Defects in thermosensitive colloidal crystals

Poly-N-Isopropylacrylamide (PNIPAM) colloidal particles form crystal phases that show a thermosensitive behaviour and can be used as atomic model systems. This polymer has both hydrophilic and hydrophobic character and has interesting stimuli-responsive properties in aqueous solution, of which the most important is the temperature response. Above a certain temperature, called Lower Critical Solution Temperature (LCST), the system undergoes a volume phase transition (VPT). Above the LCST, the water is expelled from the polymer network and the swollen state at low temperature transforms into a shrunken state at high temperature. The thermoresponsive behaviour of PNIPAM can be influenced by pH and ionic strength, as well as by the presence of copolymers, such as acrylic acid. In a system formed both by particles of PNIPAM and PNIPAM doped with acrylic acid, one can control the size ratio of the two components by changing the temperature of the mixture, while keeping particle interactions relatively the same. It is therefore possible to obtain thermoresponsive colloidal crystal in which temperature changes induce defects whose formation processes and dynamics can be analysed in an optical microscope at a convenient spatial and temporal scale. The goal of this thesis project was to find the conditions in which such a system could be formed, by using characterization techniques such as Static Light Scattering, Dynamic Light Scattering and Confocal Laser Scanning Microscopy. Two PNIPAM-AAc systems were available, and after characterization it was possible to select a suitable one, on the basis of its low polydispersity and the lack of a VPT, regardless of the external conditions (system JPN_7). The synthesis of a PNIPAM system was attempted, with particles of dimensions matching the JPN_7 system and, unlike JPN_7, displaying a VPT, and one suitable candidate for the mixed system was finally found (system CB_5). The best conditions to obtain thermoresponsive crystal were selected, and the formation and healing of defects were investigated with CLSM temperature scans. The obtained results show that the approach is the correct one and that the present report could represent a useful start for future developments in defect analysis and defect dynamics studies.

Double-stimulus sensitive (temperature and pH) self-assemblable polymers

The rheological properties of block co-polymers in water solution at different pH have been investigated. The block copolymers are based on different architectures containing poly(ethylene glycol), poly(propylene glycol) and different blocks of polymer that change their hydrophobic/hydrophilic behavior as a function of pH. The polymer chains of the starting material were extended at their functional ends with the pH-sensitive units using ATRP; this mechanism of controlled radical polymerization was chosen because of the need to minimize polydispersity and avoid transfer reactions possibly leading to homopolymeric inpurities. The starting material were modified in order to use them as macroinitiator for ATRP. The kinetic of each ATRP reaction has been investigated, in order to be able to synthesize polymers with different degree of polymerization, stopping the reaction when the desired polymers chain length has been reached. We will use polymer chains with different basicity and degree of polymerization to link any possible effect of their presence to the conditions under which they become hydrophobic. It has been shown that the rate of polymerization changes changing the type of macroinitiator and the type of monomer synthesized. The slowest rate of polymerization is the one with the most hindered monomer synthesized using the macroinitiator with the highest molecular weight. The water solubility of the synthesized polymers changes depending on the pH of the solution and on the structure of the polymers. It has been shown using 1H-NMR that some of the synthesized polymers are capable to self-aggregation in water solution. The self-aggregation and the type of aggregation is influenced from the structure of the polymer and from the pH of the solution. Changing the structure of the polymers and the pH it is possible to obtain different type of aggregates in solution. This aggregates differ for the volume occupied from them, and for their hardness. Rheological measurements have been demonstrated that the synthesized polymers are capable to form gel phases. The gelation temperature changes changing the structure of the aggregates in solution and it is possible to correlate the changing in the gelation temperature with the changing in the structure of the polymer.

