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.

‘State failure’ and the extraterritorial use of force in self-defence against non-state actors

The thesis is first and foremost the examination of the notion and consequences of ‘state failure’ in international law. The disputes surrounding criteria for creation and recognition of states pertain to efforts to analyse legal and factual issues unravelling throughout the continuing existence of states, as best evidenced by the ‘state failure’ phenomenon. It is argued that although the ‘statehood’ of failed states remains uncontested, their sovereignty is increasingly considered to be dependent on the existence of effective governments. The second part of this thesis focuses on the examinations of the legal consequences of the continuing existence of failed states in the context of jus ad bellum. Since the creation of the United Nations the ability of states to resort to armed force without violating what might be considered as the single most important norm of international law, has been considerably limited. State failure and increasing importance of non-state actors has become a greatly topical issue within recent years in both scholarship and the popular imagination. There have been important legal developments within international law, which have provoked much academic, and in particular, legal commentary. On one level, the thesis contributes to this commentary. Despite the fact that the international community continues to perpetuate a notion of ‘statehood’ which allows the state-centric system of international law to exist, when dealing with practical and political realities of state failure, international law may no longer consider external sovereignty of states as an undeniable entitlement to statehood. Accordingly, the main research question of this thesis is whether the implicit and explicit invocation of the state failure provides sufficient legal basis for the intervention in self-defence against non-state actors in located in failed states. It has been argued that state failure has a profound impact, the extent of which is yet to be fully explored, on the modern landscape of peace and security.

Institutional Persistence and Change in England's Common Law: 1700-1865

Institutions are widely regarded as important, even ultimate drivers of economic growth and performance. A recent mainstream of institutional economics has concentrated on the effect of persisting, often imprecisely measured institutions and on cataclysmic events as agents of noteworthy institutional change. As a consequence, institutional change without large-scale shocks has received little attention. In this dissertation I apply a complementary, quantitative-descriptive approach that relies on measures of actually enforced institutions to study institutional persistence and change over a long time period that is undisturbed by the typically studied cataclysmic events. By placing institutional change into the center of attention one can recognize different speeds of institutional innovation and the continuous coexistence of institutional persistence and change. Specifically, I combine text mining procedures, network analysis techniques and statistical approaches to study persistence and change in England’s common law over the Industrial Revolution (1700-1865). Based on the doctrine of precedent - a peculiarity of common law systems - I construct and analyze the apparently first citation network that reflects lawmaking in England. Most strikingly, I find large-scale change in the making of English common law around the turn of the 19th century - a period free from the typically studied cataclysmic events. Within a few decades a legal innovation process with low depreciation rates (1 to 2 percent) and strong past-persistence transitioned to a present-focused innovation process with significantly higher depreciation rates (4 to 6 percent) and weak past-persistence. Comparison with U.S. Supreme Court data reveals a similar U.S. transition towards the end of the 19th century. The English and U.S. transitions appear to have unfolded in a very specific manner: a new body of law arose during the transitions and developed in a self-referential manner while the existing body of law lost influence, but remained prominent. Additional findings suggest that Parliament doubled its influence on the making of case law within the first decades after the Glorious Revolution and that England’s legal rules manifested a high degree of long-term persistence. The latter allows for the possibility that the often-noted persistence of institutional outcomes derives from the actual persistence of institutions.

Reconciling History and International Law: Territorial and Maritime Claims in the South China Sea and East China Sea

