Magnetic properties of jet-printer inks containing dispersed magnetite nanoparticles

Two ferrofluid inks for jet-printing, containing magnetite NPs of slightly different average radius (sample A: 6 nm; sample B: 8 nm) were prepared by adding a dispersion of magnetite nanopowders in n-hexane to an insulating ink. Isothermal magnetization loops of inks were measured by means of a vibrating sample magnetometer in the temperature interval 5–300 K up to 70 kOe. The inks were then ejected at room temperature on standard paper by means of either a thermal ink jet head (TIJ; sample A) or a piezoelectric ink jet head (PIJ; sample B). Magnetic properties of prints on paper (FC/ZFC curves, isothermal magnetic loops and related hysteretic properties) were measured between 10 and 300 K using an alternating gradient force magnetometer up to 20 kOe. The inks display a different magnetic behavior with respect to both prints. In particular, the dispersed NPs are characterized by an effective radius (and ensuing magnetic interaction) larger than expected on the basis of the properties of the starting powders. Instead, the NP radii in both prints are closer to the starting values. The printed magnetic films show an almost perfect superparamagnetic (SP) response around room temperature; however, at temperatures lower than 100 K the SP scaling is not observed and both samples behave as interacting superparamagnetic (ISP) materials. The evolution from the SP to the ISP regime is marked by a steady increase in the hysteretic properties of both samples. Particular attention will be paid to the study of magnetic interactions occurring among NPs. The effect of the ejection process on the degree of aggregation of magnetite NPs will be here studied.     

Magnetic properties of Co implanted TlInS2 and TlGaSe2 crystals

The results of investigations of magnetic properties of ternary layered TlInS₂ and TlGaSe₂ ferroelectric crystals implanted with 40 keV Co⁺ ions at the fluency of 1.0×10¹⁷ ion cm^?2 are presented. It has been revealed that high-fluence implantation with Co ions results in metal nanoparticle formation in the near-surface irradiated region. The calculations of Co concentration profiles and SEM studies show that the metal nanoparticles are located under the surface at the depth of about 20 nm, and they originate the irregular-shaped bumps on the surface. The Co-implanted samples exhibited superparamagnetic behaviour at high temperatures and ferromagnetic state at temperatures lower than T_b, where T_b is a “blocking temperature” of superparamagnetic nanoparticles. It has been suggested that the observed phenomena can be discussed on the basis of strong magnetic dipolar interaction between Co nanoparticles inside the granular composite film formed as a result of implantation.     

Aggregation resistant zwitterated superparamagnetic nanoparticles

Superparamagnetic nanoparticles (NPs) are promising for biomedical applications since they can be directed toward the organ of interest using an external magnetic field. They are also good contrast agents for magnetic resonance imaging and have potential for the treatment of malignant tumors (i.e., hyperthermia). Therefore, there is a need to produce stable, non-aggregating superparamagnetic nanomaterials that can withstand the in vivo environment. In this work, the colloidal stability of a dispersion of iron oxide NPs was enhanced by functionalizing them with a short zwitterionic siloxane shell in aqueous media. The stabilization procedure yields superparamagnetic nanomaterials, ca. 10 nm in diameter, with saturation magnetization of about 54 emu/g that resist aggregation at physiological salt concentration, temperature, and pH. The loading of the zwitterionic shell was established with diffuse reflectance infrared spectroscopy and thermal gravimetric analysis. X-ray and electron diffraction verified the starting magnetite phase, and that no change in phase occurred on surface functionalization.     

Effects of dipolar interactions on magnetic properties of granular solids

The magnetic behavior of superparamagnetic Co nanoparticles (2–4 nm in diameter) dispersed in an amorphous, insulating SiO₂ matrix was studied. Conventional fittings of magnetization curves present mean magnetic moments which diminish with decrease in temperature. In order to treat this anomalous behavior, we have applied the interacting superparamagnetic model (ISP). Mean diameters obtained from transmission electron microscopy (TEM) were compared with values obtained applying ISP model.     

