Gravity on Earth limits the study of the properties of pure fluids near critical point because they become stratified under their own weight. Near the critical point, all thermodynamic properties either diverge or converge and the heating and cooling cause instabilities of the convective flow as a consequence of the expansibility divergence. In order to study boiling, fluctuation and phase separation processes near the critical point of pure fluids without the influence of the Earth's gravity, a number of experiments were performed in the weightlessness of Mir space station. The experimental setup called ALICE II instrument was designed to suppress sedimentation and buoyancy-driven flow. Another set of experiments were carried out on Earth using a carefully density matched system of deuterated methanolcycloxexane to observe critical fluctuations directly. The set of experiments performed on board of Mir space station studied boiling and wetting film dynamics during evaporation near the critical point of two pure fluids (sulfur hexafluoride and carbon dioxide) using a defocused grid method. The specially designed cell containing the pure fluid was heated and, as a result, a low contrast line appeared on the wetting film that corresponded to a sharp change in the thickness of the film. A large mechanical response was observed in response to the cell heating and we present quantitative results about the receding contact lines. It is found that the vapor recoil force is responsible for the receding contact line. Local density fluctuations were observed by illuminating a cylindrical cell filled with the pure fluid near its liquid- gas critical point and recorded using a microscope and a video recorder. Microscopic fluctuations were analyzed both in sulfur hexafluoride and in a binary mixture of methanol cyclohexane. Using image processing techniques, we were able to estimate the properties of the fluid from the recorded images showing fluctuations of the transmitted and scattered light. We found that the histogram of an image can be fitted to a Gaussian relationship and by determining its width we were able to estimate the position of the critical point. The characteristic length of the fluctuations corresponding to the maximum of the radial average of the power spectrum was also estimated. The power law growth for the early stage of the phase separation was determined for two different temperature quenches in pure fluid and these results are in agreement with other experimental results and computational simulations.

<p>This thesis is divided in three parts. In the first part, a study of materials aimed for spintronics applications is presented. More specifically, calculations of the critical temperature in diluted magnetic semiconductors (DMS) and half-metallic ferromagnets are presented using a combination of electronic structure and statistical methods. It is shown that disorder and randomness of the magnetic atoms in DMS materials play a very important role in the determination of the critical temperature.</p><p>The second part treats materials in reduced dimensions. Studies of multilayer and trilayer systems are presented. A theoretical model that incorporates interdiffusion in a multilayer is developed that gives better agreement with experimental observations. Using Monte Carlo simulations, the observed magnetic properties in the trilayer system Ni/Cu/Co at finite temperatures are qualitatively reproduced.</p><p>In the third part, electronic structure calculations of complex Mn-based compounds displaying noncollinear magnetism are presented. The calculations reproduce with high accuracy the observed magnetic properties in these compounds. Furthermore, a model based on the electronic structure of the necessary conditions for noncollinear magnetism is presented.</p>

It is generally believed that one of the key parameterscontrolling the normal state and superconducting properties ofhigh temperature superconductors is the charge carrierconcentrationpin the CuO2planes.By changing the non-isovalent dopingconcentration on the RE site as well as the oxygen content in(RE)Ba2Cu3O7−δ, an excellent tool is obtained tovary the hole concentration over a wide range from theunderdoped up to the overdoped regime.In the present thesis thefocus is on the doping effects on the structural and normalstate electrical properties in Nd-123 doped with Ca, La, Pr,Ca-Pr, and Ca-Th.T he effects of doping have been investigatedby X-ray and neutron powder diffraction, and by measurements ofthe resistivity, thermoelectric powerS, and Hall coefficient RH.T he thermoelectric power is a powerful tool forstudies of high temperature superconductivity and is highlysensitive to details of the electronic band structure.Sas a function of temperature has been analyzed in twodifferent two band models.The parameters of these models arerelated to charactristic features of the electron bands and asemiempirical physical description of the doping dependence ofSis obtained.So me important results are following: (i)The valence of Pr in the RE-123 family.Results from thestructural investigations, the critical temperature Tc, and thethermoelectric power indicated a valence +4 at low dopingconcentration, which is in agreement with results of chargeneutral doping in the RE-123 family.(ii)Hole localization. The results of bond valence sum (BVS)calculations from neutron diffraction data showed that holelocalization on the Pr+4site was the main reason for the decrease of thehole concentration p.Differ ent types of localization wereinferred by S measurements for Ca-Th and Ca-Pr dopings.(iii)Competition between added charge and disorder. Theresults of RH measurements indicated that Ca doping introduceddisorder in the CuO2planes in addition to added charge.This could bethe main reason for the observed small decrease of thebandwidth of the density of states in the description of aphenomenological narrow band model.(iv) Empirical parabolic relation between γ and p.S data were analyzed and well described by a two-band modelwith an additional linear T term, γT.An empiricalparabolic relation for γ as a function of holeconcentration has been found. <b>Key words:</b>high temperature superconductors, criticaltemperature, resistivity, thermoelectric power, Hallcoefficient, X-ray diffraction, Neutron diffraction, NdBa2Cu3O7−δ, hole concentration,substitution.

