Field dependent transition to the non-linear regime in magnetic hyperthermia experiments: Comparison between maghemite, copper, zinc, nickel and cobalt ferrite nanoparticles of similar sizes

Further advances in magnetic hyperthermia might be limited by biological constraints, such as using sufficiently low frequencies and low field amplitudes to inhibit harmful eddy currents inside the patient's body. These incite the need to optimize the heating efficiency of the nanoparticles, referred to as the specific absorption rate (SAR). Among the several properties currently under research, one of particular importance is the transition from the linear to the non-linear regime that takes place as the field amplitude is increased, an aspect where the magnetic anisotropy is expected to play a fundamental role. In this paper we investigate the heating properties of cobalt ferrite and maghemite nanoparticles under the influence of a 500 kHz sinusoidal magnetic field with varying amplitude, up to 134 Oe. The particles were characterized by TEM, XRD, FMR and VSM, from which most relevant morphological, structural and magnetic properties were inferred. Both materials have similar size distributions and saturation magnetization, but strikingly different magnetic anisotropies. From magnetic hyperthermia experiments we found that, while at low fields maghemite is the best nanomaterial for hyperthermia applications, above a critical field, close to the transition from the linear to the non-linear regime, cobalt ferrite becomes more efficient. The results were also analyzed with respect to the energy conversion efficiency and compared with dynamic hysteresis simulations. Additional analysis with nickel, zinc and copper-ferrite nanoparticles of similar sizes confirmed the importance of the magnetic anisotropy and the damping factor. Further, the analysis of the characterization parameters suggested core-shell nanostructures, probably due to a surface passivation process during the nanoparticle synthesis. Finally, we discussed the effect of particle-particle interactions and its consequences, in particular regarding discrepancies between estimated parameters and expected theoretical predictions. Copyright 2012 Author(s). This article is distributed under a Creative Commons Attribution 3.0 Unported License. [http://dx.doi. org/10.1063/1.4739533]

Layer-by-Layer assembled cobalt ferrite nanoparticles for chemical sensing

Ultra-thin (thicknesses of 50-90 nm) nanocomposite films of cobalt ferrite nanoparticles (np-CoFe2O4, 18 nm in diameter) and polyelectrolytes (doped polyaniline-PANI, poly-3,4-ethylenedioxy thiophene: polystyrene sulfonic acid-PEDOT:PSS, and sulfonated lignin-SL) are assembled layer-by-layer onto interdigitated microelectrodes aiming at to create novel nanostructured sensoactive materials for liquid media chemical sensors. The nanocomposites display a distinctive globular morphology with nanoparticles densely-packed while surrounded by polyelectrolytes. Due to the presence of np-CoFe2O4 the nanocomposites display low electrical conductivity according to impedance data. On the other hand, this apparent shortcoming turns such nanocomposites much more sensitive to the presence of ions in solution than films made exclusively of conducting polyelectrolytes. For example, the electrical resistance of np-CoFe2O4/PEDOT:PSS and PANI/SL/np-CoFe2O4/SL architectures has a 10-fold decrease when they are immersed in 20 mmol. L-1 NaCl solution. Impedance spectra fitted with the response of an equivalent circuit model suggest that the interface created between nanoparticles and polyelectrolytes plays a major role on the nanocomposites electrical/dielectrical behavior. Since charge transport is sensitive to nanoparticle-polyelectrolyte interfaces as well as to the physicochemical conditions of the environment, the np-CoFe2O4-based nanocomposites can be used as sensing elements in chemical sensors operated under ac regime and room temperature.

Dielectric properties of cobalt ferrite nanoparticles in ultrathin nanocomposite films

Multilayered nanocomposite films (thickness 50-90 nm) of cobalt ferrite nanoparticles (np-CoFe2O4, 18 nm) were deposited on top of interdigitated microelectrodes by the layer-by-layer technique in order to study their dielectric properties. For that purpose, two different types of nanocomposite films were prepared by assembling np-CoFe2O4 either with poly(3,4-ethylenedioxy thiophene):poly(styrene sulfonic acid) or with polyaniline and sulfonated lignin. Despite the different film architectures, the morphology of both was dominated by densely-packed layers of nanoparticles surrounded by polyelectrolytes. The dominant effect of np-CoFe2O4 was also observed after impedance spectroscopy measurements, which revealed that dielectric behavior of the nanocomposites was largely influenced by the charge transport across nanoparticle-polyelectrolyte interfaces. For example, nanocomposites containing np-CoFe2O4 exhibited a single low-frequency relaxation process, with time constants exceeding 15 ms. At 1 kHz, the dielectric constant and the dissipation factor (tan ᵟ) of these nanocomposites were 15 and 0.15, respectively. These values are substantially inferior to those reported for pressed pellets made exclusively of similar nanoparticles. Impedance data were further fitted with equivalent circuit models from which individual contributions of particle's bulk and interfaces to the charge transport within the nanocomposites could be evaluated. The present study evidences that such nanocomposites display a dielectric behavior dissimilar from that exhibited by their individual counterparts much likely due to enlarged nanoparticle- polyelectrolyte interfaces.