Numerical study on viscoelastic behavior of polypropylene fiber reinforced concrete subjected to temperature variations using LDPM theory

This thesis is focused on the viscoelastic behavior of macro-synthetic fiber-reinforced concrete (MSFRC) with polypropylene studied numerically when subjected to temperature variations (-30 oC to +60 oC). LDPM (lattice discrete particle model), a meso-scale model for heterogeneous composites, is used. To reproduce the MSFRC structural behavior, an extended version of LDPM that includes fiber effects through fiber-concrete interface micromechanics, called LDPM-F, is applied. Model calibration is performed based on three-point bending, cube, and cylinder test for plain concrete and MSFRC. This is followed by a comprehensive literature study on the variation of mechanical properties with temperature for individual fibers and plain concrete. This literature study and past experimental test results constitute inputs for final numerical simulations. The numerical response of MSFRC three-point bending test is replicated and compared with the previously conducted experimental test results; finally, the conclusions were drawn. LDPM numerical model is successfully calibrated using experimental responses on plain concrete. Fiber-concrete interface micro-mechanical parameters are subsequently fixed and LDPM-F models are calibrated based on MSFRC three-point bending test at room temperature. Number of fibers contributing crack bridging mechanism is computed and found to be in good agreement with experimental counts. Temperature variations model for individual constituents of MSFRC, fibers and plain concrete, are implemented in LDPM-F. The model is validated for MSFRC three-point bending stress-CMOD (crack mouth opening) response reproduced at -30 oC, -15 oC, 0 oC, +20 oC, +40 oC and +60 oC. It is found that the model can well describe the temperature variation behavior of MSFRC. At positive temperatures, simulated responses are in good agreement. Slight disagreement in negative regimes suggests an in-depth study on fiber-matrix interface bond behavior with varying temperatures.