Magnetite nanoparticles embedded in biodegradable porous silicon

Magnetite nanoparticles, which are coated with oleic acid in a hexane solution and exhibit an average diameter of 7.7 nm, were embedded in a porous silicon (PS) matrix by immersion under defined parameters (e.g. concentration, temperature, time). The porous silicon matrix is prepared by anodization of a highly n-doped silicon wafer in an aqueous HF-solution. Magnetic characterization of the samples has been performed by SQUID-magnetometry. The superparamagnetic behaviour of the magnetite nanoparticles is represented by temperature-dependent magnetization measurements. Zero field (ZFC)/field cooled (FC) experiments indicate magnetic interactions between the particles. For the infiltration into the PS-templates different concentrations of the magnetite nanoparticles are used and magnetization measurements are performed in respect with magnetic interactions between the particles. The achieved porous silicon/magnetite specimens are not only interesting due to their transition between superparamagnetic and ferromagnetic behaviour, and thus for magnetic applications but also because of the non-toxicity of both materials giving the opportunity to employ the system in medical applications as drug delivery or in medical diagnostics.     

Synthesis and characterization of permalloy nanostructured films by deposition of laser ablated nanoparticles

A permalloy (Ni₈₁Fe₁₉; at%) microparticle (MP) aerosol was ablated to produce a nanoparticle (NP) aerosol that was then impacted at high velocity onto a substrate to produce porous thick films. The structure of the NPs was analyzed by transmission electron microscopy and the morphologies of the NPs and the nanostructured films were studied using high-resolution transmission electron microscopy and scanning electron microscopy. These analyses showed that the original composition and structure of the MPs were preserved in the NPs and films. The majority of NPs that were produced ranged in size between 2 and 15 nm with some larger particles present. Magnetization-temperature curves showed that the films consisted of a mixture of small superparamagnetic NPs and larger ferromagnetic NPs. A high saturation magnetization of 62.3 emu/g at 300 K was retained in the films indicating that they remained free of significant oxidation.     

Physical and chemical properties of nanoscale magnetite-based solvent extractant

Nanoscale magnetite bearing magnetic carrier with an adsorbed layer of dibenzo-18-crown-6 was evaluated for removing radionuclides from nuclear waste solutions using magnetically assisted separation method. TEM results indicate that the average size of the base magnetite particles is ∼19 nm. The results of Mössbauer spectroscopy and field cooled (FC) and zero field cooled (ZFC) magnetization confirm the superparamagnetic behaviour of the magnetite particles in the polymer beads at room temperature and hence meet the requirement of magnetic filter regeneration capability.     

Irreversible magnetization in nickel nanoparticles

We report magnetic studies on nickel nanoparticle films of average particle size of 10 nm. Magnetization as a function of field and temperature show that the system behaves like a random magnet with a strongly field-dependent irreversible temperature, below which the magnetization relax logarithmically with time. The effective barrier extrapolated increases strongly with temperature for a given field. The time dependence suggests the dominant dipole–dipole interaction in this magnetic nanoparticle system.     

Synthesis of multiwall carbon nanotubes by chemical vapor deposition of ferrocene alone

Multiwall carbon nanotubes (MWNTs) filled with Fe nanoparticles (NPs) have been synthesized by thermal chemical vapor deposition of ferrocene alone as the precursor. The MWNTs were grown at different temperatures: 980 and 800 ^°C. Characterization of as-prepared MWNTs was done by scanning and transmission electron microscopy, and X-ray diffraction. The transmission electron microscopy study revealed that Fe NPs encapsulated in MWNTs grown at 980 and 800 ^°C are spherical and rod shaped, respectively. Room-temperature vibrating sample magnetometer studies were done on the two samples up to a field of 1 T. The magnetization versus magnetic field loop reveals that the saturation magnetization for the two samples varies considerably, almost by a factor of 4.6. This indicates that Fe is present in different amounts in the MWNTs grown at the two different temperatures.     

