Theoretical investigation of mechanisms of formation and interaction of nanoparticles

In this thesis an investigation into theoretical models for formation and interaction of nanoparticles is presented. The work presented includes a literature review of current models followed by a series of five chapters of original research. This thesis has been submitted in partial fulfilment of the requirements for the degree of doctor of philosophy by publication and therefore each of the five chapters consist of a peer-reviewed journal article. The thesis is then concluded with a discussion of what has been achieved during the PhD candidature, the potential applications for this research and ways in which the research could be extended in the future. In this thesis we explore stochastic models pertaining to the interaction and evolution mechanisms of nanoparticles. In particular, we explore in depth the stochastic evaporation of molecules due to thermal activation and its ultimate effect on nanoparticles sizes and concentrations. Secondly, we analyse the thermal vibrations of nanoparticles suspended in a fluid and subject to standing oscillating drag forces (as would occur in a standing sound wave) and finally on lattice surfaces in the presence of high heat gradients. We have described in this thesis a number of new models for the description of multicompartment networks joined by a multiple, stochastically evaporating, links. The primary motivation for this work is in the description of thermal fragmentation in which multiple molecules holding parts of a carbonaceous nanoparticle may evaporate. Ultimately, these models predict the rate at which the network or aggregate fragments into smaller networks/aggregates and with what aggregate size distribution. The models are highly analytic and describe the fragmentation of a link holding multiple bonds using Markov processes that best describe different physical situations and these processes have been analysed using a number of mathematical methods. The fragmentation of the network/aggregate is then predicted using combinatorial arguments. Whilst there is some scepticism in the scientific community pertaining to the proposed mechanism of thermal fragmentation,we have presented compelling evidence in this thesis supporting the currently proposed mechanism and shown that our models can accurately match experimental results. This was achieved using a realistic simulation of the fragmentation of the fractal carbonaceous aggregate structure using our models. Furthermore, in this thesis a method of manipulation using acoustic standing waves is investigated. In our investigation we analysed the effect of frequency and particle size on the ability for the particle to be manipulated by means of a standing acoustic wave. In our results, we report the existence of a critical frequency for a particular particle size. This frequency is inversely proportional to the Stokes time of the particle in the fluid. We also find that for large frequencies the subtle Brownian motion of even larger particles plays a significant role in the efficacy of the manipulation. This is due to the decreasing size of the boundary layer between acoustic nodes. Our model utilises a multiple time scale approach to calculating the long term effects of the standing acoustic field on the particles that are interacting with the sound. These effects are then combined with the effects of Brownian motion in order to obtain a complete mathematical description of the particle dynamics in such acoustic fields. Finally, in this thesis, we develop a numerical routine for the description of "thermal tweezers". Currently, the technique of thermal tweezers is predominantly theoretical however there has been a handful of successful experiments which demonstrate the effect it practise. Thermal tweezers is the name given to the way in which particles can be easily manipulated on a lattice surface by careful selection of a heat distribution over the surface. Typically, the theoretical simulations of the effect can be rather time consuming with supercomputer facilities processing data over days or even weeks. Our alternative numerical method for the simulation of particle distributions pertaining to the thermal tweezers effect use the Fokker-Planck equation to derive a quick numerical method for the calculation of the effective diffusion constant as a result of the lattice and the temperature. We then use this diffusion constant and solve the diffusion equation numerically using the finite volume method. This saves the algorithm from calculating many individual particle trajectories since it is describes the flow of the probability distribution of particles in a continuous manner. The alternative method that is outlined in this thesis can produce a larger quantity of accurate results on a household PC in a matter of hours which is much better than was previously achieveable.

Investigation of mechanisms governing emission of odorants

The literature identifies several models that describe inter-phase mass transfer, key to the emission process. While the emission process is complex and these models may be more or less successful at predicting mass transfer rates, they identify three key variables for a system involving a liquid and an air phase in contact with it: • A concentration (or partial pressure) gradient driving force; • The fluid dynamic characteristics within the liquid and air phases, and • The chemical properties of the individual components within the system. In three applied research projects conducted prior to this study, samples collected with two well-known sampling devices resulted in very different odour emission rates. It was not possible to adequately explain the differences observed. It appeared likely, however, that the sample collection device might have artefact effects on the emission of odorants, i.e. the sampling device appeared to have altered the mass transfer process. This raised the obvious question: Where two different emission rates are reported for a single source (differing only in the selection of sampling device), and a credible explanation for the difference in emission rate cannot be provided, which emission rate is correct? This research project aimed to identify the factors that determine odour emission rates, the impact that the characteristics of a sampling device may exert on the key mass transfer variables, and ultimately, the impact of the sampling device on the emission rate itself. To meet these objectives, a series of targeted reviews, and laboratory and field investigations, were conducted. Two widely-used, representative devices were chosen to investigate the influence of various parameters on the emission process. These investigations provided insight into the odour emission process generally, and the influence of the sampling device specifically.

