The amounts of data collected from each sample of e.g. chemical or biological materials have increased by orders of magnitude since the beginning of the 20th century. Furthermore, the number of ways to collect data from observations is also increasing. Such configurations with several massive data sets increase the demands on the methods used to analyse them. Methods that handle such data are called multiblock methods and they are the topic of this thesis. Data collected from advanced analytical instruments often contain variation from diverse mutually independent sources, which may confound observed patterns and hinder interpretation of latent variable models. For this reason, new methods have been developed that decompose the data matrices, placing variation from different sources of variation into separate parts. Such procedures are no longer merely pre-processing filters, as they initially were, but have become integral elements of model building and interpretation. One strain of such methods, called OPLS, has been particularly successful since it is easy to use, understand and interpret. This thesis describes the development of a new multiblock data analysis method called OnPLS, which extends the OPLS framework to the analysis of multiblock and path models with very general relationships between blocks in both rows and columns. OnPLS utilises OPLS to decompose sets of matrices, dividing each matrix into a globally joint part (a part shared with all the matrices it is connected to), several locally joint parts (parts shared with some, but not all, of the connected matrices) and a unique part that no other matrix shares. The OnPLS method was applied to several synthetic data sets and data sets of “real” measurements. For the synthetic data sets, where the results could be compared to known, true parameters, the method generated global multiblock (and path) models that were more similar to the true underlying structures compared to models without such decompositions. I.e. the globally joint, locally joint and unique models more closely resembled the corresponding true data. When applied to the real data sets, the OnPLS models revealed chemically or biologically relevant information in all kinds of variation, effectively increasing the interpretability since different kinds of variation are distinguished and separately analysed. OnPLS thus improves the quality of the models and facilitates better understanding of the data since it separates and separately analyses different kinds of variation. Each kind of variation is purer and less tainted by other kinds. OnPLS is therefore highly recommended to anyone engaged in multiblock or path model data analysis.

High performance engineering materials, poly(arylene ether)s, having very good mechanical properties, excellent oxidative and hydrolytic stability are promising candidates for alternative materials used in the field of Proton Exchange Membrane Fuel Cells (PEMFCs) and Reverse Osmosis (RO) applications. In particular, wholly aromatic sulfonated poly(arylene ether sulfone)s are of considerable interest in the field of PEMFCs and RO, due to their affordability, high Tg, and the ease of sulfonation. Proton exchange membrane fuels cells (PEMFCs) are one of the primary alternate source of energy. A Proton exchange membrane (PEM) is one of the key component in a PEMFC and it needs to have good proton conductivity under partially humidified conditions. One of the strategies to increase proton conductivity under partially RH conditions is to synthesize hydrophobic-hydrophilic multiblock copolymers with high Ion exchange capacity (IEC) values to ensure sufficient ion channel size. In this thesis two multiblock systems were synthesized incorporating trisulfonated hydrophilic oligomers and were characterized in the first two chapters of the thesis. The first multiblock system incorporated a non-fluorinated biphenol-based hydrophobic block. The second study was focused on synthesizing a fluorinated benzonitrile-based hydrophobic block. A fluorinated monomer was incorporated with the aim to improve phase separation which might lead to increased performance under partially humidified conditions. The third study featured synthesis and characterization of a novel hydroquinone-based random copolymer system precursor, which after post-sulfonation, shall form mono-sulfonated polysulfone materials with potential applications in reverse osmosis. The ratio of the amount of hydroquinone incorporated in the copolymer were varied during the synthesis of the precursor to facilitate control over the post-sulfonation process. The simple and low cost process of post-sulfonating the random copolymer enables the precursor to be a promising material to be used in the reverse osmosis application. / Master of Science

