Aging effects in the electrokinetics of colloidal iron oxides.

We analyze in this contribution the effect of aging on the electrokinetic properties of magnetite (Fe(3)O(4)) and hematite (alpha-Fe(2)O(3)). In both cases, high-purity commercial samples and monodisperse synthetic particles were studied. Commercial magnetite showed a rather erratic dependence of its electrophoretic mobility u(e) with the concentration of NaCl. Furthermore, sufficient concentrations of the latter were able to change the sign of the mobility. When KNO(3) solutions were used, although no such change was observed, no clear effect of [KNO(3)] on the mobility was found, and, in addition, an intense aging effect was detected, as the mobility became increasingly positive in suspensions that were stored over 1 day. The picture was radically different with synthetic magnetite spheres, as the expected overall decrease of u(e) with either NaCl or KNO(3) concentration was measured. However, also in this case the aging effect was clearly observed: u(e) tended in this case to more negative values upon suspension storage, and a steady value of the mobility was reached only after 5 days in NaCl (and even longer in KNO(3) solutions). Because of the crystal structure similarities between magnetite and maghemite (gamma-Fe(2)O(3)), it has been shown that the final step of magnetite oxidation is maghemite. This is confirmed in the present study, as the mobility-pH trends of magnetite progressively approach those of maghemite after about 7 days of storage. Since hematite is chemically more stable than magnetite, our study focused in this case on the comparison between commercial and synthetic particles. The former showed a negative mobility at pH 5.5 under all conditions, suggesting an isoelectric point well below the value accepted for hematite (>/=7). The effect of aging on commercial samples was again very significant, as u(e) decreased in absolute value, apparently without limit as the time since preparation was longer. In contrast, synthetic hematite showed a more predictable dependence on ionic strength, and more limited aging effects, as u(e) reached equilibrium values after around 5 days in NaCl; longer times were required in KNO(3) solutions.

Stability of dispersions of colloidal hematite/yttrium oxide core-shell particles.

The colloidal stability of suspensions of hematite/yttria core/shell particles is investigated in this work and compared with that of the pure hematite cores. The different electrical surface characteristics of yttrium and iron oxides, as well as the diameters of both types of spherical particles, dominate the overall process of particle aggregation. The aggregation kinetics of the suspensions was followed by measuring their optical absorbance as a function of time. By previously calculating the extinction cross section of particle doublets, it was demonstrated that for both core and core/shell particles the turbidity of the suspensions should increase on aggregation. Such an increase was in fact found in the systems in spite of the ever-present tendency of the particles to settle under gravity. The authors used the initial slope of the turbidity increment time plots as a measure of the ease of aggregation between particles. Thus, they found that the essential role played by pH on the charge generation on the two oxides and the shift of one pH unit between the isoelectric points of hematite and yttria manifest in two features: (i) the stability decreases on approaching the isoelectric point from either the acid or basic side and (ii) the maximum instability is found for hematite at pH 7 and for hematite/yttria at pH 8, that is, close to the isoelectric points of alpha-Fe(2)O(3) and Y(2)O(3), respectively. The role of added electrolyte is simply to yield the suspensions of either type more unstable. Using the surface free energy of the particles, the authors could estimate their Hamaker constants in water. From these and their zeta potentials, the DLVO theory of stability was used to quantitatively explain their results.

Synthesis and characterization of poly(ethyl-2-cyanoacrylate) nanoparticles with a magnetic core.

A method is described to prepare composite colloidal nanoparticles, consisting of a magnetic core (magnetite) and a biodegradable polymeric shell (poly(ethyl-2-cyanoacrylate) or PE-2-CA). The method is based on the so-called anionic polymerization procedure, often used in the synthesis of PE-2-CA nanospheres designed for drug delivery. In the present work, the heterogeneous structure of the particles can confer both magnetic-field responsiveness and potential applicability as a drug carrier. In order to investigate to what extent this target is achieved, we compare the structure, chemical composition, and surface properties of the core/shell particles with those of both the nucleus and the coating material. This preliminary study shows that the synthetic new material displays an intermediate behavior between that of magnetite and PE-2-CA spheres. Thus, electrophoresis measurements as a function of pH and as a function of KNO3 concentration, show great similarity between the core/shell and pure polymer nanoparticles. A similar conclusion is reached when a surface thermodynamic study is performed on the three types of particles: the electron-donor component of the surface free energy of the solids is the quantity that appears to be most sensitive to the surface composition. The fact that PE-2-CA is close to being a non-polar material gives rise to a measurable decrease in the electron-donor component of the surface free energy of core/shell particles as compared to magnetite.

Synthesis and Characterization of Spherical Magnetite/Biodegradable Polymer Composite Particles.

A method for preparing colloidal particles formed by a magnetite nucleus and a biodegradable poly(DL-lactide) polymer coating is first described. The method is based on the so-called double-emulsion technique, employed to obtain polymeric spheres loaded with therapeutic drugs, to be used as drug delivery vectors. The aim of this work was to obtain, in a reproducible and rather simple way, colloidal particles that were both magnetic field responsive, and useful as drug delivery systems. In order to investigate to what extent is this target achieved, we compare the structure, chemical composition, and surface properties of the composite particles with those of the nucleus and the coating material. Although the surface properties of the magnetite core are not completely masked, this preliminary study shows that the synthetic new material displays a behavior intermediate between that of magnetite and poly(DL-lactide) spheres. Thus, electrophoresis measurements as a function of pH shows that the isoelectric point (pH(iep)=5.2) of core/shell colloids is in between those of magnetite (pH(iep)=7) and polymer (pH(iep)<2). A similar conclusion is reached when a surface thermodynamic study is performed on the three types of particles: the electron-donor component of the surface free energy of the solids is the quantity that appears to be most sensitive to the surface composition. The fact that poly(DL-lactide) is close to being a nonpolar material gives rise to a measurable decrease in the electron-donor component of the surface free energy, although the effect of coating is also observable in the electron-acceptor and the apolar van der Waals component. Copyright 2001 Academic Press.

Magnetic Properties of Composite Hematite/Yttrium Oxide Colloidal Particles.

The effect of the shell thickness and density on the magnetic properties of composite colloidal particles consisting of a hematite (alpha-Fe(2)O(3)) core and an yttrium oxide (Y(2)O(3)) layer is described. Pure iron oxide colloidal spheres show two clearly different trends of variation of their magnetic susceptibility, chi(m), with temperature. Below T(M) approximately 220 K, chi(m) shows a slight increase when the particles are heated; a sharp transition is observed at such a critical temperature, whereby chi(m) increases almost 3 times in a very narrow temperature interval, decreasing slowly afterward. This is the result of a well-known transition from perfect to imperfect antiferromagnetism (canted antiferromagnetism). Three types of core/shell particles have been prepared, and a gradual change is observed in chi(m) from that of hematite to that of pure Y(2)O(3). Even the most efficiently covered particles still show a change in their chi(m)-T trends around T(M), and are clearly distinct from Y(2)O(3) particles. Magnetization curves show that coating of hematite particles induces significant changes in the coercivity of the samples. The latter is always larger for composite than for core particles. Copyright 2001 Academic Press.