High-ranking Chinese military officials are often quoted in international media as stating that China cannot afford to lose even an inch of Chinese territory, as this territory has been passed down from Chinese ancestors. Such statements are not new in Chinese politics, but recently this narrative has made an important transition. While previously limited to disputes over land borders, such rhetoric is now routinely applied to disputes involving islands and maritime borders. China is increasingly oriented toward its maritime borders and seems unwilling to compromise on delimitation disputes, a transition mirrored by many states across the globe. In a similar vein, scholarship has found that territorial disputes are particularly intractable and volatile when compared with other types of disputes, and a large body of research has grappled with producing systematic knowledge of territorial conflict. Yet in this wide body of literature, an important question has remained largely unanswered - how do states determine which geographical areas will be included in their territorial and maritime claims? In other words, if nations are willing to fight and die for an inch of national territory, how do governments draw the boundaries of the nation? This dissertation uses in-depth case studies of some of the most prominent territorial and maritime disputes in East Asia to argue that domestic political processes play a dominant and previously under-explored role in both shaping claims and determining the nature of territorial and maritime disputes. China and Taiwan are particularly well suited for this type of investigation, as they are separate claimants in multiple disputes, yet they both draw upon the same historical record when establishing and justifying their claims. Leveraging fieldwork in Taiwan, China, and the US, this dissertation includes in-depth case studies of China’s and Taiwan’s respective claims in both the South China Sea and East China Sea disputes. Evidence from this dissertation indicates that officials in both China and Taiwan have struggled with how to reconcile history and international law when establishing their claims, and that this struggle has introduced ambiguity into China's and Taiwan's claims. Amid this process, domestic political dynamics have played a dominant role in shaping the options available and the potential for claims to change in the future. In Taiwan’s democratic system, where national identity is highly contested through party politics, opinions vary along a broad spectrum as to the proper borders of the nation, and there is considerable evidence that Taiwan’s claims may change in the near future. In contrast, within China’s single-party authoritarian political system, where nationalism is source of regime legitimacy, views on the proper interpretation of China’s boundaries do vary, but along a much more narrow range. In the dissertation’s final chapter, additional cases, such as South Korea’s position on Dokdo and Indonesia’s approach to the defense of Natuna are used as points of comparison to further clarify theoretical findings.

Solidarity, the network and the history of workers' self-management from the Gdańsk Agreement to shock therapy

This PhD thesis is an empirical research project in the field of modern Polish history. The thesis focuses on Solidarity, the Network and the idea of workers’ self-management. In addition, the thesis is based on an in-depth analysis of Solidarity archival material. The Solidarity trade union was born in August 1980 after talks between the communist government and strike leaders at the Gdansk Lenin Shipyards. In 1981 a group called the Network rose up, due to cooperation between Poland’s great industrial factory plants. The Network grew out of Solidarity; it was made up of Solidarity activists, and the group acted as an economic partner to the union. The Network was the base of a grass-roots, nationwide workers’ self-management movement. Solidarity and the self-management movement were crushed by the imposition of Martial Law in December 1981. Solidarity revived itself immediately, and the union created an underground society. The Network also revived in the underground, and it continued to promote self-management activity where this was possible. When Solidarity regained its legal status in April 1989, workers’ self-management no longer had the same importance in the union. Solidarity’s new politico-economic strategy focused on free markets, foreign investment and privatization. This research project ends in July 1990, when the new Solidarity-backed government enacted a privatization law. The government decided to transform the property ownership structure through a centralized privatization process, which was a blow for supporters of workers’ self-management. This PhD thesis provides new insight into the evolution of the Solidarity union from 1980-1990 by analyzing the fate of workers’ self-management. This project also examines the role of the Network throughout the 1980s. There is analysis of the important link between workers’ self-management and the core ideas of Solidarity. In addition, the link between political and economic reform is an important theme in this research project. The Network was aware that authentic workers’ self-management required reforms to the authoritarian political system. Workers’ self-management competed against other politico-economic ideas during the 1980s in Poland. The outcome of this competition between different reform concepts has shaped modern-day Polish politics, economics and society.