Poly(arylene ether)s are a well-established class of thermoplastics that are known for their mechanical toughness, thermal stability, and fabrication into membranes. These materials can undergo a myriad of modifications including backbone structure variability, sulfonation, and crosslinking. In this dissertation, structure-property relationships are considered for poly(arylene ether)s with regard to membrane applications for proton exchange and gas separation membranes. All of the proton exchange membranes in this dissertation focus on a disulfonated poly(arylene ether sulfone) based hydrophilic structure to produce hydrophilic-hydrophobic multiblock copolymers. The hydrophobic segments were based upon poly(arylene ether benzonitrile) polymers and copolymers. The oligomers were synthesized and isolated separately, then reacted under mild conditions to form the alternating multiblock copolymers. Structure-property relationships were considered for two different proton exchange membrane applications. One multiblock copolymer system was for H2/air fuel cells, and the other for direct methanol fuel cells (DMFCs). The H2/air fuel cells operate under harsh conditions and varying levels of relative humidity, while the DMFCs operate in an aqueous environment with a methanol-water mixture (typically 0.5-1 M MeOH). Thus two different approaches were taken for the multiblock copolymers. All of the multiblock copolymers were cast into membranes and after annealing resulted in drastically reduced water uptake as compared to random and non-annealed systems. The membranes were characterized with regard to composition, mechanical properties, morphology, water uptake, proton conductivity, and molecular weight. Membranes were also sent to collaborators to elicit the fuel cell performance of the proton exchange membranes. In H2/air fuel cells the approach was to increase charge density by bisphenol choice in the hydrophilic phase. This was performed by switching to a lower molecular weight monomer, hydroquinone, and a monosulfonated hydroquinone. This produced higher charge density in the hydrophilic phase, and the corresponding multiblock copolymer. With increased hydrophilicity the multiblock copolymers showed increased phase separation, proton conductivity, and better performance under relative humidity testing. In the second system for DMFCs, the primary goal was to reduce methanol permeability by bisphenol selection in the hydrophobic phase. This was done with by replacing fifty mole percent of the fluorinated monomer with a series of increasing hydrophobicity bisphenols. Addition of benzylic methyl groups on the bisphenols, was the method undertaken to increase the hydrophobicity. The combination of reduced fluorine content along with the addition of methyl groups resulted in multiblock copolymers with extremely low water uptake and methanol permeability. This allowed for a PEM with better performance than Nafion® in 1M MeOH in DMFC testing. The gas separation membranes presented in this dissertation are based upon poly(arylene ether ketone)s. Two systems were presented: one with a polymer directly synthesized with a bisphenol containing benzylic methyl groups and 4,4'-difluorobenzophenone, and the other a difunctional poly(phenylene oxide) oligomer polymerized with 4,4'-difluorobenzophenone. These systems were crosslinked via UV light through excitation of the ketone group to the triplet state and then hydrogen abstraction from the benzylic methyl. Confirmation of crosslinking was performed via differential scanning calorimetry and infrared spectroscopy. Changes in the glass transitions between crosslinked and non-crosslinked materials were characterized with respect to the concentration of ketones to elicit the effects of crosslink density on the polymers and copolymers. Gas transport properties showed a strong dependence on the ketone percentage as the selectivity was much higher for the homopolymer, while the permeability was higher for the PPO copolymer in the CO2/CH4 and O2/N2 gas pairs. / Ph. D.

Work here presented is the result of basic research in key aspects of the currently available engineering tools and methodologies for the design, optimisation and development of thermal systems and equipment: turbulence modelling, high performance computing and quality tests and procedures so as to assess credibility to the numerical solutions (verification and validation). The thesis comprises six main chapters written in a paper format. Two of them have already been published in international journals, one in the proceedings of a Spanish conference and two in proceedings of international conferences on Computational Fluid Dynamics and heat transfer. The last chapter has recently been submitted for publication to an international journal. Therefore, all the chapters are written so as to be self-contained, complete and concise. As a consequence, some contents of the chapters such those describing the governing equations, or the verification procedure used to assess the credibility of the numerical solutions, are repeated in several of them. Furthermore, as only minor changes have been introduced in the chapters respect to the original papers, each of them reflects the know-how of the CTTC (Heat and Mass Transfer Technological Centre were the research has been carried out) when they were published.Papers presented in chapters 1 and 2 deal with turbulence modelling. A general overview is given on the formulation and numerical techniques of the different levels of turbulence modelling: Direct Numerical Simulation (DNS), Large Eddy Simulation (LES) and Reynolds Averaged Navier-Stokes Simulation (RANS). Main attention is focussed on the eddy viscosity two-equation RANS models. Their formulation is presented in more detail, and numerical solutions of the most extended. Benchmark problems on turbulence modelling are given compared to the available experimental data.Chapters 3 and 4 focus on the use of the multiblock method (domain decomposition method), as a numerical technique that combined with the parallel computing may allow reducing the demanding computational time and memory (high performance computing). The multiblock approach used is based on the conservation of all the physical quantities (fully conservative method) and on an explicit information exchange between the different blocks of the domain. The goal of the work presented in these two chapters is to verify that such a multiblock approach does not introduce additional uncertainty in the numerical solutions.Chapter 5 presents a tool that has been developed at the CTTC for the verification of finite volume computations. In fact, this tool is also partially used and described in the results presented in the previous chapters. Here, it is described and discussed in detail and it is applied to a set of different CFD and heat transfer problems in two and three dimensions, with free and forced convection, with reactive and non-reactive flows and with laminar and turbulent flows.The last chapter shows a complete study for the development of a credible heat transfer relation for the heat evacuated from a ventilation channel. Such study comprises all the different steps that have to be accomplished so as to develop credible and applicable results in mechanical engineering. It comprises a description of the mathematical model to represent the physical phenomena in the channel, the numerical model to solve the set of coupled differential equations of the mathematical model, the construction and testing of an ad-hoc experimental set-up, and a verification and validation (V&V) test that guarantees that the numerical solution is an accurate enough approximation of the mathematical model (verification), and that it properly predicts the reality (validation).

