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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
661

Two-dimensional infrared correlation spectroscopy and multivariate curve resolution methods: application to quantitative monitoring of curing process

Spegazzini, Nicolás 29 April 2010 (has links)
Goal and Scope of this thesisThe curing process of epoxy resin directly affects the properties of the final polymer, so it is of great interest to develop analytical methods that allows knowing the pathway of the curing processes. There have been numerous research studies about the evolution of the curing and on the quantification of the corresponding kinetic parameters using several techniques such as: Differential Scanning Calorimetry (DSC), Differential Scanning Calorimetry with Temperature Modulation (MTDSC), Thermogravimetric analysis (TGA), Fluorescence, Raman spectroscopy, Nuclear Magnetic Resonance (NMR), High-Resolution Liquid Chromatography (HPLC), Infrared spectroscopy Fourier Transform (FTIR) and Near infrared spectroscopy (NIR). Usually, those studies are done in model reactions due to the fact that is very difficult, and sometimes even impossible, to isolate the intermediate products that are involved in the curing process. In that sense, the goal of the present thesis is to explore the possibilities of the multidimensional correlation spectroscopy for the quantitative monitorization of curing processes by means of infrared spectroscopy and curve resolution methods. The thesis is focused in a complex reaction in which several and side reactions might take place, most or all of them almost at the same time. This main goal is structured in the following items: 1. Analysis of Generalized two-dimensional correlation spectroscopy and Perturbation-correlation mowing-windows two-dimensional correlation spectroscopy as a tool to obtain information about the reaction pathway.2. Analysis of sample-sample two-dimensional correlation spectroscopy as a tool to obtain concentration profiles of the chemical species involved in the curing process.3. Quantitative resolution of the curing process by means of multivariate curve resolution methods - alternating least squares (MCR-ALS) taking into account the information coming from multidimensional correlation spectroscopy analysis. StructureThe thesis is structured in different chapters each one containing the following information.Chapter 1: This chapter presents the background of the thesis, so it is highlighted the interest of the study of resins epoxy. A brief review of the theory of the multidimensional spectroscopy and the chemometrics tools (multivariate curve resolution methods) used is presented focusing on the novelties introduced in the thesis and offering the proper references for the basic concepts already known.Chapter 2: This chapter concerns the experimental work done. It has been included a brief description of the instrumental analytical techniques used to monitor the curing process. Two main curing reactions are described: experimental conditions and scheme of the reaction between the phenylglycidylether (PGE) and -butyrolactone monitored by NIR and of the copolymerization between the diglycidyl ether of bisphenol A (DGEBA) and -valerolactone by FTIR/ATR. Also the conditions of the DGEBA homopolymerization are presented. And finally, the 1H and 13C NMR experimental condition to obtain the spectrum of the final product in the first reaction between PGE and -butyrolactone is described.Chapter 3: This chapter is addressed to the results obtained as a consequence of the studies done. It is articulated in five published works and each one is introduced by a brief description of the main goal and the content of it. The five articles are presented in a sequential order according the main goal of the thesis.Chapter 4: Finally, the thesis ends with a conclusion chapter in which the achieved goals are outlined.As each paper presented in chapter 3, contains its specific conclusion section, in this chapter there are emphasized the thesis conclusions according to the goals formulated in the scope. In that sense the first and general conclusion is that Multidimensional correlation spectroscopy and multivariate curve resolution method are useful spectroscopic and chemometric methods to quantitative monitoring a curing process using infrared spectroscopy.Concretely it can be also stated that: - Generalized and perturbation-correlation moving-windows two-dimensional correlation spectroscopy, are valuable methods to obtain information about the reaction pathway in the case studied which is representative of a curing process.- Sample-sample two-dimensional correlation spectroscopy is very useful method to obtain concentration profiles of the chemical species involved in the curing process.- And finally, MCR-ALS is a very useful method for the quantitative resolution of the curing process. / El proceso de curado la resina epoxi afecta directamente las propiedades finales del polímero, por lo que es de gran interés para el desarrollo de métodos de análisis que permite conocer la vía de los procesos de polimerización. Por lo general, esos estudios se hacen en reacciones modelo, debido al hecho, que es muy difícil, a veces o incluso imposible, aislar los productos intermedios que intervienen en el proceso de curado. En ese sentido, el objetivo de la tesis es explorar las posibilidades de la espectroscopia de correlación multidimensional para la monitorización cuantitativa de los procesos de curado por medio de espectroscopia infrarrojo y métodos de resolución de la curva. La tesis se centra en una reacción compleja en la que varias reacciones secundarias y puede tener lugar, la mayoría o la totalidad de ellos casi al mismo tiempo.Las conclusiones de la tesis de acuerdo a los objetivos son formulados en el ámbito de aplicación, métodos espectroscópicos y quimiométricos. En ese sentido, la primera conclusión general y es que la espectroscopia de correlación multidimensional y método de resolución de curva multivariante son útiles para el seguimiento de un proceso de curado mediante espectroscopía de infrarrojo.Concretamente, puede ser también señaló que: - La espectroscopia generalizada de correlación bidimensional y espectroscopia de correlación de la perturbación por ventana móvil, son métodos valiosos para obtener información sobre el camino de reacción en el caso estudiado, que es representativa de un proceso de curado.- La espectroscopia de correlación bidimensional muestra-muestra es un metodo útil para obtener perfiles de concentración de las especies químicas involucradas en el proceso de curado.- Por último, MCR-ALS es un método muy útil para la resolución cuantitativa del proceso de curado.
662

