Confinement Effects and Magnetic Interactions in Magnetic Nanostructures

Multifunctional nanocomposites are promising for a variety of applications ranging from microwave devices to biomedicine. High demand exists for magnetically tunable nanocomposite materials. My thesis focuses on synthesis and characterization of novel nanomaterials such as polymer nanocomposites (PNCs) and multi-walled carbon nanotubes (MWCNTs) with magnetic nanoparticle (NP) fillers. Magnetite (Fe3O4) and cobalt ferrite (CoFe2O4) NPs with controlled shape, size, and crystallinity were successfully synthesized and used as PNC fillers in a commercial polymer provided by the Rogers Corporation and poly(vinylidene fluoride). Magnetic and microwave experiments were conducted under frequencies of 1-6 GHz in the presence of transverse external magnetic fields of up to 4.5 kOe. Experiments confirm strong magnetic field dependence across all samples. When incorporated in to a cavity resonator device, tangent losses were reduced, quality factor increased by 5.6 times, and tunability of the resonance frequency was demonstrated, regardless of NP-loading. Work on PNC materials revealed the importance of NP interactions in confined spaces and motivated the study of confinement effects of magnetic NPs in more controlled environments, such as MWCNTs with varying diameters. MWCNTs were synthesized with diameters of 60 nm, 100 nm, 250 nm, and 450 nm to contain magnetic NP fillers (~10 nm) consisting of ferrites of the form MFe2O4, where M = Co2+, Ni2+, or Fe2+. All confined samples exhibit superparamagnetic-like behavior with stronger magnetic response with respect to increasing MWCNT diameter up to 250 nm due to the enhancement of interparticle interactions. This thesis provides the first systematic study of this class of nanocomposites, which paves the way to inclusion of novel nanostructured materials in real-world applications

Superparamagnetic properties of carbon nanotubes filled with NiFe2O4 nanoparticles

Multi walled carbon nanotubes (MWCNTs) were successfully synthesized using custom-made 80 nm pore-size alumina templates, and were uniformly filled with nickel ferrite (NFO) nanoparticles of 7.4 ± 1.7 nm diameter using a novel magnetically assisted capillary action method. X-ray diffraction confirmed the inverse spinel phase for the synthesized NFO. Transmission electron microscopy confirms spherical NFO nanoparticles with an average diameter of 7.4 nm inside MWCNTs. Magnetometry indicates that both NFO and NFO-filled MWCNTs present a blocking temperature around 52 K, with similar superparamagnetic-like behavior, and weak dipolar interactions, giving rise to a super-spin-glass-like behavior at low temperatures. These properties along with the uniformity of sub-100 nm structures and the possibility of tunable magnetic response in variable diameter carbon nanotubes make them ideal for advanced biomedical and microwave applications.Research at USF was supported by USAMRMC through Grant Nos. W81XWH-07-1-0708 and W81XWH1020101/3349 (synthesis of nanoparticles and nanotubes, structural characterization) and U.S. DoE, Office of Basic Energy Sciences through Award No. DE FG02 07ER46438 (magnetic measurements and analysis). Research at ICMM/CSIC was supported by the Regional Government of Madrid under Project Nanobiomagnet, S2009/MAT-1726. Javier Alonso acknowledges the financial support provided through a postdoctoral fellowship from the Basque Government

Exchange Bias Effects in Iron Oxide-Based Nanoparticle Systems

The exploration of exchange bias (EB) on the nanoscale provides a novel approach to improving the anisotropic properties of magnetic nanoparticles for prospective applications in nanospintronics and nanomedicine. However, the physical origin of EB is not fully understood. Recent advances in chemical synthesis provide a unique opportunity to explore EB in a variety of iron oxide-based nanostructures ranging from core/shell to hollow and hybrid composite nanoparticles. Experimental and atomistic Monte Carlo studies have shed light on the roles of interface and surface spins in these nanosystems. This review paper aims to provide a thorough understanding of the EB and related phenomena in iron oxide-based nanoparticle systems, knowledge of which is essential to tune the anisotropic magnetic properties of exchange-coupled nanoparticle systems for potential applications

Remotely Controlled Micromanipulation by Buckling Instabilities in Fe₃O₄ Nanoparticle Embedded Poly(<i>N</i>‑isopropylacrylamide) Surface Arrays

The micromanipulation of biological samples is important for microbiology, pharmaceutical science, and related bioengineering fields. In this work, we report the fabrication and characterization of surface-attached microbeam arrays of 20 μm width and 25 μm height made of poly­(<i>N</i>-isopropylacrylamide), a thermoresponsive polymer, with embedded spherical or octopod Fe₃O₄ nanoparticles. Below 32 °C, the microbeams imbibe water and buckle with an amplitude of approximately 20 μm. Turning on an AC-magnetic field induces the microbeam array to expel water due to the heating effect of the nanoparticles (magnetic hyperthermia), leading to a reversible transition from a buckled to nonbuckled state. It is observed that the octopod nanoparticles have a heating rate 30% greater (specific absorption rate, SAR) than that of the spherical nanoparticles, which shortens the time scale of the transition from the buckled and nonbuckled state. The return of the microbeams to the buckled state is accomplished by turning off the AC magnetic field, the rate of which is dictated by dissipation of heat and is independent of the type of nanoparticle. It is further demonstrated that this transition can be used to propel 50 μm spherical objects along a surface. While the motion is random, this study shows the promise of harnessing shape-shifting patterns in microfluidics for object manipulation

Magnetically tunable organic semiconductors with superparamagnetic nanoparticles

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