This thesis is divided in three parts. In the first part, a study of materials aimed for spintronics applications is presented. More specifically, calculations of the critical temperature in diluted magnetic semiconductors (DMS) and half-metallic ferromagnets are presented using a combination of electronic structure and statistical methods. It is shown that disorder and randomness of the magnetic atoms in DMS materials play a very important role in the determination of the critical temperature. The second part treats materials in reduced dimensions. Studies of multilayer and trilayer systems are presented. A theoretical model that incorporates interdiffusion in a multilayer is developed that gives better agreement with experimental observations. Using Monte Carlo simulations, the observed magnetic properties in the trilayer system Ni/Cu/Co at finite temperatures are qualitatively reproduced. In the third part, electronic structure calculations of complex Mn-based compounds displaying noncollinear magnetism are presented. The calculations reproduce with high accuracy the observed magnetic properties in these compounds. Furthermore, a model based on the electronic structure of the necessary conditions for noncollinear magnetism is presented.

<p>It is generally believed that one of the key parameterscontrolling the normal state and superconducting properties ofhigh temperature superconductors is the charge carrierconcentration<i>p</i>in the CuO₂planes.By changing the non-isovalent dopingconcentration on the RE site as well as the oxygen content in(RE)Ba₂Cu₃O_7−δ, an excellent tool is obtained tovary the hole concentration over a wide range from theunderdoped up to the overdoped regime.In the present thesis thefocus is on the doping effects on the structural and normalstate electrical properties in Nd-123 doped with Ca, La, Pr,Ca-Pr, and Ca-Th.T he effects of doping have been investigatedby X-ray and neutron powder diffraction, and by measurements ofthe resistivity, thermoelectric power<i>S</i>, and Hall coefficient R_H.T he thermoelectric power is a powerful tool forstudies of high temperature superconductivity and is highlysensitive to details of the electronic band structure.<i>S</i>as a function of temperature has been analyzed in twodifferent two band models.The parameters of these models arerelated to charactristic features of the electron bands and asemiempirical physical description of the doping dependence of<i>S</i>is obtained.So me important results are following:</p><p>(i)<i>The valence of Pr in the RE-123 family.</i>Results from thestructural investigations, the critical temperature Tc, and thethermoelectric power indicated a valence +4 at low dopingconcentration, which is in agreement with results of chargeneutral doping in the RE-123 family.(ii)<i>Hole localization</i>. The results of bond valence sum (BVS)calculations from neutron diffraction data showed that holelocalization on the Pr⁺⁴site was the main reason for the decrease of thehole concentration p.Differ ent types of localization wereinferred by S measurements for Ca-Th and Ca-Pr dopings.(iii)<i>Competition between added charge and disorder</i>. Theresults of RH measurements indicated that Ca doping introduceddisorder in the CuO₂planes in addition to added charge.This could bethe main reason for the observed small decrease of thebandwidth of the density of states in the description of aphenomenological narrow band model.(iv) Empirical parabolic relation between γ and p.S data were analyzed and well described by a two-band modelwith an additional linear T term, γT.An empiricalparabolic relation for γ as a function of holeconcentration has been found.</p><p><b>Key words:</b>high temperature superconductors, criticaltemperature, resistivity, thermoelectric power, Hallcoefficient, X-ray diffraction, Neutron diffraction, NdBa₂Cu₃O_7−δ, hole concentration,substitution.</p>