An Analysis of Fourier Transform Infrared Spectroscopy Data to Predict Herpes Simplex Virus 1 Infection

Champion, Patrick D 20 November 2008 (has links)
The purpose of this analysis is to evaluate the usefulness of Fourier Transform Infrared (FTIR) spectroscopy in the detection of Herpes Simplex Virus 1 (hsv1) infection at an early stage. The raw absorption values were standardized to eliminate inter-sampling error. Wilcoxon-Mann-Whitney (WMW) statistic's Z score was calculated to select significant spectral regions. Partial least squares modeling was performed because of multicollinearity. Kolmogorov-Smirnov statistic showed models for healthy tissues from different time groups were not from same distribution. The additional 24 hour dataset was evaluated using the following methods. Variables were selected by WMW Z score. Difference of Composites statistic, DC, was created as a disease indicator and evaluated using area under the ROC curve, specificities, and confidence intervals using bootstrap algorithm. The specificity of DC was high, however the confidence intervals were large. Future studies are required with larger sample sizes to test this statistic's usefulness.
663

Higher-Order Spectral/HP Finite Element Technology for Structures and Fluid Flows

Vallala, Venkat Pradeep 16 December 2013 (has links)
This study deals with the use of high-order spectral/hp approximation functions in the finite element models of various nonlinear boundary-value and initial-value problems arising in the fields of structural mechanics and flows of viscous incompressible fluids. For many of these classes of problems, the high-order (typically, polynomial order p greater than or equal to 4) spectral/hp finite element technology offers many computational advantages over traditional low-order (i.e., p < 3) finite elements. For instance, higher-order spectral/hp finite element procedures allow us to develop robust structural elements for beams, plates, and shells in a purely displacement-based setting, which avoid all forms of numerical locking. The higher-order spectral/hp basis functions avoid the interpolation error in the numerical schemes, thereby making them accurate and stable. Furthermore, for fluid flows, when combined with least-squares variational principles, such technology allows us to develop efficient finite element models, that always yield a symmetric positive-definite (SPD) coefficient matrix, and thereby robust direct or iterative solvers can be used. The least-squares formulation avoids ad-hoc stabilization methods employed with traditional low-order weak-form Galerkin formulations. Also, the use of spectral/hp finite element technology results in a better conservation of physical quantities (e.g., dilatation, volume, and mass) and stable evolution of variables with time in the case of unsteady flows. The present study uses spectral/hp approximations in the (1) weak-form Galerkin finite element models of viscoelastic beams, (2) weak-form Galerkin displacement finite element models of shear-deformable elastic shell structures under thermal and mechanical loads, and (3) least-squares formulations for the Navier-Stokes equations governing flows of viscous incompressible fluids. Numerical simulations using the developed technology of several non-trivial benchmark problems are presented to illustrate the robustness of the higher-order spectral/hp based finite element technology.
664