Effect of dipolar interaction on the magnetization state of chains of rectangular particles located either head-to-tail or side-by-side

Magnetostatic coupling in arrays of closely spaced magnetic elements is becoming an important issue in the path to the fabrication of spintronic devices. Dense chains of rounded-corners rectangular particles (dots) of lateral size 1025 × 450 nm², with interdot spacing variable in the range between 55 and 700 nm, have been patterned by deep UV lithography, followed by the lift-off of two permalloy films of thickness 20 and 40 nm. Magneto-optical Kerr effect (MOKE) and magnetic force microscopy (MFM) experiments, together with micromagnetic simulations, were performed to study the dependence of the magnetization configuration on the dipolar coupling. Both MOKE measurements and MFM images clearly show that, at remanence, the magnetic state of isolated particles of thickness 20 nm takes the form of a distorted single domain (C-state or S-State configurations). Instead, when the particle thickness is double (40 nm), closure states characterized by one, two or three vortices occur at remanence. However, when the 40 nm thick dots are placed in chains along the easy axis (head to tail), as the separation is progressively reduced, the single domain state is stabilized at remanence. On the other hand, when the 40 nm thick particles are placed side by side in chains the effect of dipolar interactions is to favour the nucleation of vortex states. For small inter-element separation, there is only one vortex per particle and it has the same chirality in adjacent particles, due to the dipolar interaction. Different from this, for the 20 nm thick samples and sub-100 nm separation, adjacent particles are single-domain but with antiparallel magnetization in neighbour elements, like in an artificial antiferromagnet.     

Pinning of domain walls in two-layer ferromagnetic nanowire with scattering fields of nanoparticles

The results of a micromagnetic simulation of the pinning-depinning processes of a domain wall (DW) in a rectangular ferromagnetic nanowire (NW) consisting of two magnetic layers with scattering fields of two rectangular two-layer nanoparticles (NPs) located on NW opposite sides and oriented perpendicular to its axis are presented. The features of magnetization reversal of this system in the external magnetic field are studied depending on direction of the magnetic moments of the nanoparticle layers. The value of the depinning field in such a system depends essentially on mutual orientation of NP magnetic moments and NW magnetization. The possibility to realize a magnetic logic cell performing the “conjunction” operation of ternary logic is discussed.     

Space-selective modification of the magnetic properties of transparent Fe3+-doped glass by femtosecond-laser irradiation

We have demonstrated spatially selective modification of the magnetic properties of transparent iron-oxide-doped glass by femtosecond- (fs-) laser irradiation and subsequent annealing. A near-infrared fs-laser beam with a wavelength of 775 nm was focused 1 mm below the surfaces of glass samples. This produces absorption peaks due to the formation of hole-trap centers in the irradiated region. Transparency was recovered after annealing at 450°C. A ferrimagnetic component was observed in the M–H curve even at room temperature, whereas the diamagnetic component dominated in the M–H curve of the as-prepared glass sample. This indicates that fs-laser irradiation enhanced the magnetization in the irradiated area. The irradiated and annealed glass sample also exhibited superparamagnetic blocking in the temperature dependence of the magnetization with a blocking temperature higher than room temperature. This change in magnetism is presumably due to local crystallization of ferrimagnetic nanoparticles, such as magnetite, induced by fs-laser irradiation and annealing. The magnetic and optical properties of glass that had been annealed but not irradiated by a fs-laser beam remained unchanged.     

Ultrasmall iron oxide nanoparticles: Magnetic and NMR relaxometric properties

Ultrasmall iron oxide (USPIO) nanoparticles, with diameter mostly less than 3 nm dispersed in an organic carrier fluid were synthesized by polyol route. The evolution of ZFC-FC magnetization curves with temperature, as well as the shift of the ac susceptibility peaks upon changing the frequency, reveal that the nanoparticles in the fluid are non-interacting and superparamagnetic with the blocking temperature T_B ∼10 K. The Mössbauer spectra analysis proposed the core/shell structure of the nanoparticles consisting of stoichiometric γ-Fe₂O₃ core and non-stoichiometric shell. The nanoparticle surface layer has a great influence on their properties which is principally manifested in significant reduction of the magnetization and in a large increase in magnetic anisotropy. Magnetic moments do not saturate in fields up to 5 T, even at the lowest measured temperature, T = 5 K. The average magnetic particle diameter is changed from 1.3 to 1.8 nm with increasing magnetic field from 0 to 5 T which is noticeably smaller than the particle sizes measured by TEM. The estimated effective magnetic anisotropy constant value, K_eff = 2 × 10⁵ J/m³, is two orders of magnitude higher than in the bulk maghemite. Measurements of the longitudinal and transverse NMR relaxivity parameters on water diluted nanoparticle dispersions at 1.5 T gave the values r₁ = 0.028 mmol⁻¹ s⁻¹, r₂ = 0.050 mmol⁻¹ s⁻¹ and their ratio r₂/r₁ = 1.8. Continuous increase of the T₁-weighted MRI signal intensity with increasing Fe concentration in the nanoparticle dispersions was observed which makes this ferrofluid to behave as a positive T₁ contrast agent.     

