Miha Drofenik

SYNTHESIS OF MATERIALS WITHIN REVERSE MICELLES

Reverse micelles as nanosized aqueous droplets existing at certain compositions of water-in-oil microemulsions are widely used today in the synthesis of many types of nanoparticles. However, without a rich conceptual network that would correlate the properties and compositions of reverse micellar microemulsions to the properties of to-be-obtained particles, the design procedures in these cases usually rely on a trial-and-error approach. As like every other science, what is presently known is merely the tip of the iceberg compared to the uninvestigated vastness still lying below. The aim of this article is to present readers with most of the major achievements from the field of materials synthesis within reverse micelles since the first such synthesis was performed in 1982 until today, to possibly open up new perspectives of viewing the typical problems that nowadays dominate the field, and to hopefully initiate the observation and generation of their actual solutions. We intend to show that by refining the oversimplified representations of the roles that reverse micelles play in the processes of nanoparticles synthesis, steps toward a more complex and realistic view of the concerned relationships can be made.The first two sections of the review are of introductory character, presenting the reader with the basic concepts and ideas that serve as the foundations of the field of reverse micellar synthesis of materials. Applications of reverse micelles, other than as media for materials synthesis, as well as their basic structures and origins, together with experimental methods for evaluating their structural and dynamic properties, basic chemicals used for their preparation and simplified explanations of the preparation of materials within, will be reviewed in these two introductory sections. In Secs. 3 and 4, we shall proceed with reviewing the structural and dynamic properties of reverse micelles, respectively, assuming that knowledge of both static and dynamic parameters of microemulsions and changes induced thereof, are a necessary step prior to putting forth any correlations between the parameters that define the properties of microemulsions and the parameters that define the properties of materials synthesized within. Typical pathways of synthesis will be presented in Sec. 5, whereas basic parameters used to describe correlations between the properties of microemulsion reaction media and materials prepared within, including reagent concentrations, ionic strength, temperature, aging time and some of the normally overlooked influences, will be mentioned in Sec. 6. The whole of Sec. 7 is devoted to reviewing water-to-surfactant molar ratio as the most often used parameter in materials design by performing reverse micellar synthesis routes. The mechanisms of particle formation within precipitation synthesis in reverse micelles is discussed in Sec. 8. Synthesis of composites, with special emphasis on silica composites, is described in Sec. 9. All types of materials, classified according to their chemical compositions, that were, to our knowledge, synthesized by using reverse micelles up-to-date, will be briefly mentioned and pointed to the corresponding references in Sec. 10. In Sec. 11, some of the possible future directions for the synthesis of nanostructured materials within reverse micelles, found in combining reverse micellar syntheses and various other synthesis procedures with the aim of reaching self-organizing nanoparticle systems, will be outlined.

Ferromagnetism in suspensions of magnetic platelets in liquid crystal

More than four decades ago, Brochard and de Gennes proposed that colloidal suspensions of ferromagnetic particles in nematic (directionally ordered) liquid crystals could form macroscopic ferromagnetic phases at room temperature. The experimental realization of these predicted phases has hitherto proved elusive, with such systems showing enhanced paramagnetism but no spontaneous magnetization in the absence of an external magnetic field. Here we show that nanometre-sized ferromagnetic platelets suspended in a nematic liquid crystal can order ferromagnetically on quenching from the isotropic phase. Cooling in the absence of a magnetic field produces a polydomain sample exhibiting the two opposing states of magnetization, oriented parallel to the direction of nematic ordering. Cooling in the presence of a magnetic field yields a monodomain sample; magnetization can be switched by domain wall movement on reversal of the applied magnetic field. The ferromagnetic properties of this dipolar fluid are due to the interplay of the nematic elastic interaction (which depends critically on the shape of the particles) and the magnetic dipolar interaction. This ferromagnetic phase responds to very small magnetic fields and may find use in magneto-optic devices.

Hydrothermal synthesis of ultrafine barium hexaferrite nanoparticles and the preparation of their stable suspensions

The hydrothermal treatment of an appropriate suspension of Ba and Fe hydroxides in the presence of a large excess of OH(-) results in the formation of Ba hexaferrite at temperatures as low as 150 degrees C. This low formation temperature enables the synthesis of uniform, ultrafine Ba hexaferrite nanoparticles. These nanoparticles have a disc-like shape, approximately 10 nm wide, but only approximately 3 nm thick. When the temperature of the hydrothermal treatment is increased, large platelet Ba hexaferrite crystals appear as a consequence of secondary re-crystallization (Ostwald ripening). In this work, this undesired process of secondary re-crystallization has been evaluated. We show that the secondary re-crystallization can be totally suppressed with the use of an oleic acid surfactant. The addition of oleic acid enabled the synthesis of uniform, ultrafine nanoparticles at temperatures up to 240 degrees C. The nanoparticles were hydrophobic and could be suspended in nonpolar liquids to form relatively concentrated ferrofluids. Such stable suspensions of hexaferrite nanoparticles will be technologically important, especially as precursors for the preparation of new nanostructured materials, for example nanocomposites or nanostructured ceramic films.

Preparation and properties of water-based magnetic fluids.