iv In this thesis, numerical solutions of a 2D stator compressor cascade at a given inlet Mach number (0.7) and four values of incidence (49&deg / , 51&deg / , 53&deg / and 55&deg / ) are obtained. Reynolds averaged, thin layer, compressible Navier Stokes equations are solved. Different grid types have been generated. Finite differencing approach and LU - ADI splitting technique are used. Three block parallel Euler and Navier Stokes solutions are compared with the experimental results. Baldwin-Lomax turbulence model is used in the turbulent predictions and boundary layer comparisons and numerical results are in good agreement with the experiment. On the last part of the study, a rotor wake in the inlet flow has been introduced in the steady and unsteady analyses. The influence of this wake and the wake location in the inlet flow, to the total force and pressure is presented. The results have been showed that there is a relationship between the wake position and the incidence value of the case.

No description available.

In modern biological research, OMICs techniques, such as genomics, proteomics or metabolomics, are often employed to gain deep insights into metabolic regulations and biochemical perturbations in response to a specific research question. To gain complementary biologically relevant information, multiOMICs, i.e., several different OMICs measurements on the same specimen, is becoming increasingly frequent. To be able to take full advantage of this complementarity, joint analysis of such multiOMICs data is necessary, but this is yet an underdeveloped area. In this thesis, a theoretical background is given on general component-based methods for dimensionality reduction such as PCA, PLS for single block analysis, and multiblock PLS for co-analysis of OMICs data. This is followed by a rotation of an unsupervised analysis method. The aim of this method is to divide dimensionality-reduced data in block-distinct and common variance partitions, using the DISCO-SCA approach. Finally, an algorithm for a similar rotation of a supervised (PLS) solution is presented using data available in the literature. To the best of our knowledge, this is the first time that such an approach for rotation of a supervised analysis in block-distinct and common partitions has been developed and tested.This newly developed DISCO-PLS algorithm clearly showed an increased potential for visualisation and interpretation of data, compared to standard PLS. This is shown bybiplots of observation scores and multiblock variable loadings.

Ring-opening polymerization (ROP) is a promising approach to accessing well-defined polyesters with superior (bio)degradability and recyclability. However, the living/controlled polymerization of glycolide (GL), a well-known sustainable monomer derived from carbon mono/di-oxide, has never been reported due to the extremely low solubility of its polymer in common solvents. Herein, we report the first living/controlled anionic ROP of GL in strong protic fluoroalcohols (FAs), which are conventionally considered incompatible with anionic polymerization. Well-defined polyglycolide (PGA, Ð < 1.15, Mn up to 55.4 kg mol-1) and various PGA-based macromolecules are obtained at room temperature for the first time. NMR titration and computational studies revealed that FAs simultaneously activate the chain-end and monomer without being involved in initiation. Low boiling point FAs and PGA can be recycled through simple distillation and sublimation at 220 oC in vacuo, respectively, providing a promising sustainable alternative for tackling plastic pollution problems. Well-defined multicrystalline multiblock polymers are essential model polymers for advancing crystallization physics, phase separation, self-assembly, and improving the mechanical properties of materials. However, due to the different chain properties and incompatible synthetic methodology, multicrystalline multiblock polymers with more than two crystallites are rarely reported. Herein, by combining polyhomologation, ring-opening polymerization, and “catalyst switch” strategy, we synthesized the first pentacrystalline pentablock quintopolymer, polyethylene-b-poly(ethylene oxide)-b-poly(e-caprolactone)-b-poly(L-lactide)-b-polyglycolide (PE-b-PEO-b-PCL-b-PLLA-b-PGA). The novel “fluoroalcohol-assisted catalyst switch” enables the first successful incorporation of a high melting point polyglycolide into the complex multiblock polymer. Solid-state NMR spectroscopy, X-ray diffraction, and differential scanning calorimetry revealed the existence of five different crystalline phases.