Evidence for magnetic interactions among magnetite nanoparticles dispersed in photoreticulated PEGDA-600 matrix

Magnetite nanoparticles having mean diameter of about 8 nm have been prepared by a thermo-chemical route. Different amounts (5 and 10% wt) of a stable dispersion of magnetite nanoparticles in n-hexane were added to polyethylene glycol diacrylate (PEGDA-600) oligomer containing 2% wt of radicalic photoinitiator. The homogenized mixture was poured on a silica glass substrate and the resulting film was photoreticulated in N₂ atmosphere using a UV lamp. As a result, a polymer-based magnetic nanocomposite was obtained, where the magnetic nanoparticles are dispersed in the diamagnetic matrix, as checked by SEM. Morphology, composition, and size of as-prepared nanoparticles were checked by SEM and X-ray diffraction. The magnetic properties of magnetite nanoparticles prior to and after inclusion in the polymeric matrix have been studied by means of an alternating-gradient magnetometer (T interval: 10–300 K, H_MAX: 18 kOe). FC-ZFC curves were obtained in the same temperature interval. The results show that the nanocomposites cannot be simply described as containing superparamagnetic particles undergoing an anisotropy-driven blocking and that collective magnetic interactions play a non-negligible role. Low-temperature hysteretic properties indicate that the polymeric matrix affects the effective anisotropy of magnetite nanoparticles. Dispersion of magnetite NPs in PEGDA has non-trivial consequences on their magnetic properties.     

Size-controlled synthesis of superparamagnetic iron oxide nanoparticles and their surface coating by gold for biomedical applications

The size mono-dispersity, saturation magnetization, and surface chemistry of magnetic nanoparticles (NPs) are recognized as critical factors for efficient biomedical applications. Here, we performed modified water-in-oil inverse nano-emulsion procedure for preparation of stable colloidal superparamagnetic iron oxide NPs (SPIONs) with high saturation magnetization. To achieve mono-dispersed SPIONs, optimization process was probed on several important factors including molar ratio of iron salts [Fe³⁺ and Fe²⁺], the concentration of ammonium hydroxide as reducing agent, and molar ratio of water to surfactant. The biocompatibility of the obtained NPs, at various concentrations, was evaluated via MTT (3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide) assay and the results showed that the NPs were non-toxic at concentrations <0.1 mg/mL. Surface functionalization was performed by conformal coating of the NPs with a thin shell of gold (∼4 nm) through chemical reduction of attached gold salts at the surface of the SPIONs. The Fe₃O₄ core/Au shell particles demonstrate strong plasmon resonance absorption and can be separated from solution using an external magnetic field. Experimental data from both physical and chemical determinations of the changes in particle size, surface plasmon resonance optical band, phase components, core–shell surface composition, and magnetic properties have confirmed the formation of the mono-dispersed core–shell nanostructure.     

Iron oxide nanoparticles modified with oleic acid: Vibrational and phase determination

A simple path methodology to detect the phase composition of iron oxide nanoparticles modified with oleic acid based on vibrational spectroscopy is present here and applied on three different nanoparticles prepared by co-precipitation method. Firstly, the phase composition, magnetite, maghemite, and hematite, is determined using a reference intensity ratio methodology on X-ray diffraction pattern. Also, the size of each sample was calculated by Scherrer equation. Scanning, transmission electron microscopy, microanalysis and electron diffraction show a core magnetite particles size of around 10 nm for all particles. Based on lattice vibrations, we find a concentration of around 80% of magnetite and a hematite phase lower than 5%. Whereas, the magnetite composition from X-ray diffraction shows 76%. We also investigate the metal-organic interaction and disorder degree of organic molecule conformation by infrared and Raman spectroscopy analysis. Hematite lattice vibrations show more alterations as it interacts with the organic acid. Finally, magnetic measurements at room temperature of the modified particles, suggest a superparamagnetic behavior and high saturation magnetization.     