Bioremediation of PAHs - Limitations and soultions

Introduction 1.1 Occurrence of polycyclic aromatic hydrocarbons (PAH) in the environment Worldwide industrial and agricultural developments have released a large number of natural and synthetic hazardous compounds into the environment due to careless waste disposal, illegal waste dumping and accidental spills. As a result, there are numerous sites in the world that require cleanup of soils and groundwater. Polycyclic aromatic hydrocarbons (PAHs) are one of the major groups of these contaminants (Da Silva et al., 2003). PAHs constitute a diverse class of organic compounds consisting of two or more aromatic rings with various structural configurations (Prabhu and Phale, 2003). Being a derivative of benzene, PAHs are thermodynamically stable. In addition, these chemicals tend to adhere to particle surfaces, such as soils, because of their low water solubility and strong hydrophobicity, and this results in greater persistence under natural conditions. This persistence coupled with their potential carcinogenicity makes PAHs problematic environmental contaminants (Cerniglia, 1992; Sutherland, 1992). PAHs are widely found in high concentrations at many industrial sites, particularly those associated with petroleum, gas production and wood preserving industries (Wilson and Jones, 1993). 1.2 Remediation technologies Conventional techniques used for the remediation of soil polluted with organic contaminants include excavation of the contaminated soil and disposal to a landfill or capping - containment - of the contaminated areas of a site. These methods have some drawbacks. The first method simply moves the contamination elsewhere and may create significant risks in the excavation, handling and transport of hazardous material. Additionally, it is very difficult and increasingly expensive to find new landfill sites for the final disposal of the material. The cap and containment method is only an interim solution since the contamination remains on site, requiring monitoring and maintenance of the isolation barriers long into the future, with all the associated costs and potential liability. A better approach than these traditional methods is to completely destroy the pollutants, if possible, or transform them into harmless substances. Some technologies that have been used are high-temperature incineration and various types of chemical decomposition (for example, base-catalyzed dechlorination, UV oxidation). However, these methods have significant disadvantages, principally their technological complexity, high cost , and the lack of public acceptance. Bioremediation, on the contrast, is a promising option for the complete removal and destruction of contaminants. 1.3 Bioremediation of PAH contaminated soil & groundwater Bioremediation is the use of living organisms, primarily microorganisms, to degrade or detoxify hazardous wastes into harmless substances such as carbon dioxide, water and cell biomass Most PAHs are biodegradable unter natural conditions (Da Silva et al., 2003; Meysami and Baheri, 2003) and bioremediation for cleanup of PAH wastes has been extensively studied at both laboratory and commercial levels- It has been implemented at a number of contaminated sites, including the cleanup of the Exxon Valdez oil spill in Prince William Sound, Alaska in 1989, the Mega Borg spill off the Texas coast in 1990 and the Burgan Oil Field, Kuwait in 1994 (Purwaningsih, 2002). Different strategies for PAH bioremediation, such as in situ , ex situ or on site bioremediation were developed in recent years. In situ bioremediation is a technique that is applied to soil and groundwater at the site without removing the contaminated soil or groundwater, based on the provision of optimum conditions for microbiological contaminant breakdown.. Ex situ bioremediation of PAHs, on the other hand, is a technique applied to soil and groundwater which has been removed from the site via excavation (soil) or pumping (water). Hazardous contaminants are converted in controlled bioreactors into harmless compounds in an efficient manner. 1.4 Bioavailability of PAH in the subsurface Frequently, PAH contamination in the environment is occurs as contaminants that are sorbed onto soilparticles rather than in phase (NAPL, non aqueous phase liquids). It is known that the biodegradation rate of most PAHs sorbed onto soil is far lower than rates measured in solution cultures of microorganisms with pure solid pollutants (Alexander and Scow, 1989; Hamaker, 1972). It is generally believed that only that fraction of PAHs dissolved in the solution can be metabolized by microorganisms in soil. The amount of contaminant that can be readily taken up and degraded by microorganisms is defined as bioavailability (Bosma et al., 1997; Maier, 2000). Two phenomena have been suggested to cause the low bioavailability of PAHs in soil (Danielsson, 2000). The first one is strong adsorption of the contaminants to the soil constituents which then leads to very slow release rates of contaminants to the aqueous phase. Sorption is often well correlated with soil organic matter content (Means, 1980) and significantly reduces biodegradation (Manilal and Alexander, 1991). The second phenomenon is slow mass transfer of pollutants, such as pore diffusion in the soil aggregates or diffusion in the organic matter in the soil. The complex set of these physical, chemical and biological processes is schematically illustrated in Figure 1. As shown in Figure 1, biodegradation processes are taking place in the soil solution while diffusion processes occur in the narrow pores in and between soil aggregates (Danielsson, 2000). Seemingly contradictory studies can be found in the literature that indicate the rate and final extent of metabolism may be either lower or higher for sorbed PAHs by soil than those for pure PAHs (Van Loosdrecht et al., 1990). These contrasting results demonstrate that the bioavailability of organic contaminants sorbed onto soil is far from being well understood. Besides bioavailability, there are several other factors influencing the rate and extent of biodegradation of PAHs in soil including microbial population characteristics, physical and chemical properties of PAHs and environmental factors (temperature, moisture, pH, degree of contamination). Figure 1: Schematic diagram showing possible rate-limiting processes during bioremediation of hydrophobic organic contaminants in a contaminated soil-water system (not to scale) (Danielsson, 2000). 1.5 Increasing the bioavailability of PAH in soil Attempts to improve the biodegradation of PAHs in soil by increasing their bioavailability include the use of surfactants , solvents or solubility enhancers.. However, introduction of synthetic surfactant may result in the addition of one more pollutant. (Wang and Brusseau, 1993).A study conducted by Mulder et al. showed that the introduction of hydropropyl-ß-cyclodextrin (HPCD), a well-known PAH solubility enhancer, significantly increased the solubilization of PAHs although it did not improve the biodegradation rate of PAHs (Mulder et al., 1998), indicating that further research is required in order to develop a feasible and efficient remediation method. Enhancing the extent of PAHs mass transfer from the soil phase to the liquid might prove an efficient and environmentally low-risk alternative way of addressing the problem of slow PAH biodegradation in soil.

