Dynamical measurements with quartz resonators

Dynamische Messungen mit Quarzresonatoren Die Resonanzfrequenz von Quarzoszillatoren liegt im MHz-Bereich. Die Resonanzen haben hohe Gueten und sind somit empfindlich auf kleine Aenderungen an der Resonatoroberflaeche. 1. Es wurde ein Aufbau entwickelt, um Reibung bei hohen Oberflaechengeschwindigkeiten zu messen (v = 1 m/s). Bei Annaeherung einer Kugel steigen Resonanzfrequenz sowie -breite des Schwingquarzes an. Für groeßere Normalkraefte entsteht ein elastischer Kontakt, der die Frequenzerhoehung erklaert. Kurz vor Eintreten dieses Kontaktes durchlaeuft die Daempfung ein Maximum, das charakteristisch ist für das Auftreten von Reibung. Bei Erhoehung der Schichtdicke (0,4-2,5 nm) einer Schmiermittelbeschichtung (Perfluoropolyether) verringern sich sowohl die Hoehe als auch die Breite dieses Maximums. Es verschwindet mit vollstaendiger Belegung mit einer Monolage (ca. 2 nm). Dies wird durch einen intermittierenden Kontakt der beiden Oberflaechen erklaert. 2. Die Schwingquarzoberfläche wurde mit Polymerbuersten verschiedener Schichtdicken (12-230 nm) beschichtet. Der Loesungsmittelgehalt in diesen Filmen variiert mit dem Dampfdruck der umgebenden Toluolatmosphaere. Bei Trocknung durchlaufen die Filme einen loesungsmittelinduzierten Glasuebergang. Die Sorptionskurven (Loesungsmittelgehalt gegen Dampfdruck) zeigen eine Knick beim Glasuebergang, ihre Ableitungen dagegen eine Stufe. Fuer duenner werdende Schichten verschiebt sich diese Stufe zu niedrigerem Dampfdruck sowie geringerem Loesungsmittelgehalt. Außerdem wird sie breiter und ihre Hoehe nimmt ab.

Characterization of igneous terranes by zircon dating: implications for the UHP relicts occurrences and suture identification in the Central Rhodope, Northern Greece

One of the key for the understanding of an orogenic belt is the characterization of the terranes involved and the identification of the suture(s) separating crustal blocks: these are essential information for large-scale paleo-reconstructions. In addition, the structural relationships between the terranes involved in the collisional processes and the eventual UHP relicts may provide first order inputs to exhumation models of subducted rocks. The structure of the Rhodope Massif (northern Greece and southern Bulgaria) results from the stacking of high-grade nappes during a continental collision, which age is comprised between Latest-Jurassic and Early-Cenozoic. UHP and HP relicts, associated with oceanic and ultramafic material, suggest the presence of a dismembered suture zone within the massif. The location of this suture remains unclear; furthermore, up to now, the UHP and eclogitic localities represent isolated spots and no synthesis on their structural position within the massif has been proposed. The first aim of this work is to define the relationships between HP-UHP relicts, crustal blocks, shear zones and amphibolitic material. To achieve this objective, we characterized the accreted blocks in terms of protoliths ages of the orthogneisses mainly along two cross sections on the Greek part of the belt. Geochemical affinities of meta-igneous rocks served as a complementary tool for terrane characterization and geodynamic interpretation. Single-zircon Pb-Pb evaporation and zircon U-Pb SHRIMP dating of orthogneiss protoliths define two groups of intrusion-ages: Permo-Carboniferous and Late Jurassic-Early Cretaceous. Structurally, these two groups correspond to distinct units: the Late Jurassic gneissic complex overthrusts the one bearing the Permo-Carboniferous orthogneisses. Mylonites, eclogites, amphibolites of oceanic affinities, and UHP micaschists, mark a “melange” zone, intensively sheared towards the SW, which separates the two units. Thus, we interpret them as two distinct terranes, the Rhodope and Thracia terranes, separated by the Nestos suture. The correlation of our findings in northern Greece to the Bulgarian part of the Massif suggests a northern rooting of the Nestos Suture. This configuration results of the closure of a marginal oceanic basin of the Tethys system by a north-directed subduction. This interpretation is supported by the geochemical affinities of the orthogneisses: the Late-Jurassic igneous rocks formed by subduction-related magmatism, pprobably the same north-directed subduction that gave rise to the UHP metamorphism of the metasediments of the “melange” zone. It is noteworthy that the UHP-HP relicts seem to be restricted to the contact between the two terranes suggesting that the UHP relicts are exhumed only within the suture zone. Furthermore, the singularity of the suture suggests that the Late-Jurassic subduction explains the occurrence of UHP and eclogite relicts in the Central Rhodope despite the large age range previously attributed the UHP and/or HP stage.