Water-soluble magnetic nanoparticles with biologically active stabilizers

We present the results of the interaction of iron oxide nanoparticles with some biologically active surfactants, namely, oleic acid and cytotoxic alkanolamine derivatives. Physico-chemical properties, as magnetization, magnetite concentration and particle diameter, of the prepared magnetic samples were studied. The nanoparticle size of 11 nm for toluene magnetic fluid determined by TEM is in good agreement with the data obtained by the method of magnetogranulometry. In vitro cytotoxic effect of water-soluble nanoparticles with different iron oxide:oleic acid molar ratio were revealed against human fibrosarcoma and mouse hepatoma cells. In vivo results using a sarcoma mouse model showed observable antitumor action.     

Nickel nanoparticles deposited into an activated porous carbon: synthesis,microstructure and magnetic properties

Activated carbons (AC) are commonly used as efficient adsorbents to remove contaminants. The incorporation of a magnetic material into the AC could greatly enhance its manipulation through magnetic separation. However, the composite material will need to have sufficiently saturated magnetization, and as low as possible coercivity to be easily attracted by commercial permanent magnets. In this letter we report on the correlation between microstructure and magnetic behaviour of Ni nanoparticles (NPs) embedded in an amorphous activated porous carbon (Ni–AC). The Ni–AC powders have been synthesized by means of an easy and low‐cost procedure. The addition of sucrose during the preparation process provides effective protection in acid media. This Ni–AC composite has a microstructure composed of crystalline NPs with diameters in the range of 7–25 nm, and exhibits superparamagnetic behaviour at room temperature, with saturation magnetization values around 3 A m² kg^–1 under applied magnetic fields of 200 mT. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

EDXRF for elemental determination of nanoparticle-related agricultural samples

The number of studies dealing with nanoparticles (NPs) and plants has increased. They subsidize the advances of agriculture in the 21st century; however, so far, beneficial as well as detrimental results have been reported. In this context, analytical tools for monitoring macronutrients and micronutrients in plants exposed to NPs, with adequate performance and low cost, are required. This work assesses the use of energy-dispersive X-ray fluorescence (EDXRF) spectrometry for elemental content evaluation in NP-containing agricultural samples. For Phaseolus vulgaris (common bean) seedlings treated with ZnO NP, CuO NP, and Fe₃O₄ NP, the limits of detection (LODs) were 0.4 mg kg⁻¹ for Zn and Cu and 0.6 mg kg⁻¹ for Fe after dry-ashing digestion, thus being suitable for NP oxide monitoring in seed priming. For submicron suspension fertilizers, Mn, Cu, and Zn were quantified as thin films after sample dilution. The LODs for Mn, Cu, and Zn were 0.09, 0.1, and 0.08 mg L⁻¹, respectively. Finally, for P. vulgaris plants exposed to 300-nm ZnO NP, we monitored P, S, K, Ca, and Zn directly in powdered leaves, whose LODs ranged from 1.3 to 27 mg kg⁻¹. No critical spectral interference was observed, and notable repeatability and suitable trueness were found in the cases of studies. EDXRF revealed itself a simple, fast, and reliable alternative to evaluate the elemental content in suspensions or the uptake of NP by plants.     

From pure superparamagnetic regime to glass collective state of magnetic moments in γ-Fe2O3 nanoparticle assemblies

Studies of the frequency dependence of the temperature of the AC susceptibility peak, of the thermal variation of the nonlinear DC susceptibility, and of ageing effects on the magnetization relaxation in γ-Fe₂O₃ 4.7 nm nanoparticle assemblies with interparticle interactions of varying strength, give evidence of three magnetic regimes: pure superparamagnetic, superparamagnetic modified by the interactions, and collective. The properties of the latter regime, called glass collective state, are close to those of a canonical spin glass.