Studies on the brookite-rutile transformation

Brookite, the orthorhombic modification of titanium dioxide, transforms to the tetragonal modification, rutile, on heating. The kinetics and energetics of the transformation have been studied. Below 715±10°C, the rate of transformation is extremely slow. There appears to be little or no induction time. The kinetic data can be fitted reasonably well by the first-order equation. The energy of activation is about 60 kcal/mole and the frequency factor is of the order of 1013 h-1. The entropy of activation from Eyring's theory is about -18 cal/mole deg. at 800°C. The heat of this transformation is -100±75 cal/mole. The kinetic results may be explained qualitatively in terms of various analogies but more clearly by the application of the order-disorder theory to diffusionless transformation in solids. It has been shown that the ratio of propagation rate constant to the nucleation rate constant is small and that there is little or negligible phase aggregation.

The Path to a Porous Semiconductor Multilayer

Thin films are the basis of much of recent technological advance, ranging from coatings with mechanical or optical benefits to platforms for nanoscale electronics. In the latter, semiconductors have been the norm ever since silicon became the main construction material for a multitude of electronical components. The array of characteristics of silicon-based systems can be widened by manipulating the structure of the thin films at the nanoscale - for instance, by making them porous. The different characteristics of different films can then to some extent be combined by simple superposition. Thin films can be manufactured using many different methods. One emerging field is cluster beam deposition, where aggregates of hundreds or thousands of atoms are deposited one by one to form a layer, the characteristics of which depend on the parameters of deposition. One critical parameter is deposition energy, which dictates how porous, if at all, the layer becomes. Other parameters, such as sputtering rate and aggregation conditions, have an effect on the size and consistency of the individual clusters. Understanding nanoscale processes, which cannot be observed experimentally, is fundamental to optimizing experimental techniques and inventing new possibilities for advances at this scale. Atomistic computer simulations offer a window to the world of nanometers and nanoseconds in a way unparalleled by the most accurate of microscopes. Transmission electron microscope image simulations can then bridge this gap by providing a tangible link between the simulated and the experimental. In this thesis, the entire process of cluster beam deposition is explored using molecular dynamics and image simulations. The process begins with the formation of the clusters, which is investigated for Si/Ge in an Ar atmosphere. The structure of the clusters is optimized to bring it as close to the experimental ideal as possible. Then, clusters are deposited, one by one, onto a substrate, until a sufficiently thick layer has been produced. Finally, the concept is expanded by further deposition with different parameters, resulting in multiple superimposed layers of different porosities. This work demonstrates how the aggregation of clusters is not entirely understood within the scope of the approximations used in the simulations; yet, it is also shown how the continued deposition of clusters with a varying deposition energy can lead to a novel kind of nanostructured thin film: a multielemental porous multilayer. According to theory, these new structures have characteristics that can be tailored for a variety of applications, with precision heretofore unseen in conventional multilayer manufacture.

The Feminist Transformation of Bioethics : An Analysis of Theoretical Perspectives and Practical Applications in Feminist Bioethics

The purpose of this study is to examine how transformation is defining feminist bioethics and to determine the nature of this transformation. Behind the quest for transformation is core feminism and its political implications, namely, that women and other marginalized groups have been given unequal consideration in society and the sciences and that this situation is unacceptable and should be remedied. The goal of the dissertation is to determine how feminist bioethicists integrate the transformation into their respective fields and how they apply the potential of feminism to bioethical theories and practice. On a theoretical level, feminist bioethicists wish to reveal how current ways of knowing are based on inequality. Feminists pay special attention especially to communal and political contexts and to the power relations endorsed by each community. In addition, feminist bioethicists endorse relational ethics, a relational account of the self in which the interconnectedness of persons is important. On the conceptual level, feminist bioethicists work with beliefs, concepts, and practices that give us our world. As an example, I examine how feminist bioethicists have criticized and redefined the concept of autonomy. Feminist bioethicists emphasize relational autonomy, which is based on the conviction that social relationships shape moral identities and values. On the practical level, I discuss stem cell research as a test case for feminist bioethics and its ability to employ its methodologies. Analyzing these perspectives allowed me first, to compare non-feminist and feminist accounts of stem cell ethics and, second, to analyze feminist perspectives on the novel biotechnology. Along with offering a critical evaluation of the stem cell debate, the study shows that sustainable stem cell policies should be grounded on empirical knowledge about how donors perceive stem cell research and the donation process. The study indicates that feminist bioethics should develop the use of empirical bioethics, which takes the nature of ethics seriously: ethical decisions are provisional and open for further consideration. In addition, the study shows that there is another area of development in feminist bioethics: the understanding of (moral) agency. I argue that agency should be understood to mean that actions create desires.

