Scanning probe microscopy studies of interaction forces between particles: emphasis on magnetite, bentonite and silica

Sammanfattning: Scanning probe microscopy (SPM), such as the atomic force microscope (AFM), using colloidal probes is a highly suitable technique to probe single particle-particle interactions in aqueous solution. The interaction force between a colloidal probe on the AFM cantilever and sample surface is measured. Ultrasmall intermolecular and surface forces, down to the piconewton level, can reliably be measured under controlled experimental conditions with AFM. The interaction between magnetite, bentonite and silica particles plays an important role in many different applications. One important application is in the steel production process where high-quality iron ore pellets are used. Moreover, the interaction between magnetite nanoparticles with Ca2+ ions and with silica particles has high importance in several medical applications and for nanoelectronics. It is known and widely studied that particle surface properties significantly affect the particle dispersion and aggregation. Also, the particles are often treated in aqueous suspensions or in moist conditions prior to the final aggregation, for instance in a pelletizing processes. Thus, different dissolved chemical species may modify the magnetite, bentonite and silica surfaces, which causes the surface properties to change. However, the exact mechanism how the dissolved chemical species influence the direct particle-particle interaction and particle adhesion is not well known.The main focus of this thesis was the study of magnetite particle force interaction with natural and synthetic magnetite, silica and bentonite particles in aqueous solution with SPM. In addition, complimentary methods, such as scanning electron microscopy (SEM), vertical scanning interferometry (VSI), energy dispersive spectroscopy (SEM-EDS), x-ray diffraction (XRD) and electrophoresis techniques were used for surface morphology investigation, chemical characterization, determination of atomic structure and measurements of zeta-potential. The particle interaction forces were examined in solutions with various Ca2+ ion concentrations and in NaCl solution to determine the effect of Ca2+ ions on the surface properties. Also, the effect of pH at various concentrations was studied. The colloidal probes in the studies were natural magnetite and bentonite particles, micrometer-sized spherical silica particles. Sample surfaces were natural magnetite particles, smooth layers of synthetic magnetite nanoparticles and bentonite flakes.Qualitative changes in adhesion forces, i.e. interaction trends, and forces on approach for magnetite-magnetite, magnetite-silica, magnetite-bentonite and bentonite-silica interaction systems with an increase of Ca2+ ion concentration and pH were measured and evaluated. The interaction trends were consistent in most cases with zeta-potential measurements. Possible surface modification and formation of calcium silicates and calcium carbonates at pH 10 on the magnetite surfaces was discussed. The long-range repulsive interaction, similar to a steric-like interaction, was observed in the interactions for bentonite-silica and magnetite-silica systems, likely due to the swelling of bentonite layers and rising of bentonite flakes from the surface. The rising of bentonite flakes in water was verified with cryo-scanning electron microcopy investigation. Furthermore, the measured adhesion forces were compared with calculated adhesion forces, which were evaluated with the use of a few contact mechanics models. The comparison revealed discrepancies, which could be explained by the particle surface roughness. Additionally, a comparison of VSI and AFM techniques for surface characterization was performed on samples possessing sharp periodic surface structures and three stage plateaux honed cast iron surface. This comparison is of high relevance to the accurate calculation of tribological surface roughness parameters. Moreover, force measurements on biological samples and between magnetic particles are also briefly discussed in the thesis.The work within this thesis shows that SPM methods can be successfully applied to measure and predict forces between natural particles, such as magnetite and bentonite, in solution. The obtained and presented results are new and of high interest in applications where the knowledge of the dispersion and aggregation of studied particle interaction is important.