An Analysis of the Law, Practice and Policy of the WTO Agreement on Technical Barriers to Trade in relation to International Standards and the International Organization for Standardization: Implications for Least Developed Countries in Africa.

Okwenye, Tonny. January 2007 (has links)
<p><font face="Times New Roman"> <p align="left">This study examines the legal and policy objectives of the World Trade Organisation (WTO) Agreement on Technical Barriers to Trade (TBT) with specific reference to international standards and the International Organisation for Standardisation (ISO). The study sets out the history and development of the TBT Agreement and the relationship between the TBT Agreement and selected WTO Agreements. The study also explores the application and interpretation of the TBT Agreement under the WTO dispute settlement system. More importantly, the study addresses the legal, policy and practical implications of the TBT Agreement for Least Developed Countries (LDCs) in Africa. A central argument put forward in this study is that, albeit international standards have been recognised as an important tool for LDCs in Africa to gain access to foreign markets, there is no significant &lsquo / political will&rsquo / and commitment from the key players in standardisation work, that is, the national governments, the private sector and the ISO. At the same time, some developed and developing countries tend to use their influence and involvement in the activities of the ISO as a means of promoting the use and adoption of their homegrown standards. The study proposes, among others, that a more participatory approach which encompasses representatives from consumer groups, the private sector and non-governmental organisations (NGOs) from these LDCs in Africa, should be adopted.</p> </font></p>
665

TRAINING TEACHING ASSISTANTS TO IMPLEMENT SYSTEMIC TEACHING STRATEGIES IN PRESCHOOL CLASSROOMS WITH RELIABILITY

Crawford, Rebecca V 01 January 2014 (has links)
We are currently in an era of accountability, so the need for measuring fidelity of implementation is gaining attention. However, there is little research in the area of fidelity of implementation and an inclusive early childhood classroom. In addition, most of the research is conducted using teachers. This study examined the fidelity of implementation by two teaching assistants using the teaching strategies of time delay and system of least prompts with children with and without disabilities in an inclusive early childhood setting. A multiple-probe design with conditions across two behaviors and across two participants design was used to determine the effects of teaching assistants’ fidelity of implementation of evidence-based teaching strategies. Also a multiple probe across two behaviors, replicated across children was used. Most importantly, the results showed that teaching assistants could implement systematic teaching strategies with fidelity. Secondly, the children were able to make progress towards their target skills.
666

Assessment of Strategic Management Practices in Small Agribusiness Firms in Tanzania

Dominic, Theresia 11 May 2015 (has links)
No description available.
667

Connecting the dots : Network analysis, landscape ecology, and practical application