Synthesis, structure, transformation studies and catalytic properties of open-framework cadmium thiosulfate compounds

Five new thiosulfate based inorganic-organic hybrid open-framework compounds have been synthesized employing mild reaction conditions. Of the five compounds, [Na-2(H2O)(8)][Cd(C10H8N2)( S2O3)(2)]center dot 2H(2)O, I and [Cd-2(C10H8N2)(2)(HS2O3)(2)(S2O3)(2)][(C10H9N2)(2)(C10H8N2)(2)]center dot 8H(2)O, II have one-dimensional (1D) structures and [Cd(C10H8N2)(H2O)(2)(S2O3)]center dot 2H(2)O, III, [Cd-2(C10H8N2)(3)(S2O3)(2)], IV and [Cd-2(C10H8N2)(2.5)(S2O3)(2)], V have three- dimensional (3D) structures. The 1D structures are somewhat related, formed by the bonding between tetrahedral Cd centers (CdN2S2) and 4,4'-bipyridine (bpy) units. The inter-chain spaces are occupied by the hanging thiosulfate units in both the cases along with Na(H2O)(6) chains in I and free bpy units in II. The three 3D structures have one-dimensional cadmium thiosulfate chains linked by bpy units. Interpenetration has been observed in all the 3D structures. The 3D structures appear to be related and can be derived from fgs net. Transformation studies on the 1D compound, [Na-2(H2O)(8)][Cd(C10H8N2)(S2O3)(2)]center dot 2H(2)O, I, indicated a facile formation of [Cd(C10H8N2)(H2O)(2)(S2O3)]center dot 2H(2)O, III. Prolonged heating of I gave rise to a 3D cadmium sulfate phase, [Cd-2(C10H8N2)(2)(H2O)(3)(SO4)(2)]center dot 2H(2)O, VI. Compound VI has one-dimensional cadmium sulfate chains formed by six-membered rings connected by bpy units to form a 3D structure, which appears to resemble the topological arrangement of III. Transformation studies of III indicates the formation of IV and V, and at a higher temperature a new 3D cadmium sulfate, [Cd(C10H8N2)(SO4)], VII. Compound VII has a 4 x 4 grid cadmium sulfate layers pillared by bpy units. All the compounds were characterized by PXRD, TGA, IR and UV-visible studies. Preliminary studies on the possible use of the 3D compounds (III-VII) in heterogeneous cyanosilylation of imines appear to be promising.

On the use of a coordinate transformation for analysis of axisymmetric vibration of polar orthotropic annular plates

Estimates of natural frequencies corresponding to axisymmetric modes of flexural vibration of polar orthotropic annular plates have been obtained for various combinations of clamped, simply supported and free edge conditions. A coordinate transformation in the radial direction has been used to obtain effective solutions by the classical Rayleigh-Ritz method. The analysis with this transformation has been found to be advantageous in computations, particularly for large hole sizes, over direct analysis. Numerical results have been obtained for various values of hole sizes and rigidity ratio. The eigenvalue parameter has been found to vary more or less linearly with the rigidity ratio. A comparison with the results for isotropic plates has brought out some interesting features.

Increasing Knowledge Focus - a Means for Entrepreneurs to Remain on a Growth Path: Essays on the Role and Nature of Knowledge Management in Finnish SMEs (summary section only)

This study explores the role and nature of knowledge management (KM) in small and medium-sized companies (SMEs). Even though the role of knowledge as a competitive advantage is commonly recognized in the SME sector, almost no attention has been paid to the managing and developing of knowledge in SMEs. This thesis consists of three different sub-studies that were reported in four individual essays. The results of the questionnaire study indicate that nearly all companies that responded to the questionnaire (N = 108) found intangible assets, i.e. knowledge resources to be their main source of competitive advantage. However, only less than a third of the companies actively deal with knowledge management. The results also indicate a significant correlation between activity in knowledge management and sustainable organic growth of the company. The interview study (N = 10) explored the context and motives of the SMEs for managing their intangible assets, and the concrete practices of knowledge management. It turned out that KM facilitated change management, clarification of the vision and new strategy formulation. All the interviewed companies were aiming at improved innovation process, new ways of doing business and attaining an increased “knowledge focus” in their business. Nearly all also aspired to grow significantly. Thus, KM provides a strategy for these SMEs to guarantee their survival and sustainability in the turbulent markets. The action research was a process to assess and develop intangible resources in three companies. The experienced benefits were the clarification of future focus and strategy, creation of a common language to discuss strategic issues within the company, as well as improved balance of different categories of intangible assets. After the process all the case companies had developed in the chosen key areas. Thus, by systematic knowledge management the implementation of new strategic orientation (knowledge focusing) was facilitated. The findings can be summarized in two main points. First, knowledge management seems to serve the purpose of change, renewal and new strategic orientation in the SMEs. It also seems to be closely related to organic growth and innovation. All of these factors can be considered dimensions of entrepreneurship. Second, the conscious development of intangible assets can increase the balance of different categories of intangible assets and the overall knowledge focusing of business. In the case companies, this in turn facilitated the path to the improved overall performance.