Mechanisms of change in negative thinking and urinary monoamines in depressed patients during acute treatment with group cognitive behavior therapy and antidepressant medication

This naturalistic study investigated the mechanisms of change in measures of negative thinking and in 24-h urinary metabolites of noradrenaline (norepinephrine), dopamine and serotonin in a sample of 43 depressed hospital patients attending an eight-session group cognitive behavior therapy program. Most participants (91%) were taking antidepressant medication throughout the therapy period according to their treating Psychiatrists' prescriptions. The sample was divided into outcome categories (19 Responders and 24 Non-responders) on the basis of a clinically reliable change index [Jacobson, N.S., & Truax, P., 1991. Clinical significance: a statistical approach to defining meaningful change in psychotherapy research. Journal of Consulting and Clinical Psychology, 59, 12–19.] applied to the Beck Depression Inventory scores at the end of the therapy. Results of repeated measures analysis of variance [ANOVA] analyses of variance indicated that all measures of negative thinking improved significantly during therapy, and significantly more so in the Responders as expected. The treatment had a significant impact on urinary adrenaline and metadrenaline excretion however, these changes occurred in both Responders and Non-responders. Acute treatment did not significantly influence the six other monoamine metabolites. In summary, changes in urinary monoamine levels during combined treatment for depression were not associated with self-reported changes in mood symptoms.

Managing a portfolio of corporate venture units : challenges in achieving within-unit focus and between-unit coordination

Principal Topic: There is increasing recognition that the organizational configurations of corporate venture units should depend on the types of ventures the unit seeks to develop (Burgelman, 1984; Hill and Birkinshaw, 2008). Distinction have been made between internal and external as well as exploitative versus explorative ventures (Hill and Birkinshaw, 2008; Narayan et al., 2009; Schildt et al., 2005). Assuming that firms do not want to limit themselves to a single type of venture, but rather employ a portfolio of ventures, the logical consequence is that firms should employ multiple corporate venture units. Each venture unit tailor-made for the type of venture it seeks to develop. Surprisingly, there is limited attention in the literature for the challenges of managing multiple corporate venture units in a single firm. Maintaining multiple venture units within one firm provides easier access to funding for new ideas (Hamel, 1999). It allows for freedom and flexibility to tie the organizational systems (Rice et al., 2000), autonomy (Hill and Rothaermel, 2003), and involvement of management (Day, 1994; Wadwha and Kotha, 2006) to the requirements of the individual ventures. Yet, the strategic objectives of a venture may change when uncertainty around the venture is resolved (Burgelman, 1984). For example, firms may decide to spin-in external ventures (Chesbrough, 2002) or spun-out ventures that prove strategically unimportant (Burgelman, 1984). This suggests that ventures might need to be transferred between venture units, e.g. from a more internally-driven corporate venture division to a corporate venture capital unit. Several studies suggested that ventures require different managerial skills across their phase of development (Desouza et al., 2007; O'Connor and Ayers, 2005; Kazanjian and Drazin, 1990; Westerman et al., 2006). To facilitate effective transfer between venture units and manage the overall venturing process, it is important that firms set up and manage integrative linkages. Integrative linkages provide synergies and coordination between differentiated units (Lawrence and Lorsch, 1967). Prior findings pointed to the important role of senior management (Westerman et al., 2006; Gilbert, 2006) and a shared organizational vision (Burgers et al., 2009) to coordinate venture units with mainstream businesses. We will draw on these literatures to investigate the key question of how to integratively manage multiple venture units. ---------- Methodology/Key Propositions: In order to seek an answer to the research question, we employ a case study approach that provides unique insights into how firms can break up their venturing process. We selected three Fortune 500 companies that employ multiple venturing units, IBM, Royal Dutch/ Shell and Nokia, and investigated and compared their approaches. It was important that the case companies somewhat differed in the type of venture units they employed as well as the way they integrate and coordinate their venture units. The data are based on extensive interviews and a variety of internal and external company documents to triangulate our findings (Eisenhardt, 1989). The key proposition of the article is that firms can best manage their multiple venture units through an ambidextrous design of loosely coupled units. This provides venture units with sufficient flexibility to employ organizational configurations that best support the type of venture they seek to develop, as well as provides sufficient integration to facilitate smooth transfer of ventures between venture units. Based on the case findings, we develop a generic framework for a new way of managing the venturing process through multiple corporate venture units. ---------- Results and Implications: One of our main findings is that these firms tend to organize their venture units according to phases in the venture development process. That is, they tend to have venture units aimed at incubation of venture ideas as well as units aimed more at the commercialization of ventures into a new business unit for the firm or a start-up. The companies in our case studies tended to coordinate venture units through integrative management skills or a coordinative venture unit that spanned multiple phases. We believe this paper makes two significant contributions. First, we extend prior venturing literature by addressing how firms manage a portfolio of venture units, each achieving different strategic objectives. Second, our framework provides recommendations on how firms should manage such an approach towards venturing. This helps to increase the likelihood of success of their venturing programs.

Deconstructing neurobiological coordination

Inherent indeterminacy of neurobiological systems has been revealed by research on coordination of multiarticular actions. We consider three important issues that these investigations raise for biomechanical measurement and performance modeling. These issues highlight the role of dynamic systems theory as a platform for integration of motor control and biomechanics in exercise and sports science.