A Phenomenological Exploration of Black Male Law Enforcement Officers' Perspectives of Racial Profiling and Their Law Enforcement Career Exploration and Commitment

This phenomenological study explored Black male law enforcement officers’ perspectives of how racial profiling shaped their decisions to explore and commit to a law enforcement career. Criterion and snow ball sampling was used to obtain the 17 participants for this study. Super’s (1990) archway model was used as the theoretical framework. The archway model “is designed to bring out the segmented but unified and developmental nature of career development, to highlight the segments, and to make their origin clear” (Super, 1990, p. 201). Interview data were analyzed using inductive, deductive, and comparative analyses. Three themes emerged from the inductive analysis of the data: (a) color and/or race does matter, (b) putting on the badge, and (c) too black to be blue and too blue to be black. The deductive analysis used a priori coding that was based on Super’s (1990) archway model. The deductive analysis revealed the participants’ career exploration was influenced by their knowledge of racial profiling and how others view them. The comparative analysis between the inductive themes and deductive findings found the theme “color and/or race does matter” was present in the relationships between and within all segments of Super’s (1990) model. The comparative analysis also revealed an expanded notion of self-concept for Black males – marginalized and/or oppressed individuals. Self-concepts, “such as self-efficacy, self-esteem, and role self-concepts, being combinations of traits ascribed to oneself” (Super, 1990, p. 202) do not completely address the self-concept of marginalized and/or oppressed individuals. The self-concept of marginalized and/or oppressed individuals is self-efficacy, self-esteem, traits ascribed to oneself expanded by their awareness of how others view them. (DuBois, 1995; Freire, 1970; Sheared, 1990; Super, 1990; Young, 1990). Ultimately, self-concept is utilized to make career and life decisions. Current human resource policies and practices do not take into consideration that negative police contact could be the result of racial profiling. Current human resource hiring guidelines penalize individuals who have had negative police contact. Therefore, racial profiling is a discriminatory act that can effectively circumvent U.S. Equal Employment Opportunities Commission laws and serve as a boundary mechanism to employment (Rocco & Gallagher, 2004).

Financial and Criminal Responsibility for Public Funds – Protection of the Constitutional Fundamental Social Law of Health

Abstract: The implementation of Fundamental Constitutional Health and Social Rights is necessary, appropriate and proportionate, following the demands of the population. Accountability and self-responsibility play a very important role. This requires the development of constitutional principles that protect public funds against corruption and offer a constitutional right to health protection. Financial and criminal liability might provide an incentive to improve the management of public funds and reinforce fundamental constitutional principles, particularly regarding the right to health. Constitutional, administrative and criminal issues, as well as public management and administration and the science of good governance, should be articulated in a single strategy also in the health sector. In Portugal and Brazil, as examples, the Federal Court / Constitutional Court, the Supreme Court / High Court of Justice or the Court of Auditors should be considered together.

El rol de la Unión Africana (UA) en el Cuerno de África a partir del caso de Somalia - AMISOM (2007-2013)

El propósito de esta monografía es comprender cuál ha sido el rol de la Unión Africana (UA), dentro de la misión de paz AMISOM en el periodo de 2007- 2013. Por ello, el trabajo abarca aspectos geopolíticos e históricos, que han influido en la configuración del conflicto armado de Somalía y que han llevado progresivamente a la creación, evolución e implementación de mecanismos como las misiones de paz. Además, se abarcan los planteamientos del neo-funcionalismo y el neo-regionalismo para comprender las estructuras y las dinámicas propias de la UA y así, comprender la naturaleza tanto de sus acciones, como de sus propósitos; propósitos que aclaman el fomento del panafricanismo. Desde aquí se puede entender como su rol ha contribuido con el crecimiento del mercado de la industria militar en la región, a costa de la responsabilidad de proteger. Por último, se concluye que dichas dinámicas han llevado a la creación de comunidades de inseguridad.

Toward Self-Organising Service Communities

This paper discusses a framework in which catalog service communities are built, linked for interaction, and constantly monitored and adapted over time. A catalog service community (represented as a peer node in a peer-to-peer network) in our system can be viewed as domain specific data integration mediators representing the domain knowledge and the registry information. The query routing among communities is performed to identify a set of data sources that are relevant to answering a given query. The system monitors the interactions between the communities to discover patterns that may lead to restructuring of the network (e.g., irrelevant peers removed, new relationships created, etc.).