The potential success of a proton exchange membrane (PEM) fuel cell as an alternative energy source depends highly upon the development of high performance PEMs. Typically, state-of-the-art PEMs have been perfluorinated sulfonated ionomer membranes such as Nafion® by DuPont. Although these membranes demonstrate good mechanical and electrochemical properties under moderate operating conditions (e.g., < 80 ºC), their performance at high temperature (e.g., > 80 ºC) and low relative humidity (RH) drastically deteriorates. To overcome these problems, PEM materials with enhanced properties are essential. Recently, the McGrath group has shown that PEM materials with hydrophilic-hydrophobic segments can significantly improve proton conductivity under low RH by forming enhanced hydrophilic domain connectivity. In this dissultation, novel multiblock copolymers based on disulfonated hydrophilic-hydrophobic multiblocks were synthesized and investigated for their potential application as PEMs. The relationship between copolymer chemical composition and resulting properties was probed with a variety of hydrophilic and hydrophobic segments. Most multiblock copolymers in this research were developed with fully disulfonated poly(arylene ether sulfone) (BPS100) as the hydrophilic segment, and various high performance polymers including polyimides, poly(arylene ether sulfone)s, and poly(arylene ether ketone)s as the hydrophobic segment. Ionic groups on the hydrophilic blocks act as proton conducting sites, while the non-ionic hydrophobic segments provide mechanical and dimensional stability. The correlation between the fuel cell performances and the hydrophilic-hydrophobic sequences was also evaluated. The morphological structures of the multiblock copolymers were investigated using tapping mode atomic force microscopy (TM-AFM), transmission electron microscopy (TEM), and dynamic mechanical analysis (DMA). The experiments demonstrated a well-defined nanophase separated morphology. Moreover, changes in block length had a pronounced effect on the development of phase separated morphology of the system. Proton conductivity measurements elucidated the transport process in the system, with the multiblock copolymers demonstrating higher conductivities compared to Nafion and random copolymer systems with similar ion exchange capacity (IEC) values. The new materials are strong candidates for use in PEM systems. / Ph. D.

This thesis research focused on the synthesis and characterization of disulfonated poly(arylene ether sulfone) hydrophilic-hydrophobic segmented and multiblock copolymers for application as proton exchange membranes (PEMs) in fuel cells or as reverse osmosis (RO) membranes for water desalination. The first objective was to demonstrate that synthesizing blocky copolymers using a one oligomer, two monomer segmented copolymerization afforded copolymers with similar properties to those which used a previous approach of coupling two preformed oligomers. A 4,4′-biphenol based hydrophilic block of disulfonated poly(arylene ether sulfone) oligomer of controlled number average molecular weight (Mn) with phenoxide reactive end groups was first synthesized and isolated. It was then reacted with a calculated amount of hydrophobic monomers, forming that block in-situ. Copolymer and membrane properties, such as intrinsic viscosity, tensile strength, water uptake, and proton conductivity, were consistent with those of multiblock copolymers synthesized via the oligomer-oligomer approach. The segmented polymerization technique was then used to synthesize a variety of other copolymers for PEM applications. The well known bisphenol phenolphthalein was explored as a comonomer for either the hydrophilic and hydrophobic blocks of the copolymer. Membrane properties were explored as a function of block length for both series of copolymers. Both series showed that as block length increases, proton conductivity increases across the entire range of relative humidity (30-100%), as does, water uptake. This was consistent with earlier research which showed that the water self-diffusion coefficient scaled with block length. Copolymers produced with phenolphthalein had higher tensile strength, but lower ultimate elongation than the 4,4′-biphenol based copolymers. Multiblock copolymers were also synthesized and characterized to assess their feasibility as RO membranes. A new series of multiblock copolymers was synthesized by coupling hydrophilic disulfonated poly(arylene ether sulfone) (BisAS100) oligomer with hydrophobic unsulfonated poly(arylene ether sulfone) (BisAS0) oligomer. Both oligomers were derived using 4,´-isopropylidenediphenol (Bis-A) as the bisphenol. Phenoxide-terminated BisAS100 was end-capped with decafluorobiphenyl and reacted at relatively low temperatures (~ 100 oC) with phenoxide-terminated BisAS0. Basic properties were characterized as a function of block length. The initial membrane characterization suggested these copolymers may be suitable candidates for reverse osmosis applications, and water and salt permeability testing should be conducted to determine desalination properties. The latter measurements are being conducted at the University of Texas, Austin and will be reported separately. / Ph. D.