Changes in a nanoparticle's spectroscopic signal mediated by the local environment

Using a first-principles theoretical model the adsorption of a methyl radical on different sized silver nanoparticles is compared to the adsorption of the same radical on model surfaces. Calculations of our structural, dynamical and electronic properties indicated that small changes in the local environment will lead to small changes in infrared (IR) wavenumbers, but in dramatic changes in the IR signal. Our calculations indicate the lower the adsorption site coordination, the higher is the signal strength, suggesting that small changes in the electronic charge distribution will result in bigger changes in the polarizability and hence in the spectroscopic signal intensity. This effect explains, among others, the signal magnification observed for nanoparticles in surface enhanced Raman spectroscopic (SERS) experiments.

Recent Advances in the Development of Magnetically Recoverable Metal Nanoparticle Catalysts

The aim of this Account is to provide an overview of our current research activities on the design and modification of superparamagnetic nanomaterials for application in the field of magnetic separation and catalysis. First, an introduction of magnetism and magnetic separation is done. Then, the synthetic strategies that have been developed for generating superparamagnetic nanoparticles spherically coated by silica and other oxides, with a focus on well characterized systems prepared by methods that generate samples of high quality and easy to scale- up, are discussed. A set of magnetically recoverable catalysts prepared in our research group by the unique combination of superparamagnetic supports and metal nanoparticles is highlighted. This Account is concluded with personal remarks and perspectives on this research field.

Predicting Delta Ferrite Content in Stainless Steel Castings

The distribution of delta ferrite fraction was measured with the magnetic method in specimens of different stainless steel compositions cast by the investment casting (lost wax) process. Ferrite fraction measurements published in the literature for stainless steel cast samples were added to the present work data, enabling an extensive analysis about practical methods to calculate delta ferrite fractions in stainless steel castings. Nineteen different versions of practical methods were formed using Schaeffler, DeLong, and Siewert diagrams and the nickel and chromium equivalent indexes suggested by several authors. These methods were evaluated by a detailed statistical analysis, showing that the Siewert diagram, including its equivalent indexes and iso-ferrite lines, gives the lowest relative errors between calculated and measured delta ferrite fractions. Although originally created for stainless steel welds, this diagram gives relative errors lower than those for the current ASTM standard method (800/A 800M-01), developed to predict ferrite fractions in stainless steel castings. Practical methods originated from a combination of different chromium/nickel equivalent indexes and the iso-ferrite lines from Schaeffler diagram give the lowest relative errors when compared with combinations using other iso-ferrite line diagrams. For the samples cast in the present work, an increase in cooling rate from 0.78 to 2.7 K/s caused a decrease in the delta ferrite fraction, but a statistical hypothesis test revealed that this effect is significant in only 50% of the samples that have ferrite in their microstructures.

Gold nanoparticle formation in diamond-like carbon using two different methods: Gold ion implantation and co-deposition of gold and carbon

We describe work in which gold nanoparticles were formed in diamond-like carbon (DLC), thereby generating a Au-DLC nanocomposite. A high-quality, hydrogen-free DLC thin film was formed by filtered vacuum arc plasma deposition, into which gold nanoparticles were introduced using two different methods. The first method was gold ion implantation into the DLC film at a number of decreasing ion energies, distributing the gold over a controllable depth range within the DLC. The second method was co-deposition of gold and carbon, using two separate vacuum arc plasma guns with suitably interleaved repetitive pulsing. Transmission electron microscope images show that the size of the gold nanoparticles obtained by ion implantation is 3-5 nm. For the Au-DLC composite obtained by co-deposition, there were two different nanoparticle sizes, most about 2 nm with some 6-7 nm. Raman spectroscopy indicates that the implanted sample contains a smaller fraction of sp(3) bonding for the DLC, demonstrating that some sp(3) bonds are destroyed by the gold implantation. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4757029]

Subdivision of Hysteresis Loss in Mn-Zn Ferrite Toroidal Cores

The hysteresis loss subdivision method proved to be a strong tool to help in the analysis of different energy dissipation mechanisms along the quasi-static hysteresis loop measured on electrical steels. This paper used the samemethod to discuss the mechanisms involving the energy loss dissipation in Mn-Zn ferrite toroidal cores. The samples, sintered under controlled atmosphere in industrial conditions, were measured under triangular waveform excitation at very low frequency (5 mHz) and peak flux densities varying from 0.05 T to 0.45 T. The results show a different behavior between the low inductions hysteresis loss (WLI) and the high induction hysteresis loss (WHI) which proves the existence of different energy dissipation mechanisms affecting these loss components.