Service Productivity: Toward a Conceptualisation of the Transformation of inputs

The productivity of a process is related to how effectively input resources are transformed into value for customers. For the needs of manufacturers of physical products there are widely used productivity concepts and measurements instruments. However, in service processes the underlying assumptions of these concepts and models do not hold. For example, manufacturing-based productivity models assume that an altered configuration of input resources in the production process does not lead to quality changes in outputs (the constant-quality assumption). However, in a service context changes in the production resources and productions systems do affect the perceived quality of services. Therefore, using manufacturing-oriented productivity models in service contexts are likely to give managers wrong directions for action. Research into the productivity of services is still scarce, because of the lack of viable models. The purpose of the present article is to analyse the requirements for the development of a productivity concept for service operations. Based on the analysis, a service productivity model is developed. According to this model, service productivity is a function of 1) how effectively input resources into the service (production) process are transformed to outputs in the form of services (internal or cost efficiency), 2) how well the quality of the service process and its outcome is perceived (external or revenue efficiency), and 3) how effectively the capacity of the service process is utilised (capacity efficiency). In addition, directions for developing measurement models for service productivity are discussed.

Narratives of Travel and the Travelling Concept of Narrative: Genre Blending and the Art of Transformation

In this article I shall argue that understandings of what constitutes narrative, how it functions, and the contexts in which it applies have broadened in line with cultural, social and intellectual trends which have seen a blurring, if not the dissolution, of boundaries between ‘fact’ and ‘fiction’; ‘literary’ and ‘non-literary’ narrative spaces; history and story; concepts of time and space, text and image, teller and tale, representation and reality.To illustrate some of the ways in which the concept of narrative has travelled across disciplinary and generic boundaries, I shall look at The Art of Travel (de Botton 2003), with a view to demonstrating how the blending of genres works to produce a narrative that is at once personal and philosophical; visual and verbal; didactic and poetic. I shall show that such a text constitutes a site of interrogation of concepts of narrative, even as it depends on the reader’s ability to narrativize experience.

Synthesis, Structure, and Solid-State Transformation Studies of Phosphonoacetate Based Hybrid Compounds of Uranium and Thorium

Three new phosphonoacetate hybrid frameworks based on the actinide elements uranium and thorium have been synthesized. The compounds [C4N2H14][(UO2)(2)(O3PCH2COO)(2)]center dot H2O, I,[C4N2H14][(UO2)(2)(C2O4)(O3PCH2COOH)(2)], II, and Th(H2O)(2)(O3PCH2COO)(C2O4)(0.5). H2O, III, are built up from the connectivity between the metal polyhedra and the phosphonoacetate/oxalate units. Compound II has been prepared using a solvent-free approach, by a solid state reaction at 150 degrees C. It has been shown that II can also be prepared through a room temperature mechanochemical (grinding) route. The layer arrangement in III closely resembles to that observed in I. The compounds have been characterized by powder X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and fluorescence studies.

Philosophy as a Path to Happiness : Attainment of Happiness in Arabic Peripatetic and Ismaili Philosophy

The aim of the dissertation is to explore the idea of philosophy as a path to happiness in classical Arabic philosophy. The starting point is in comparison of two distinct currents between the 10th and early 11th centuries, Peripatetic philosophy, represented by al-Fārābī and Ibn Sīnā, and Ismaili philosophy represented by al-Kirmānī and the Brethren of Purity. They initially offer two contrasting views about philosophy in that the attitude of the Peripatetics is rationalistic and secular in spirit, whereas for the Ismailis philosophy represents the esoteric truth behind revelation. Still, they converge in their view that the ultimate purpose of philosophy lies in its ability to lead man towards happiness. Moreover, they share a common concept of happiness as a contemplative ideal of human perfection, which refers primarily to an otherworldly state of the soul s ascent to the spiritual world. For both the way to happiness consists of two parts: theory and practice. The practical part manifests itself in the idea of the purification of the rational soul from its bodily attachments in order for it to direct its attention fully to the contemplative life. Hence, there appears an ideal of philosophical life with the goal of relative detachment from the worldly life. The regulations of the religious law in this context appear as the primary means for the soul s purification, but for all but al-Kirmānī they are complemented by auxiliary philosophical practices. The ascent to happiness, however, takes place primarily through the acquisition of theoretical knowledge. The saving knowledge consists primarily of the conception of the hierarchy of physical and metaphysical reality, but all of philosophy forms a curriculum through which the soul gradually ascends towards a spiritual state of being along an order that is inverse to the Neoplatonic emanationist hierarchy of creation. For Ismaili philosophy the ascent takes place from the exoteric religious sciences towards the esoteric philosophical knowledge. For Peripatetic philosophers logic performs the function of an instrument enabling the ascent, mathematics is treated either as propaedeutic to philosophy or as a mediator between physical and metaphysical knowledge, whereas physics and metaphysics provide the core of knowledge necessary for the attainment of happiness.