Zetterberg, Andreas January 2011 (has links)
Humans have a profound impact on ecosystems, and land-use change constitutes a primary driving force in the loss of biodiversity. Habitat loss and fragmentation are key factors in this process by seriously impeding the habitat availability and movement of species, leading to a significant decrease in population viability. Landscape connectivity management able of crossing administrative and ecological spatial and temporal scales has been identified as one of the most important measures to counteract these negative impacts. The use of graph-theory and network-based landscape-ecological tools has become established as a promising way forward to address these issues. Despite urgent needs to adapt and implement such tools in planning, assessment and decision-making, surprisingly little attention has been paid to developing approaches for their effective practical application. This thesis presents the development of a toolbox with network-based, landscape-ecological methods and graph-theoretic indicators, which can be effectively implemented by practitioners within environmental assessment, physical planning and design, to analyze landscape connectivity. Recent advances in network analysis and landscape ecology are brought together and adapted for practical application, bridging the gap between science and practice. The use of participatory approaches was identified as key to successful development, and several workshops, meetings, interviews, as well as prototype testing of the developed software were conducted throughout the study. Input data and selection of species were based on the experience gained through seven real-world cases, commissioned by different governmental organizations within Stockholm County. The practitioners’ perspectives on effective practical application of the proposed toolbox were then assessed through an interview-study. The respondents anticipated improved communication with other actors in addition to being able to better assess critical ecological structures within the landscape. The toolbox was finally tested in a large-scale network analysis of impacts of the regional development plan (RUFS 2010), leading to important insights on the planning of connectivity in an urbanizing region. / <p>QC 20111125</p>
668

On the Relationship between Conjugate Gradient and Optimal First-Order Methods for Convex Optimization

Karimi, Sahar January 2014 (has links)
In a series of work initiated by Nemirovsky and Yudin, and later extended by Nesterov, first-order algorithms for unconstrained minimization with optimal theoretical complexity bound have been proposed. On the other hand, conjugate gradient algorithms as one of the widely used first-order techniques suffer from the lack of a finite complexity bound. In fact their performance can possibly be quite poor. This dissertation is partially on tightening the gap between these two classes of algorithms, namely the traditional conjugate gradient methods and optimal first-order techniques. We derive conditions under which conjugate gradient methods attain the same complexity bound as in Nemirovsky-Yudin's and Nesterov's methods. Moreover, we propose a conjugate gradient-type algorithm named CGSO, for Conjugate Gradient with Subspace Optimization, achieving the optimal complexity bound with the payoff of a little extra computational cost. We extend the theory of CGSO to convex problems with linear constraints. In particular we focus on solving $l_1$-regularized least square problem, often referred to as Basis Pursuit Denoising (BPDN) problem in the optimization community. BPDN arises in many practical fields including sparse signal recovery, machine learning, and statistics. Solving BPDN is fairly challenging because the size of the involved signals can be quite large; therefore first order methods are of particular interest for these problems. We propose a quasi-Newton proximal method for solving BPDN. Our numerical results suggest that our technique is computationally effective, and can compete favourably with the other state-of-the-art solvers.
669

Contribution to multipath channel estimation in an OFDM modulation context.

Savaux, Vincent 29 November 2013 (has links) (PDF)
In wireless communications systems, the transmission channel between the transmitter and the receiver antennas is one of the main sources of disruption for the signal. The multicarrier modulations, such as the orthogonal frequency division multiplexing (OFDM), are very robust against the multipath effect, and allow to recover the transmitted signal with a low error rate, when they are combined with a channel encoding. The channel estimation then plays a key role in the performance of the communications systems. In this PhD thesis, we study techniques based on least square (LS) and minimum mean square error (MMSE) estimators. The MMSE is optimal, but is much more complex than LS, and requires the a priori knowledge of the second order moment of the channel and the noise. In this presentation, two methods that allow to reach a performance close to the one of LMMSE while getting around its drawback are investigated. In another way, a third part of the presentation investigates the errors of estimation due to the interpolations.
670

Estimation In The Simple Linear Regression Model With One-fold Nested Error

Ulgen, Burcin Emre 01 June 2005 (has links) (PDF)
In this thesis, estimation in simple linear regression model with one-fold nested error is studied. To estimate the fixed effect parameters, generalized least squares and maximum likelihood estimation procedures are reviewed. Moreover, Minimum Norm Quadratic Estimator (MINQE), Almost Unbiased Estimator (AUE) and Restricted Maximum Likelihood Estimator (REML) of variance of primary units are derived. Also, confidence intervals for the fixed effect parameters and the variance components are studied. Finally, the aforesaid estimation techniques and confidence intervals are applied to a real-life data and the results are presented

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