The overall thrust of this project is to gain an insight into a class of surface-tethered cross-linked thin films of poly(N-alkylacrylamides) that display a lower critical solution temperature (LCST).The structure of the alkyl group and the modification of the amide groups determine the LCST and resultant volume-phase transition behavior. The aim of this study involves synthesis and characterization of thin films and to correlate the volume-transition behavior to the structure of the alkyl group. For better understanding the volume-transition behavior, the polymer films are perturbed by the Hofmeister salt series to examine trends between different alkyl groups. While most of the studies have been done with bulk gels, the majority of the applications require the use of gels at surfaces and interfaces. Surface attached polymer networks provide an alternative to bulk gels showing superior response times, thus efficiency. Hence it is significant to understand the impact of confinement on the phase transition behavior of a polymer network. Anchoring a polymer network to a surface produces volume phase transition perpendicular to the substrate. The parallel swelling and collapse of the network is highly restricted due to lateral confinement, thus impacting properties such as structure, mechanical properties, dynamics and permeability of the network. Several studies have been done with poly(N-isopropylacrylamide) anchored to a substrate, which have shown significantly different behavior than unconstrained networks. Notable examples include a gradual as opposed to a sharp volume-phase transition, and significantly less swelling above and below the LCST. These studies only looked at poly(NIPAAm); therefore it remains unknown if these results are universal and will apply to other LCST polymers. Hence, we expanded upon these studies to also investigate a library of different LCST polymers belonging to the category of N-alkylacrylamides. I have synthesized the copolymers comprising of N-alkylacrylamides and methacryloxybenzophenone (MaBP). The benzophenone moiety in MaBP is photoreactive, allowing us to cross-link the copolymers by UV irradiation. Surface attached thin films were fabricated by spin coating the solution of copolymers and cross-linking by UV irradiation. The volume phase transitions of the coatings were studied under the influence of temperature and the salts of the Hofmeister series. Information concerning the state of responsive layers, the precise temperature at which the collapse occurs, and the changes in the molecular environment during the transition were investigated by ellipsometry and ATR-FTIR. In a longer perspective, understanding the transition behavior and the influence of salts governing this transition provides a better understanding of the interactions of biopolymers in natural systems.

Orientador: Cláudio Luiz Carvalho / Banca: Rafael Zadorosny / Banca: Carlos Yujiro Shigue / Resumo: Com a descoberta dos supercondutores de alta temperatura crítica na década de 80, as propriedades elétricas desses materiais passaram a ser intensamente estudadas, principalmente por meio do processo de dopagem. Desta forma, este trabalho teve por objetivo estudar os efeitos da dopagem nas propriedades elétricas do sistema supercondutor BSCCO com fórmula estequiométrica Bi1,6Pb0,4Sr2-xRExCa2Cu3O10+δ, por meio da substituição do elemento terra rara (RE), lantânio (La), em sítios de Sr, onde 0≤x≤2,0, em intervalos de 0,5. As soluções precursoras foram preparadas baseadas no método de Pechini, obtendo-se uma resina polimérica submetida a tratamento térmico de 200oC/10h, resultando em um material na forma de pó, o qual foi levado novamente a tratamento térmico entre 400oC a 810oC. Com o pó, foram preparadas pastilhas, submetendo-as a um novo tratamento térmico de 810oC/+31h. Para se conhecer as principais características das amostras, foram feitas a caracterização estrutural por meio da técnica de Difratometria de Raios X (DRX) para todos os tratamentos térmicos realizados; a caracterização elétrica, pelo método de quatro pontas dc; para a caracterização morfológica e química, a técnica de microscopia eletrônica de varredura (MEV), juntamente com a técnica de Espectroscopia por Energia Dispersiva de Raios X (EDX); e medidas magnéticas ac e dc para a caracterização magnética das amostras. Os resultados apontaram uma degradação das propriedades de supercondução, além de mudanças estruturais, morfológicas e magnéticas com o aumento da concentração de dopante / Abstract: With the discovery of high critical temperature superconductors in the 80, the electrical properties of these materials became intensively studied, mainly through the doping process. Thus, the objective of this work was the study of the effects of doping on the electrical properties of BSCCO superconducting system with stoichiometric formula Bi1,6Pb0,4Sr2-xRExCa2Cu3O10+δ, by the substitution of rare earth element (RE), lanthanum (La) in the sites of Sr, where 0 ≤ x ≤ 2.0, in interval of 0.5. The precursor solutions were prepared based by Pechini method, obtaining a polymer resin subjected to heat treatment at 200° 10h, which results in a material in C/ a powder. In sequence, futher heat treatments between 400oC to 810oC were made. With the powder were prepared bulks by subjecting them to a new heat treatment at 810° C/+31h. To know the main characteristics of the samples, structural characterization were made by the technique of X-Ray Diffraction (XRD) for all heat treated samples; the electrical characterization was made by the dc four probe method; for the morphological and chemical characterization by the technique of Scanning Electron Microscopy (SEM), together with the technique of Energy Dispersive X-ray Spectroscopy (EDX); and ac and dc magnetic measurements to magnetic characterization of the sample. The results shown a degradation of superconducting properties, as a consequence of structural, morphology and magnetic changes with the dopant concentration increase / Mestre