Speleogenesis and secondary cave minerals in quartz-sandstone and quartzite environment

The main objective of this research is to improve the comprehension of the processes controlling the formation of caves and karst-like morphologies in quartz-rich lithologies (more than 90% quartz), like quartz-sandstones and metamorphic quartzites. In the scientific community the processes actually most retained to be responsible of these formations are explained in the “Arenisation Theory”. This implies a slow but pervasive dissolution of the quartz grain/mineral boundaries increasing the general porosity until the rock becomes incohesive and can be easily eroded by running waters. The loose sands produced by the weathering processes are then evacuated to the surface through processes of piping due to the infiltration of waters from the fracture network or the bedding planes. To deal with these problems we adopted a multidisciplinary approach through the exploration and the study of several cave systems in different tepuis. The first step was to build a theoretical model of the arenisation process, considering the most recent knowledge about the dissolution kinetics of quartz, the intergranular/grain boundaries diffusion processes, the primary diffusion porosity, in the simplified conditions of an open fracture crossed by a continuous flow of undersatured water. The results of the model were then compared with the world’s widest dataset (more than 150 analyses) of water geochemistry collected till now on the tepui, in superficial and cave settings. All these studies allowed verifying the importance and the effectiveness of the arenisation process that is confirmed to be the main process responsible of the primary formation of these caves and of the karst-like superficial morphologies. The numerical modelling and the field observations allowed evaluating a possible age of the cave systems around 20-30 million of years.

Mechanical microcontacts of powder particles studied with the quartz crystal microbalance

Within this work, a particle-polymer surface system is studied with respect to the particle-surface interactions. The latter are governed by micromechanics and are an important aspect for a wide range of industrial applications. Here, a new methodology is developed for understanding the adhesion process and measure the relevant forces, based on the quartz crystal microbalance, QCM. rnThe potential of the QCM technique for studying particle-surface interactions and reflect the adhesion process is evaluated by carrying out experiments with a custom-made setup, consisting of the QCM with a 160 nm thick film of polystyrene (PS) spin-coated onto the quartz and of glass particles, of different diameters (5-20µm), deposited onto the polymer surface. Shifts in the QCM resonance frequency are monitored as a function of the oscillation amplitude. The induced frequency shifts of the 3rd overtone are found to decrease or increase, depending on the particle-surface coupling type and the applied oscillation (frequency and amplitude). For strong coupling the 3rd harmonic decreased, corresponding to an “added mass” on the quartz surface. However, positive frequency shifts are observed in some cases and are attributed to weak-coupling between particle and surface. Higher overtones, i.e. the 5th and 7th, were utilized in order to derive additional information about the interactions taking place. For small particles, the shift for specific overtones can increase after annealing, while for large particle diameters annealing causes a negative frequency shift. The lower overtones correspond to a generally strong-coupling regime with mainly negative frequency shifts observed, while the 7th appears to be sensitive to the contact break-down and the recorded shifts are positive.rnDuring oscillation, the motion of the particles and the induced frequency shift of the QCM are governed by a balance between inertial forces and contact forces. The adherence of the particles can be increased by annealing the PS film at 150°C, which led to the formation of a PS meniscus. For the interpretation, the Hertz, Johnson-Kendall-Roberts, Derjaguin-Müller-Toporov and the Mindlin theory of partial slip are considered. The Mindlin approach is utilized to describe partial slip. When partial slip takes place induced by an oscillating load, a part of the contact ruptures. This results in a decrease of the effective contact stiffness. Additionally, there are long-term memory effects due to the consolidation which along with the QCM vibrations induce a coupling increase. However, the latter can also break the contact, lead to detachment and even surface damage and deformation due to inertia. For strong coupling the particles appear to move with the vibrations and simply act as added effective mass leading to a decrease of the resonance frequency, in agreement with the Sauerbrey equation that is commonly used to calculate the added mass on a QCM). When the system enters the weak-coupling regime the particles are not able to follow the fast movement of the QCM surface. Hence, they effectively act as adding a “spring” with an additional coupling constant and increase the resonance frequency. The frequency shift, however, is not a unique function of the coupling constant. Furthermore, the critical oscillation amplitude is determined, above which particle detach. No movement is detected at much lower amplitudes, while for intermediate values, lateral particle displacement is observed. rnIn order to validate the QCM results and study the particle effects on the surface, atomic force microscopy, AFM, is additionally utilized, to image surfaces and measure surface forces. By studying the surface of the polymer film after excitation and particle removal, AFM imaging helped in detecting three different meniscus types for the contact area: the “full contact”, the “asymmetrical” and a third one including a “homocentric smaller meniscus”. The different meniscus forms result in varying bond intensity between particles and polymer film, which could explain the deviation between number of particles per surface area measured by imaging and the values provided by the QCM - frequency shift analysis. The asymmetric and the homocentric contact types are suggested to be responsible for the positive frequency shifts observed for all three measured overtones, i.e. for the weak-coupling regime, while the “full contact” type resulted in a negative frequency shift, by effectively contributing to the mass increase of the quartz..rnThe interplay between inertia and contact forces for the particle-surface system leads to strong- or weak-coupling, with the particle affecting in three mentioned ways the polymer surface. This is manifested in the frequency shifts of the QCM system harmonics which are used to differentiate between the two interaction types and reflect the overall state of adhesion for particles of different size.rn