Multitasking, cognitive coordination and cognitive shifts during web searching

As Web searching becomes more prolific for information access worldwide, we need to better understand users’ Web searching behaviour and develop better models of their interaction with Web search systems. Web search modelling is a significant and important area of Web research. Searching on the Web is an integral element of information behaviour and human–computer interaction. Web searching includes multitasking processes, the allocation of cognitive resources among several tasks, and shifts in cognitive, problem and knowledge states. In addition to multitasking, cognitive coordination and cognitive shifts are also important, but are under-explored aspects of Web searching. During the Web searching process, beyond physical actions, users experience various cognitive activities. Interactive Web searching involves many users’ cognitive shifts at different information behaviour levels. Cognitive coordination allows users to trade off the dependences among multiple information tasks and the resources available. Much research has been conducted into Web searching. However, few studies have modelled the nature of and relationship between multitasking, cognitive coordination and cognitive shifts in the Web search context. Modelling how Web users interact with Web search systems is vital for the development of more effective Web IR systems. This study aims to model the relationship between multitasking, cognitive coordination and cognitive shifts during Web searching. A preliminary theoretical model is presented based on previous studies. The research is designed to validate the preliminary model. Forty-two study participants were involved in the empirical study. A combination of data collection instruments, including pre- and post-questionnaires, think-aloud protocols, search logs, observations and interviews were employed to obtain users’ comprehensive data during Web search interactions. Based on the grounded theory approach, qualitative analysis methods including content analysis and verbal protocol analysis were used to analyse the data. The findings were inferred through an analysis of questionnaires, a transcription of think-aloud protocols, the Web search logs, and notes on observations and interviews. Five key findings emerged. (1) Multitasking during Web searching was demonstrated as a two-dimensional behaviour. The first dimension was represented as multiple information problems searching by task switching. Users’ Web searching behaviour was a process of multiple tasks switching, that is, from searching on one information problem to searching another. The second dimension of multitasking behaviour was represented as an information problem searching within multiple Web search sessions. Users usually conducted Web searching on a complex information problem by submitting multiple queries, using several Web search systems and opening multiple windows/tabs. (2) Cognitive shifts were the brain’s internal response to external stimuli. Cognitive shifts were found as an essential element of searching interactions and users’ Web searching behaviour. The study revealed two kinds of cognitive shifts. The first kind, the holistic shift, included users’ perception on the information problem and overall information evaluation before and after Web searching. The second kind, the state shift, reflected users’ changes in focus between the different cognitive states during the course of Web searching. Cognitive states included users’ focus on the states of topic, strategy, evaluation, view and overview. (3) Three levels of cognitive coordination behaviour were identified: the information task coordination level, the coordination mechanism level, and the strategy coordination level. The three levels of cognitive coordination behaviour interplayed to support multiple information tasks switching. (4) An important relationship existed between multitasking, cognitive coordination and cognitive shifts during Web searching. Cognitive coordination as a management mechanism bound together other cognitive processes, including multitasking and cognitive shifts, in order to move through users’ Web searching process. (5) Web search interaction was shown to be a multitasking process which included information problems ordering, task switching and task and mental coordinating; also, at a deeper level, cognitive shifts took place. Cognitive coordination was the hinge behaviour linking multitasking and cognitive shifts. Without cognitive coordination, neither multitasking Web searching behaviour nor the complicated mental process of cognitive shifting could occur. The preliminary model was revisited with these empirical findings. A revised theoretical model (MCC Model) was built to illustrate the relationship between multitasking, cognitive coordination and cognitive shifts during Web searching. Implications and limitations of the study are also discussed, along with future research work.

Stabilization mechanisms of soil organic matter: Implications for C-saturation of soils

The relationship between soil structure and the ability of soil to stabilize soil organic matter (SOM) is a key element in soil C dynamics that has either been overlooked or treated in a cursory fashion when developing SOM models. The purpose of this paper is to review current knowledge of SOM dynamics within the framework of a newly proposed soil C saturation concept. Initially, we distinguish SOM that is protected against decomposition by various mechanisms from that which is not protected from decomposition. Methods of quantification and characteristics of three SOM pools defined as protected are discussed. Soil organic matter can be: (1) physically stabilized, or protected from decomposition, through microaggregation, or (2) intimate association with silt and clay particles, and (3) can be biochemically stabilized through the formation of recalcitrant SOM compounds. In addition to behavior of each SOM pool, we discuss implications of changes in land management on processes by which SOM compounds undergo protection and release. The characteristics and responses to changes in land use or land management are described for the light fraction (LF) and particulate organic matter (POM). We defined the LF and POM not occluded within microaggregates (53-250 mum sized aggregates as unprotected. Our conclusions are illustrated in a new conceptual SOM model that differs from most SOM models in that the model state variables are measurable SOM pools. We suggest that physicochemical characteristics inherent to soils define the maximum protective capacity of these pools, which limits increases in SOM (i.e. C sequestration) with increased organic residue inputs.