Experimental Data on Fire-Resistance Behavior of Reinforced Concrete Structures with Example Calculations

This thesis selects concrete, steel and their relation as research subjects, mainly commentary and discusses the property changes of steel and concrete materials under and after high temperature.The differences and comparisons of reasearch methods and ways between different researchers and different papers,particularly for chinese researches and chinese papers,and partly for comparison between chinese papers methods and Euro-Amercian papers methods about Fire Resistance Behavior of Reinforced Concrete will be summarized and analyzed.The researches on fire-resistance behavior of reinforced concrete become more and more important all over the world. And I would find differences between Chinese researches results, between Chinese researches results and other countries researches results.

Shear behavior of reinforced concrete slabs under concentrated load: an investigation through Sequentially Linear Analysis

ABSTRACT (italiano) Con crescente attenzione riguardo al problema della sicurezza di ponti e viadotti esistenti nei Paesi Bassi, lo scopo della presente tesi è quello di studiare, mediante la modellazione con Elementi Finiti ed il continuo confronto con risultati sperimentali, la risposta in esercizio di elementi che compongono infrastrutture del genere, ovvero lastre in calcestruzzo armato sollecitate da carichi concentrati. Tali elementi sono caratterizzati da un comportamento ed una crisi per taglio, la cui modellazione è, da un punto di vista computazionale, una sfida piuttosto ardua, a causa del loro comportamento fragile combinato a vari effetti tridimensionali. La tesi è incentrata sull'utilizzo della Sequentially Linear Analysis (SLA), un metodo di soluzione agli Elementi Finiti alternativo rispetto ai classici approcci incrementali e iterativi. Il vantaggio della SLA è quello di evitare i ben noti problemi di convergenza tipici delle analisi non lineari, specificando direttamente l'incremento di danno sull'elemento finito, attraverso la riduzione di rigidezze e resistenze nel particolare elemento finito, invece dell'incremento di carico o di spostamento. Il confronto tra i risultati di due prove di laboratorio su lastre in calcestruzzo armato e quelli della SLA ha dimostrato in entrambi i casi la robustezza del metodo, in termini di accuratezza dei diagrammi carico-spostamento, di distribuzione di tensioni e deformazioni e di rappresentazione del quadro fessurativo e dei meccanismi di crisi per taglio. Diverse variazioni dei più importanti parametri del modello sono state eseguite, evidenziando la forte incidenza sulle soluzioni dell'energia di frattura e del modello scelto per la riduzione del modulo elastico trasversale. Infine è stato effettuato un paragone tra la SLA ed il metodo non lineare di Newton-Raphson, il quale mostra la maggiore affidabilità della SLA nella valutazione di carichi e spostamenti ultimi insieme ad una significativa riduzione dei tempi computazionali. ABSTRACT (english) With increasing attention to the assessment of safety in existing dutch bridges and viaducts, the aim of the present thesis is to study, through the Finite Element modeling method and the continuous comparison with experimental results, the real response of elements that compose these infrastructures, i.e. reinforced concrete slabs subjected to concentrated loads. These elements are characterized by shear behavior and crisis, whose modeling is, from a computational point of view, a hard challenge, due to their brittle behavior combined with various 3D effects. The thesis is focused on the use of Sequentially Linear Analysis (SLA), an alternative solution technique to classical non linear Finite Element analyses that are based on incremental and iterative approaches. The advantage of SLA is to avoid the well-known convergence problems of non linear analyses by directly specifying a damage increment, in terms of a reduction of stiffness and strength in the particular finite element, instead of a load or displacement increment. The comparison between the results of two laboratory tests on reinforced concrete slabs and those obtained by SLA has shown in both the cases the robustness of the method, in terms of accuracy of load-displacements diagrams, of the distribution of stress and strain and of the representation of the cracking pattern and of the shear failure mechanisms. Different variations of the most important parameters have been performed, pointing out the strong incidence on the solutions of the fracture energy and of the chosen shear retention model. At last a confrontation between SLA and the non linear Newton-Raphson method has been executed, showing the better reliability of the SLA in the evaluation of the ultimate loads and displacements, together with a significant reduction of computational times.