Preparation and Structural Characterization of Vulcanized Natural Rubber Nanocomposites Containing Nickel-Zinc Ferrite Nanopowders

Single-phase polycrystalline mixed nickel-zinc ferrites belonging to Ni0.5Zn0.5Fe2O4 were prepared on a nanometric scale (mean crystallite size equal to 14.7 nm) by chemical synthesis named the modified poliol method. Ferrite nanopowder was then incorporated into a natural rubber matrix producing nanocomposites. The samples were investigated by means of infrared spectroscopy, X-ray diffraction, scanning electron microscopy and magnetic measurements. The obtained results suggest that the base concentration of nickel-zinc ferrite nanoparticles inside the polymer matrix volume greatly influences the magnetic properties of nanoconnposites. A small quantity of nanoparticles, less than 10 phr, in the nanocomposite is sufficient to produce a small alteration in the semi-crystallinity of nanocomposites observed by X-ray diffraction analysis and it produces a flexible magnetic composite material with a saturation magnetization, a coercivity field and an initial magnetic permeability equal to 3.08 emu/g, 99.22 Oe and 9.42 X 10(-5) respectively.

Magnetic hyperthermia investigation of cobalt ferrite nanoparticles: Comparison between experiment, linear response theory, and dynamic hysteresis simulations

Considerable effort has been made in recent years to optimize materials properties for magnetic hyperthermia applications. However, due to the complexity of the problem, several aspects pertaining to the combined influence of the different parameters involved still remain unclear. In this paper, we discuss in detail the role of the magnetic anisotropy on the specific absorption rate of cobalt-ferrite nanoparticles with diameters ranging from 3 to 14 nm. The structural characterization was carried out using x-ray diffraction and Rietveld analysis and all relevant magnetic parameters were extracted from vibrating sample magnetometry. Hyperthermia investigations were performed at 500 kHz with a sinusoidal magnetic field amplitude of up to 68 Oe. The specific absorption rate was investigated as a function of the coercive field, saturation magnetization, particle size, and magnetic anisotropy. The experimental results were also compared with theoretical predictions from the linear response theory and dynamic hysteresis simulations, where exceptional agreement was found in both cases. Our results show that the specific absorption rate has a narrow and pronounced maxima for intermediate anisotropy values. This not only highlights the importance of this parameter but also shows that in order to obtain optimum efficiency in hyperthermia applications, it is necessary to carefully tailor the materials properties during the synthesis process. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4729271]

Synthesis of supported metal nanoparticle catalysts using ligand assisted methods

The synthesis and characterization methods of metal nanoparticles (NPs) have advanced greatly in the last few decades, allowing an increasing understanding of structure-property-performance relationships. However, the role played by the ligands used as stabilizers for metal NPs synthesis or for NPs immobilization on solid supports has been underestimated. Here, we highlight some recent progress in the preparation of supported metal NPs with the assistance of ligands in solution or grafted on solid supports, a modified deposition-reduction method, with special attention to the effects on NPs size, metal-support interactions and, more importantly, catalytic activities. After presenting the general strategies in metal NP synthesis assisted by ligands grafted on solid supports, we highlight some recent progress in the deposition of pre-formed colloidal NPs on functionalized solids. Another important aspect that will be reviewed is related to the separation and recovery of NPs. Finally, we will outline our personal understanding and perspectives on the use of supported metal NPs prepared through ligand-assisted methods.

Recent advances in the development of magnetically recoverable metal nanoparticle catalysts

The aim of this Account is to provide an overview of our current research activities on the design and modification of superparamagnetic nanomaterials for application in the field of magnetic separation and catalysis. First, an introduction of magnetism and magnetic separation is done. Then, the synthetic strategies that have been developed for generating superparamagnetic nanoparticles spherically coated by silica and other oxides, with a focus on well characterized systems prepared by methods that generate samples of high quality and easy to scale-up, are discussed. A set of magnetically recoverable catalysts prepared in our research group by the unique combination of superparamagnetic supports and metal nanoparticles is highlighted. This Account is concluded with personal remarks and perspectives on this research field.

Influence of nanoparticle size on the nonlinear optical properties of magnetite ferrofluids

The nonlinear index of refraction (n(2)) and the two-photon absorption coefficient (beta) of water-based ferrofluids made of magnetite nanocrystals of different sizes and with different coatings have been measured through the Z-scan technique, with ultrashort (femtoseconds) laser pulses. Their third-order susceptibility is calculated from the values of n(2) and beta. The influence of different particles' coatings and sizes on these nonlinear optical properties are investigated. The values of n(2) and beta depend more significantly on the nanoparticles' size than on the particular coating. We observe a decrease of beta as the nanoparticles' diameters decrease, although the optical gap is found to be the same for all samples. The results are interpreted considering modifications in the electronic orbital shape due to the particles' nanosize effect.

Enhancement of laser induced Au nanoparticle formation by femtosecond pulse shaping

We report the control of Au nanoparticle (NP) formation by using shaped 30 fs pulses, in a solution containing HAuCl4 and chitosan. By using a sinusoidal spectral phase, a periodic train of pulses is generated. When the period of the pulse train matches certain Raman resonances of chitosan, the reducing agent of the process, an enhancement of the Au NP formation is observed. Theoretical quantum chemical calculations indicate that the outer groups of the chitosan are mostly influenced by low Raman frequencies, which is in reasonably agreement with the experimental data and indicates an enhancement in the Au NP formation as the pulse train period increases (low frequency).