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Magnetic Domains and Surface Effects in Hollow Maghemite Nanoparticles

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 Added by Oscar Iglesias
 Publication date 2009
  fields Physics
and research's language is English




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In the present work, we investigate the magnetic properties of ferrimagnetic and noninteracting maghemite (g-Fe2O3) hollow nanoparticles obtained by the Kirkendall effect. From the experimental characterization of their magnetic behavior, we find that polycrystalline hollow maghemite nanoparticles are characterized by low superparamagnetic-to-ferromagnetic transition temperatures, small magnetic moments, significant coercivities and irreversibility fields, and no magnetic saturation on external magnetic fields up to 5 T. These results are interpreted in terms of the microstructural parameters characterizing the maghemite shells by means of an atomistic Monte Carlo simulation of an individual spherical shell model. The model comprises strongly interacting crystallographic domains arranged in a spherical shell with random orientations and anisotropy axis. The Monte Carlo simulation allows discernment between the influence of the structure polycrystalline and its hollow geometry, while revealing the magnetic domain arrangement in the different temperature regimes.



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We report a study on the pressure response of the anisotropy energy of hollow and solid maghemite nanoparticles. The differences between the maghemite samples are understood in terms of size, magnetic anisotropy and shape of the particles. In particular, the differences between hollow and solid samples are due to the different shape of the nanoparticles and by comparing both pressure responses it is possible to conclude that the shell has a larger pressure response when compared to the core.
Disorder among surface spins largely dominates the magnetic response of ultrafine magnetic particle systems. In this work, we examine time-dependent magnetization in high-quality, monodisperse hollow maghemite nanoparticles with a 14.8 $pm$ 0.5 nm outer diameter and enhanced surface-to-volume ratio. The nanoparticle ensemble exhibits spin-glass-like signatures in dc magnetic aging and memory protocols and ac magnetic susceptibility. The dynamics of the system slows near 50 K, and becomes frozen on experimental time scales below 20 K. Remanence curves indicate the development of magnetic irreversibility concurrent with the freezing of the spin dynamics. A strong exchange-bias effect and its training behavior point to highly frustrated surface spins that rearrange much more slowly than interior spins with bulk coordination. Monte Carlo simulations of a hollow particle reproducing the experimental morphology corroborated strongly disordered surface layers with complex energy landscapes that underlie both glass-like dynamics and magnetic irreversibility. Calculated hysteresis loops reveal that magnetic behavior is not identical at the inner and outer surfaces, with spins at the outer surface layer of the 15 nm hollow particles exhibiting a higher degree of frustration. Our study sheds light on the origin of spin-glass-like phenomena and the role of surface spins in magnetic hollow nanostructures.
Controlled assembly of single-crystal, colloidal maghemite nanoparticles is facilitated via a high-temperature polyol-based pathway. Structural characterization shows that size-tunable nanoclusters of 50 and 86 nm diameters (D), with high dispersibility in aqueous media, are composed of $sim$ 13 nm (d) crystallographically oriented nanoparticles. The interaction effects are examined against the increasing volume fraction, $phi$, of the inorganic magnetic phase that goes from individual colloidal nanoparticles ($phi$= 0.47) to clusters ($phi$= 0.72). The frozen-liquid dispersions of the latter exhibit weak ferrimagnetic behavior at 300 K. Comparative Mossbauer spectroscopic studies imply that intra-cluster interactions come into play. A new insight emerges from the clusters temperature-dependent ac susceptibility that displays two maxima in $chi$(T), with strong frequency dispersion. Scaling-law analysis, together with the observed memory effects suggest that a superspin glass state settles-in at T$_{B}$ $sim$ 160-200 K, while at lower-temperatures, surface spin-glass freezing is established at T$_{f}$ $sim$40- 70 K. In such nanoparticle-assembled systems, with increased $phi$, Monte Carlo simulations corroborate the role of the inter-particle dipolar interactions and that of the constituent nanoparticles surface spin disorder in the emerging spin-glass dynamics.
The effect of surface anisotropy on the distribution of energy barriers in magnetic fine particles of nanometer size is discussed within the framework of the $Tln(t/tau_0)$ scaling approach. The comparison between the distributions of the anisotropy energy of the particle cores, calculated by multiplying the volume distribution by the core anisotropy, and of the total anisotropy energy, deduced by deriving the master curve of the magnetic relaxation with respect to the scaling variable $Tln(t/tau_0)$, enables the determination of the surface anisotropy as a function of the particle size. We show that the contribution of the particle surface to the total anisotropy energy can be well described by a size--independent value of the surface energy per unit area which permits the superimposition of the distributions corresponding to the particle core and effective anisotropy energies. The method is applied to a ferrofluid composed of non-interacting Fe$_{3-x}$O$_{4}$ particles of 4.9 nm in average size and $x$ about 0.07. Even though the size distribution is quite narrow in this system, a relatively small value of the effective surface anisotropy constant $K_{s}=2.9times 10^{-2}$ erg cm$^{-2}$ gives rise to a dramatic broadening of the total energy distribution. The reliability of the average value of the effective anisotropy constant, deduced from magnetic relaxation data, is verified by comparing it to that obtained from the analysis of the shift of the ac susceptibility peaks as a function of the frequency.
205 - N. Noginova , F. Chen , T. Weaver 2006
Magnetic nanoparticles of gamma-Fe2O3 coated by organic molecules and suspended in liquid and solid matrices, as well as a non-diluted magnetic fluid have been studied by electron magnetic resonance (EMR) at 77-380 K. Slightly asymmetric spectra observed at room temperature become much broader, symmetric, and shift to lower fields upon cooling. An additional narrow spectral component (with the line-width of 30 G) is found in the diluted samples, its magnitude obeying the Arrhenius law with the activation temperature of about 850 K. The longitudinal spin-relaxation time, T1 >> 10 ns, was determined by the specially developed modulation method. Angular dependence of the EMR signal position in field-freezing samples unambiguously points to the domination of the uniaxial magnetic anisotropy. Substantial alignment is achieved in moderate freezing fields of 4-5 kG, suggesting formation of dipolar-coupled chains consisting from several particles separated by organic nanolayers. The shift and broadening of the spectrum upon cooling are ascribed to the role of the surface layer, which is considered with taking into acount the strong surface-related anisotropy. To describe the overall spectrum shape, a quantization model is used which includes summation of the resonances corresponding to varios orientations of the particle magnetic moment. This approach, supplemented with some phenomenological assumptions, provides satisfactory agreement with the experimental data.
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