Made available in DSpace on 2014-06-11T19:25:33Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-03-11Bitstream added on 2014-06-13T18:28:58Z : No. of bitstreams: 1 rodrigues_vd_me_ilha.pdf: 878464 bytes, checksum: d4777ee537da76b7fbdd91cfdcae18f6 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Com a descoberta dos supercondutores de alta temperatura crítica na década de 80, as propriedades elétricas desses materiais passaram a ser intensamente estudadas, principalmente por meio do processo de dopagem. Desta forma, este trabalho teve por objetivo estudar os efeitos da dopagem nas propriedades elétricas do sistema supercondutor BSCCO com fórmula estequiométrica Bi1,6Pb0,4Sr2-xRExCa2Cu3O10+δ, por meio da substituição do elemento terra rara (RE), lantânio (La), em sítios de Sr, onde 0≤x≤2,0, em intervalos de 0,5. As soluções precursoras foram preparadas baseadas no método de Pechini, obtendo-se uma resina polimérica submetida a tratamento térmico de 200oC/10h, resultando em um material na forma de pó, o qual foi levado novamente a tratamento térmico entre 400oC a 810oC. Com o pó, foram preparadas pastilhas, submetendo-as a um novo tratamento térmico de 810oC/+31h. Para se conhecer as principais características das amostras, foram feitas a caracterização estrutural por meio da técnica de Difratometria de Raios X (DRX) para todos os tratamentos térmicos realizados; a caracterização elétrica, pelo método de quatro pontas dc; para a caracterização morfológica e química, a técnica de microscopia eletrônica de varredura (MEV), juntamente com a técnica de Espectroscopia por Energia Dispersiva de Raios X (EDX); e medidas magnéticas ac e dc para a caracterização magnética das amostras. Os resultados apontaram uma degradação das propriedades de supercondução, além de mudanças estruturais, morfológicas e magnéticas com o aumento da concentração de dopante / With the discovery of high critical temperature superconductors in the 80, the electrical properties of these materials became intensively studied, mainly through the doping process. Thus, the objective of this work was the study of the effects of doping on the electrical properties of BSCCO superconducting system with stoichiometric formula Bi1,6Pb0,4Sr2-xRExCa2Cu3O10+δ, by the substitution of rare earth element (RE), lanthanum (La) in the sites of Sr, where 0 ≤ x ≤ 2.0, in interval of 0.5. The precursor solutions were prepared based by Pechini method, obtaining a polymer resin subjected to heat treatment at 200° 10h, which results in a material in C/ a powder. In sequence, futher heat treatments between 400oC to 810oC were made. With the powder were prepared bulks by subjecting them to a new heat treatment at 810° C/+31h. To know the main characteristics of the samples, structural characterization were made by the technique of X-Ray Diffraction (XRD) for all heat treated samples; the electrical characterization was made by the dc four probe method; for the morphological and chemical characterization by the technique of Scanning Electron Microscopy (SEM), together with the technique of Energy Dispersive X-ray Spectroscopy (EDX); and ac and dc magnetic measurements to magnetic characterization of the sample. The results shown a degradation of superconducting properties, as a consequence of structural, morphology and magnetic changes with the dopant concentration increase

