP-coated QDs were completely retained within the column, while more than 60 % of COOHP-coated QDs were transported through a column run under identical conditions. When PAA-OA and LA were used as coatings, effluent QD recoveries increased to more than 65 and 89 % of the injected mass, respectively. Additionally, a decrease in pH from 9.5 to 5.0, or an increase of IS from 0 to 30 mM reduced the eluted mass of PAA-OA-coated QDs by more than 2 and 15 times, respectively. The relative mobility of coated QDs (LA > PAA-OA > COOHP > PEGP) was consistent with total interaction energy profiles between QDs and sand surfaces calculated based on Derjaguin–Landau–Verwey–Overbeek (DLVO) theory. At an IS of 3 mM (NaCl) and pH 7, a linear correlation was obtained between the fraction of eluted QDs and the magnitude of the primary interaction energy barrier. These findings demonstrate the strong dependence of QD transport on coating type and indicate that interaction energies based on DLVO theory can be used to predict the relative mobility of QDs in porous media.     

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.     

Investigation of nanocrystalline CoFe 2 O 4 by positron annihilation lifetime spectroscopy

Nanoparticles of cobalt ferrite prepared by the co-precipitation method with crystallite size varying from 4.7 to 41 nm have been characterized by positron annihilation lifetime spectroscopy. Three lifetime components are fitted to the lifetime data. The shortest lifetime component is attributed to the delocalized positron lifetime shortened by defect trapping. The intermediate lifetime is assigned to the positron annihilation in diffuse vacancy clusters or microvoids at the grain boundaries and at the grain-boundary triple points. The longest component corresponds to the pick-off annihilation of ortho-positronium formed at the larger voids. The variations in these lifetimes and their relative intensities with annealing temperature and crystallite size have been studied in detail.     

CoFe2O4/空心微球复合体的制备与吸波性能

采用化学共沉淀法,在空心微球上包覆一层CoFe2O4,得到一种低密度的空心磁性微球．磁测量结果表明,磁场下退火制备的CoFe2O4样品反位缺陷减少,从而导致饱和磁化强度随退火磁场的增强而增大．吸波性能测试结果表明,包覆结构的CoFe2O4/空心球样品是一种轻质的微波吸收材料.     

CoFe_2O_4/空心微球复合体的制备与吸波性能

采用化学共沉淀法,在空心微球上包覆一层CoFe2O4,得到一种低密度的空心磁性微球.磁测量结果表明,磁场下退火制备的CoFe2O4样品反位缺陷减少,从而导致饱和磁化强度随退火磁场的增强而增大.吸波性能测试结果表明,包覆结构的CoFe2O4/空心球样品是一种轻质的微波吸收材料.     

Effect of Al3+ substitution on structural,cation distribution,electrical and magnetic properties of CoFe2O4

We present the structural, cation distribution, electrical and magnetic studies of CoAl_xFe_2−xO₄ (x = 0.0, 0.2, 0.4, 0.6, 0.8) ferrites. The Rietveld-fitted X-ray diffraction (XRD) patterns confirm the formation of single-phase cubic spinel structures with $Fd\overline{3}m$ space group for all the samples. A comprehensive analysis of XRD-based cation distribution has been performed to see the effect of Al³⁺ ions substitution on various structural parameters such as site ionic radii, edge length, bond length and interionic distances. The dielectric constant and direct current (DC) conductivity decreases with increasing Al³⁺ substitution up to x = 0.4. However, with further increase in Al³⁺ substitution, both the dielectric constant and the DC conductivity increase. The presentation of dielectric data in the complex electric modulus form reveals the presence of a non-Debye-type relaxation behaviour in the considered ferrites. The power law behaviour of alternating current (AC) conductivity indicates a strong correlation among electrons in these systems. The isothermal magnetisation versus applied field curves with high-field slope and significant coercivity suggest that the studied materials are highly anisotropic with canted spin structures. The samples exhibit ferrimagnetic behaviour at 300 K and the magnetisation decreases with increasing Al³⁺ concentration. The as-prepared samples are promising candidates for various industrial applications.     

NMR evidence for spin canting in a bilayer nu=2 quantum hall system

We investigate the electron spin states in the bilayer quantum Hall system at total Landau level filling factor nu=2 exploiting current-pumped and resistively detected NMR. The measured Knight shift, K(S), of 75As nuclei reveals continuous variation of the out-of-plane electronic spin polarization between nearly full and zero as a function of density imbalance. Nuclear spin relaxation measurements indicate a concurrent development of an in-plane spin component. These results provide direct information on the spin configuration in this system and comprise strong evidence for the spin canting suggested by previous experiments.     

High accuracy photopyroelectric investigation of dynamic thermal parameters of Fe3O4 and CoFe2O4 magnetic nanofluids

The suitability of the photopyroelectric (PPE) calorimetry in measuring the thermal parameters of nanofluids was demonstrated. The main advantages of the method (concerning nanofluids) as compared to classical calorimetric techniques are: high sensitivity and small amount of sample required. The thermal diffusivity and effusivity of some nanofluids based on Fe₃O₄ and CoFe₂O₄ type of nanoparticles (mean diameter 6.5 nm) were investigated by using two PPE detection configurations (back and front). In both cases, the information is contained in the phase of the PPE signal. Due to the high accuracy of the results (within ±0.5%) thermal diffusivity was found to be particularly sensitive to changes in relevant parameters of the nanofluid as carrier liquid, type and concentration of nanoparticles.