Continuous production of iron-based nanocrystals by laser pyrolysis. Effect of operating variables on size, composition and magnetic response.

Well dispersed iron-based magnetic nanoparticles have been prepared by gas phase laser-driven decomposition of iron pentacarbonyl. Agglomeration of the newly synthesized nanoparticles could be avoided by using a liquid collection system in which the exit stream from the laser reactor was bubbled through triethylene glycol (TREG). The effect of different experimental parameters (precursor concentration, laser power, working pressure, residence time) was studied and, by selecting the appropriate conditions, the size of the resulting magnetic nanocrystals could be tuned from ultrasmall (ca. 2.5 nm) to around 12 nm. For nanoparticle sizes around 10 nm and larger a metallic iron core could be preserved. These iron/iron oxide core-shell compositions exhibit very high values of magnetization, 127 emu g(-1).

Use of a polyol liquid collection medium to obtain ultrasmall magnetic nanoparticles by laser pyrolysis.

The present work addresses the main bottleneck in the synthesis of magnetic nanoparticles by laser pyrolysis. Since the introduction of laser pyrolysis for the production of nanoparticles nearly three decades ago, this method has been repeatedly presented as a highly promising alternative, on account of two main characteristics: (i) its flexibility, since nanoparticles can be formed from a wide variety of precursors in both gas and liquid phase, and (ii) its continuous nature, avoiding the intrinsic variability of batch processing. However, the results reported to date invariably show considerable aggregation of the obtained nanoparticles, which strongly limits their application in most fields. In this work, we have been able to circumvent this problem by collecting the particles in a polyol liquid medium. This method prevents the formation of aggregates and renders a uniform distribution of well dispersed ultrasmall nanoparticles (<4 nm) in a water-compatible solvent. We consider that the effectiveness of this novel collection method for the production of well-dispersed magnetic nanoparticles will be of high interest to a wide range of scientists working in the nanoparticle synthesis field and may enable new applications wherever there is a strict requirement for non-agglomerated nanoparticles.

Surface functionalization for tailoring the aggregation and magnetic behaviour of silica-coated iron oxide nanostructures.

We report here a detailed structural and magnetic study of different silica nanocapsules containing uniform and highly crystalline maghemite nanoparticles. The magnetic phase consists of 5 nm triethylene glycol (TREG)- or dimercaptosuccinic acid (DMSA)-coated maghemite particles. TREG-coated nanoparticles were synthesized by thermal decomposition. In a second step, TREG ligands were exchanged by DMSA. After the ligand exchange, the ζ potential of the particles changed from -10 to -40 mV, whereas the hydrodynamic size remained constant at around 15 nm. Particles coated by TREG and DMSA were encapsulated in silica following a sol-gel procedure. The encapsulation of TREG-coated nanoparticles led to large magnetic aggregates, which were embedded in coalesced silica structures. However, DMSA-coated nanoparticles led to small magnetic clusters inserted in silica spheres of around 100 nm. The final nanostructures can be described as the result of several competing factors at play. Magnetic measurements indicate that in the TREG-coated nanoparticles the interparticle magnetic interaction scenario has not dramatically changed after the silica encapsulation, whereas in the DMSA-coated nanoparticles, the magnetic interactions were screened due to the function of the silica template. Moreover, the analysis of the AC susceptibility suggests that our systems essentially behave as cluster spin glass systems.

Determination of the oxidation state for iron oxide minerals by energy-filtering TEM.

The oxidation state of iron oxide nanoparticles was determined using the two principally different technical realisations of energy filtering TEM, in one case using the JEOL 3010 equipped with a LaB6 cathode and a post-column GIF and in the second, the newly designed LIBRA 200FE equipped with an corrected in-column 90 degrees energy filter and a field emission gun (Schottky emitter). The samples studied were oxide-coated iron nanoparticles, and iron oxide inclusions in feldspars in granites. Five possible candidates exist for the iron-oxide phases: FeO, alpha-Fe2O3 (hematite), gamma-Fe2O3 (maghemite), Fe3O4 (magnetite) or alpha-FeO(OH) (goethite). Fingerprinting the O K-edge ELNES allows to distinguish between oxide phases with the same stochiometry and enables to make a first selection of possible candidates. The additional determination of the chemical composition allows unique identification of the phase present. For the oxide coated iron nanoparticles the most probable iron oxide phase of the shell is maghemite, which was additionally confirmed by HRTEM studies. The second studied system were iron oxide needles in alkali feldspar, where we obtained hematite as the most probable phase. There we additionally demonstrated the drastic changes of the ELNES of the O K-edge for the alkali feldspar and iron oxide needle by spatially resolved EELS.