This thesis presents the results of a research project to develop methods to carry out fire safety design of welded steel tubular trusses at elevated temperatures due to fire exposure. It deals with three subjects: resistance of welded tubular joints at elevated temperatures, effects of large truss deflection in fire on member design and effects of localised heating. The objectives of the project are achieved through numerical finite element modelling at elevated temperatures using the commercial Finite Element software ABAQUS v6.10-1 (2011). Validation of the simulation model for joints is based on comparison against the test results of Nguyen et al. (2010) and Kurobane et al. (1986). Validation of the simulation model for trusses is through checking against the test results of Edwards (2004) and Liu et al. (2010).For welded tubular joints, extensive numerical simulations have been conducted on T-, Y-, X-, N- and non-overlapped K-joints subjected to brace axial compression or tension, considering a wide range of geometrical parameters. Uniform temperature distribution was assumed for both the chord and brace members. Results of the numerical simulations indicate for gap K- and N-joints (two brace members, one in tension and the other in compression) and for T-, Y- and X-joints with the brace member under axial tensile load (one brace member only, in tension), it is suitable to use the same ambient temperature calculation equation as in the CIDECT (2010) or EN 1993-1-8 (CEN, 2005a) design guides and simply replace the ambient temperature strength of steel with the elevated temperature value. However, for T-, Y- and X-joints under brace compression load (one brace member only, in compression), the effect of large chord deformation should be considered. Large chord deformation changes the chord geometry and invalidates the assumed yield line mechanism at ambient temperature. For approximation, the results of this research indicate that it is acceptable to modify the ambient temperature joint strength by a reduction factor for the elastic modulus of steel at elevated temperatures. In the current fire safety design method for steel truss, a member based approach is used. In this approach, the truss member forces are calculated at ambient temperature based on linear elastic analysis. These forces are then used to calculate the truss member limiting temperatures. An extensive parametric study has been carried out to investigate whether this method is appropriate. The parametric study encompasses different design parameters over a wide range of values, including truss type, joint type, truss span-to-depth ratio, critical member slenderness, applied load ratio, number of brace members, initial imperfection and thermal elongation. The results of this research show that due to a truss undergoing large displacements at elevated temperatures, some truss members (compression brace members near the truss centre) experience large increases in member forces. Therefore, using the ambient temperature member force, as in the current truss fire safety design method, may overestimate the truss member critical temperature by 100 °C. A method has been proposed to analytically calculate the increase in brace compressive force due to large truss deformation. In this method, the maximum truss displacement is assumed to be span/30. A comparison of the results calculated using the proposed method against the truss parametric study results has shown good agreement with the two sets of results, with the calculation results generally being slightly on the safe side. When different members of a truss are heated to different temperatures due to localised fire exposure, the brace members in compression experience increased compression due to restrained thermal expansion. To calculate the critical temperature of a brace member in a localised heated truss, it is necessary to consider this effect of restrained thermal expansion. It is also necessary to consider the beneficial effects of the adjacent members being heated, which tends to reduce the increase in compressive force in the critical member under consideration. Again, an extensive set of parametric studies have been conducted, for different load ratio, slenderness and axial restraint ratio. The results of this parametric study suggest that to calculate the critical temperature of a brace member, it is not necessary to consider the effects of the third or further adjacent members being heated. For the remainder of the heated members, this thesis has proposed a linear elastic, static analysis method at ambient temperature to calculate the additional compressive force (some negative, indicating tension) in the critical member caused by the heated members (including the critical member itself and the adjacent members). The additional compressive force is then used to calculate the limiting temperature of the critical member. For this purpose, the approximate analytical equation of Wang et al. (2010) has been demonstrated to be suitable.

No description available.