J. van Lierop

The effect of surface spin disorder on the magnetism of γ-Fe2O3 nanoparticle dispersions

The nanomagnetism of monodisperse 7 nm γ-Fe2O3 nanoparticles exhibits unique features due to a significant amount of surface spin disorder. To correctly characterize the superparamagnetism of a dilute dispersion requires including the effects of the magnetic anisotropy and a shell of disordered spins surrounding the ordered core. The nanoparticle shells disordered spin structure is exchange coupled to that of the ordered core. This enables an exchange bias loop shift, Hex, when the nanoparticle dispersion is field cooled. The surface spin disorder also leads to an unusual exponential-like decrease of the nanoparticles total saturation magnetization with increasing temperature.

Increased surface spin stability in γ-Fe2O3 nanoparticles with a Cu shell

γ-Fe(2)O(3) nanoparticles were coated with a Cu shell in situ during synthesis. An interfacial monolayer of CuO in the Cu-coated γ-Fe(2)O(3) nanoparticles was discovered that stabilized the disordered surface spins of γ-Fe(2)O(3) nanoparticles. Element-specific x-ray absorption spectroscopy at the L-edges for Cu and Fe indicated the magnetic moment of the Cu in the shell interacted with the γ-Fe(2)O(3) nanoparticles surface magnetic moments. This exchange interaction between the Fe and Cu at the interface permitted an overall Cu moment in CuO (an antiferromagnet typically) that altered the γ-Fe(2)O(3) nanomagnetism. Increasing the Cu shell thickness also increased the total Fe magnetism of the nanoparticles.

Tailoring interfacial exchange coupling with low-energy ion beam bombardment: Tuning the interface roughness

By ascertaining NiO surface roughness in a Ni80Fe20/NiO film system, we were able to correlate the effects of altered interface roughness from low-energy ion-beam bombardment of the NiO layer and the different thermal instabilities in the NiO nanocrystallites. From experiment and by modelling the temperature dependence of the exchange bias field and coercivity, we have found that reducing the interface roughness and changing the interface texture from an irregular to striped conformation enhanced the exchange coupling strength. Our results were in good agreement with recent simulations using the domain state model that incorporated interface mixing.

Micromagnetic simulations of interacting dipoles on an fcc lattice: application to nanoparticle assemblies.

Micromagnetic simulations are used to examine the effects of cubic and axial anisotropy, magnetostatic interactions and temperature on M-H loops for a collection of magnetic dipoles on fcc and sc lattices. We employ a simple model of interacting dipoles that represent single-domain particles in an attempt to explain recent experimental data on ordered arrays of magnetoferritin nanoparticles that demonstrate the crucial role of interactions between particles in an fcc lattice. Significant agreement between the simulation and experimental results is achieved, and the impact of intra-particle degrees of freedom and surface effects on thermal fluctuations is investigated.

Exchange bias in a thin film dispersion of MnO nanocrystallites in Co

Unusually large magnetization loops shifts along the field axis, of the same order as those observed in the archetypical exchange biased system Co/CoO, have been measured in a Co/MnO thin film made using reactive ion beam assisted deposition. These large loop shifts are unexpected for a system with an antiferromagnetic anisotropy that is two orders of magnitude less than that of CoO. This magnetic behavior is attributed to the nanoscale nature of the crystallites that constitute the film, where the surface area to volume ratio is large enough so that a sizable surface magnetic contribution provides the necessary antiferromagnet to ferromagnet coupling for the large measured exchange bias.

Tuning the surface magnetism of γ-Fe2O3 nanoparticles with a Cu shell

An interfacial monolayer of CuO in Cu-coated γ-Fe2O3 nanoparticles enables significantly decreased intrinsic surface spin disorder compared to bare γ-Fe2O3 nanoparticles. Element specific x-ray absorption spectroscopy at the L-edges for Cu and Fe indicates that the magnetic moment of the CuO in the shell interacts with the γ-Fe2O3 nanoparticle’s surface magnetic moments. This exchange interaction cants the moments of the CuO resulting in a non-zero Cu moment, altering the γ-Fe2O3 nanomagnetism.

Anomalous exchange bias behavior in ion-beam bombarded NiCo/(Ni,Co)O bilayers

The structural and magnetic properties of NiCo∕(Ni,Co)O bilayers were investigated. X-ray diffractometry results have shown that the top NiCo layer consisted of a fcc NiCo phase. The bilayer bottom was either a pure (Ni,Co)O or a composite [NiCo+(Ni,Co)O] phase, depending on the percent of O2∕Ar ratio used during deposition. A double-shifted hysteresis loop exhibiting components that were from positive or negative coupling was observed in the NiCo∕(Ni,Co)O (8%O2∕Ar) bilayers. The microstructural changes, which result from a combination of deposition oxygen content and the ion-beam bombardment, will result in the unusual exchange bias behavior.

Magnetic exchange effects in a nanocomposite Ni/NiO film

The unique sample preparation technique of reactive ion beam assisted deposition has been used to make a thin film sample of interdispersed Ni and NiO nanocrystallites. The ferromagnetic and antiferromagnetic crystallites in the film provide a unique geometry that lies between that of bulk exchange biased systems and layered thin films, and provides clear evidence of exchange effects. Interphase magnetic exchange is demonstrated by suppression of the Neel and Curie temperatures of the components, as well as by the typical hysteresis loop shift that is a measure of the exchange field strength. Furthermore, a strong temperature and maximum applied field dependence for both the coercivity and exchange field strength is present, indicating competition between the exchange interaction of the Ni and NiO nanocrystallites and the external field and NiO surface magnetic coupling interactions.

Spin dynamics in CoFe2O4 nanoparticles

The bulk and local magnetisms of ∼10 nm diameter CoFe2O4 nanoparticles have been characterized from 5 to 425 K. Magnetometry results indicate that the nanoparticles have a blocking temperature around 380 K and they exhibit a temperature dependent cubic magnetocrystalline anisotropy similar to that of bulk CoFe2O4 with K(0)∼1.2×106 ergs/cm3. However, the local, atomic-level spin dynamics examined by Mossbauer spectroscopy indicates strongly that rather than exhibiting a typical static, blocked magnetism to superparamagnetism behavior, the CoFe2O4 nanoparticle moments become paramagnetic, with this transition percolating from the surface to the core of the nanoparticle with increasing temperature.

Simultaneous magnetically directed drug convection and MR imaging.

Superparamagnetic iron oxide nanoparticles (IO NPs) are of interest for their usefulness in biomedical applications. In this work, we have synthesized iron oxide nanocomposites surface-modified with different biocompatible polymers. Bovine serum albumin (BSA) was physisorbed onto these IO NPs along with an excipient during freeze-drying. The mass transport of the protein attached to the iron oxide core-shell nanoparticles (IO cs-NPs) under a gradient magnetic field of an MRI instrument was observed in vitro and in an egg as a model system for a biological fluid. From the in vitro experiments in agarose gels, it was observed that the protein gets separated from the core during mass transport for some cs-IO, but co-migration was observed for PEG-modified IO cs-NPs. These experiments demonstrated proof-of-concept for the use of IO cs-NPs in magnetically directed drug convection.