Stable suspensions of superparamagnetic iron oxide nanoparticles in water (water-based ferrofluids) were prepared using citric acid (CA) as a surfactant. The influences of different factors on the amount of nanoparticles in a stable suspension were systematically studied. These factors, including the temperature, the pH value and the concentration of CA applied during the adsorption of the CA onto the nanoparticles and during their suspension in water, were evaluated. The highest content of nanoparticles in a stable suspension was obtained when the CA was absorbed at pH values of around 5.2, where two carboxyl groups are dissociated, and when the nanoparticles were suspended at a pH of around 10, where all three carboxyl groups of the CA are in a dissociated state.

Preparation of MnZn-ferrite with microemulsion technique

Nanocrystalline MnZn-ferrite particles with different morphology were prepared from single water-in-oil microemulsion consisting of n-hexanol as an oil phase, surfactant CTAB and an aqueous solution of mixed metal sulfates. A sodium hydroxide solution was used as the precipitating agent and a hydrogen peroxide as the oxidizing reagent. The synthesized materials were characterized using an X-ray diffraction (XRD), transmission electron microscope (TEM), BET surface analyzer and magnetometry.

Electrical properties of donor- and acceptor-doped BaBi4Ti4O15

Abstract The electrical properties of the BaBi 4 Ti 4 O 15 compound, a member of the family of Aurivillius bismuth-based layer-structure perovskites, have been studied as a function of aliovalent doping and processing conditions. The samples were prepared by reaction sintering or hot forging of a mixture of BaTiO 3 and Bi 4 Ti 3 O 12 with Nb substituted for Ti, as a donor dopant, and Fe as an acceptor. The dielectric constant of BaBi 4 Ti 4 O 15 is increased by both dopants. Nb doping decreases the Curie temperature, while Fe doping increases it. The conductivity of BaBi 4 Ti 4 O 15 is p-type and it is decreased by Nb doping and increased by Fe doping. The incorporation of aliovalent dopants into the BaBi 4 Ti 4 O 15 structure, is however, preferentially compensated by the change in the composition of the compound.

Highly resistive grain boundaries in doped MnZn ferrites for high frequency power supplies

The power loss of MnZn ferrites and its relation to average grain size and grain boundary properties was investigated. The power loss was found to be dependent on the average grain size and on the highly electrically resistive grain boundaries which are formed by introduction of aliovalent ions in the outer grain region of a MnZn ferrite. Analysis of ac impedance data, assisted by Auger electron spectroscopy, elucidated the chemical and electrically diversity of doped and undoped samples and its influence on eddy current loss.

Colloidal stability of oleic- and ricinoleic-acid-coated magnetic nanoparticles in organic solvents.

The colloidal stability of oleic- and ricinoleic-acid-coated nanoparticles in organic solvents with dielectric constants ε(r) ranging from 2.0 to 9.8 was studied. Although the acids are structurally similar, there is an OH group in the ricinoleic acids tail, a marked improvement in the colloidal stability of the ricinoleic-acid-coated magnetic nanoparticles in moderately polar organic solvents and monomer methyl methacrylate was observed as a result. The bonding of both acids provokes a significant change in the surface properties of the iron-oxide nanoparticles. A clear shift from a strong electron-donor to a weak electron-donor was confirmed with the bonding of the oleic acid. The effect of ricinoleic acid bonding is even more dramatic: a clear shift toward a weak electron-acceptor is evident. A detailed analysis of the total energy of interaction, including the vOCG theory, between two particles was used to describe the different behaviors of the coated nanoparticles. In the case of the oleic acid nanoparticles in an apolar medium, such as decane, a small net attraction of ∼0.84k(B)T, which is insufficient to cause nanoparticles agglomeration, exists. In polar media the net attraction is larger than 1.5k(B)T, resulting in precipitation of the oleic-acid-coated nanoparticles. The same findings apply to the ricinoleic-acid-coated nanoparticles, but only when dispersed in the apolar medium. In the polar medium an additional repulsion due to polar solvation forces exists, resulting in a decrease of the net attraction to as low as ∼0.14k(B)T.

Sintering and properties of highly donor-doped barium titanate ceramics

The electrical properties of donor (La3+) doped BaTiO3 samples with a donor concentration in the range from 0.3 to 1.5 mol.% of La were studied. Samples were sintered at a low partial pressure of oxygen in order to facilitate anomalous grain growth and donor incorporation. In order to optimise the PTCR anomaly, the samples were annealed in air at 1100°C. Results show that with the use of a specific sintering profile PTCR ceramics containing an amount of donor dopant >0.3 mol.%, can be prepared. Heavily doped samples which do not exhibit anomalous grain growth show a core shell structure.

Sonochemical synthesis of nanocrystalline mercury sulfide, selenide and telluride in aqueous solutions

Nanocrystalline mercury chalcogenides HgE (E=S, Se, Te) were synthesized in a single step by a convenient, simple sonochemical method. Mercury nitrate, Hg(NO3)2, dissolved in 0.1 M ethylenediamine tetraacetic acid (EDTA), was used as the source of mercury and elemental chalcogenes, dissolved in a NaOH solution, as the sources of chalcogenide. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDAX). The synthesis procedure is simple and uses less toxic reagents than the previously reported methods. The results showed that the complexing agent EDTA plays a crucial role in the process.