Crystallization on the Mesoscale : Self-Assembly of Iron Oxide Nanocubes into Mesocrystals

Self-assembly of nanoparticles is a promising route to form complex, nanostructured materials with functional properties. Nanoparticle assemblies characterized by a crystallographic alignment of the nanoparticles on the atomic scale, i.e. mesocrystals, are commonly found in nature with outstanding functional and mechanical properties. This thesis aims to investigate and understand the formation mechanisms of mesocrystals formed by self-assembling iron oxide nanocubes. We have used the thermal decomposition method to synthesize monodisperse, oleate-capped iron oxide nanocubes with average edge lengths between 7 nm and 12 nm and studied the evaporation-induced self-assembly in dilute toluene-based nanocube dispersions. The influence of packing constraints on the alignment of the nanocubes in nanofluidic containers has been investigated with small and wide angle X-ray scattering (SAXS and WAXS, respectively). We found that the nanocubes preferentially orient one of their {100} faces with the confining channel wall and display mesocrystalline alignment irrespective of the channel widths.  We manipulated the solvent evaporation rate of drop-cast dispersions on fluorosilane-functionalized silica substrates in a custom-designed cell. The growth stages of the assembly process were investigated using light microscopy and quartz crystal microbalance with dissipation monitoring (QCM-D). We found that particle transport phenomena, e.g. the coffee ring effect and Marangoni flow, result in complex-shaped arrays near the three-phase contact line of a drying colloidal drop when the nitrogen flow rate is high. Diffusion-driven nanoparticle assembly into large mesocrystals with a well-defined morphology dominates at much lower nitrogen flow rates. Analysis of the time-resolved video microscopy data was used to quantify the mesocrystal growth and establish a particle diffusion-based, three-dimensional growth model. The dissipation obtained from the QCM-D signal reached its maximum value when the microscopy-observed lateral growth of the mesocrystals ceased, which we address to the fluid-like behavior of the mesocrystals and their weak binding to the substrate. Analysis of electron microscopy images and diffraction patterns showed that the formed arrays display significant nanoparticle ordering, regardless of the distinctive formation process.  We followed the two-stage formation mechanism of mesocrystals in levitating colloidal drops with real-time SAXS. Modelling of the SAXS data with the square-well potential together with calculations of van der Waals interactions suggests that the nanocubes initially form disordered clusters, which quickly transform into an ordered phase.

The Desert of the Real in Spec Ops: The Line. A Study of Simultaneous Hyperreal Experiences by Protagonist and Player : A Study of Simultaneous Hyperreal Experiences by Protagonist and Player

As an anomaly on the market of military shooters of the 21st century, Spec Ops: The Line entails a journey of undetermined realities and modern warfare consequences. In this study, the narrative is analyzed from the perspective of Jean Baudrillard’s idea that simulations have replaced our conception of reality. Both the protagonist and the player of Spec Ops will unavoidably descend into a state of the hyperreal. They experience multiple possible realities within the game narrative and end up unable to comprehend what has transpired. The hyperreal is defined as the state in which it is impossible to discern reality from simulation. The simulation of reality has proliferated itself into being the reality, and the original has been lost. The excessive use of violence, direct approach of the player through a break with the 4th wall and a deceitful narrator contribute to this loss of reality within the game. Although the game represents simulacra, being a simulation in itself, the object of study is the coexisting state of hyperreal shared between protagonist and player when comprehending events in the game. In the end, neither part can understand or discern with any certainty what transpired within the game.