Synthesis and Thermophysical Properties of Ether Functionalized Sulfonium Ionic Liquids as Potential Electrolytes for Electrochemical Applications

During this work, a novel series of hydrophobic room temperature ionic liquids (ILs) based on five ether functionalized sulfonium cations bearing the bis(trifluoromethyl)sulfonylimide, [NTf2]- anion were synthesized and characterized. Their physicochemical properties, such as density, viscosity and ionic conductivity, electrochemical window along with thermal properties including phase transition behavior and decomposition temperature, have been measured. All of these ILs showed large liquid range temperature, low viscosity and good conductivity. Additionally, by combining DFT calculations along with electrochemical characterization it appears that these novel ILs show good electrochemical stability windows, suitable for the potential application as electrolyte materials in electrochemical energy storage devices.

Nafion-based composite electrolytes for proton exchange membrane fuel cells operating above 120C with titania nanoparticles and nanotubes as fillers

FAPESP:5150

Big bang bifurcations in von Bertalanffy’s dynamics with strong and weak Allee effects

The main purpose of this work was to study population dynamic discrete models in which the growth of the population is described by generalized von Bertalanffy's functions, with an adjustment or correction factor of polynomial type. The consideration of this correction factor is made with the aim to introduce the Allee effect. To the class of generalized von Bertalanffy's functions is identified and characterized subclasses of strong and weak Allee's functions and functions with no Allee effect. This classification is founded on the concepts of strong and weak Allee's effects to population growth rates associated. A complete description of the dynamic behavior is given, where we provide necessary conditions for the occurrence of unconditional and essential extinction types. The bifurcation structures of the parameter plane are analyzed regarding the evolution of the Allee limit with the aim to understand how the transition from strong Allee effect to no Allee effect, passing through the weak Allee effect, is realized. To generalized von Bertalanffy's functions with strong and weak Allee effects is identified an Allee's effect region, to which is associated the concepts of chaotic semistability curve and Allee's bifurcation point. We verified that under some sufficient conditions, generalized von Bertalanffy's functions have a particular bifurcation structure: the big bang bifurcations of the so-called box-within-a-box type. To this family of maps, the Allee bifurcation points and the big bang bifurcation points are characterized by the symmetric of Allee's limit and by a null intrinsic growth rate. The present paper is also a significant contribution in the framework of the big bang bifurcation analysis for continuous 1D maps and unveil their relationship with the explosion birth and the extinction phenomena.

Optimization of Li-ion solid electrolytes

The synthesis and optimization of two Li-ion solid electrolytes were studied in this work. Different combinations of precursors were used to prepare La0.5Li0.5TiO3 via mechanosynthesis. Despite the ability to form a perovskite phase by the mechanochemical reaction it was not possible to obtain a pure La0.5Li0.5TiO3 phase by this process. Of all the seven combinations of precursors and conditions tested, the one where La2O3, Li2CO3 and TiO2 were milled for 480min (LaOLiCO-480) showed the best results, with trace impurity phases still being observed. The main impurity phase was that of La2O3 after mechanosynthesis (22.84%) and Li2TiO3 after calcination (4.20%). Two different sol-gel methods were used to substitute boron on the Zr-site of Li1+xZr2-xBx(PO4)3 or the P-site of Li1+6xZr2(P1-xBxO4)3, with the doping being achieved on the Zr-site using a method adapted from Alamo et al (1989). The results show that the Zr-site is the preferential mechanism for B doping of LiZr2(PO4)3 and not the P-site. Rietveld refinement of the unit-cell parameters was performed and it was verified by consideration of Vegard’s law that it is possible to obtain phase purity up to x = 0.05. This corresponds with the phases present in the XRD data, that showed the additional presence of the low temperature (monoclinic) phase for the powder sintered at 1200ºC for 12h of compositions with x ≥ 0.075. The compositions inside the solid solution undergo the phase transition from triclinic (PDF#01-074-2562) to rhombohedral (PDF#01-070-6734) when heating from 25 to 100ºC, as reported in the literature for the base composition. Despite several efforts, it was not possible to obtain dense pellets and with physical integrity after sintering, requiring further work in order to obtain dense pellets for the electrochemical characterisation of Li Zr2(PO4)3 and Li1.05Zr1.95B0.05(PO4)3.

Electrolytes for ceramic oxide fuel cells

The main objective of this dissertation is the development and processing of novel ionic conducting ceramic materials for use as electrolytes in proton or oxide-ion conducting solid oxide fuel cells. The research aims to develop new processing routes and/or materials offering superior electrochemical behavior, based on nanometric ceramic oxide powders prepared by mechanochemical processes. Protonic ceramic fuel cells (PCFCs) require electrolyte materials with high proton conductivity at intermediate temperatures, 500-700ºC, such as reported for perovskite zirconate oxides containing alkaline earth metal cations. In the current work, BaZrO3 containing 15 mol% of Y (BZY) was chosen as the base material for further study. Despite offering high bulk proton conductivity the widespread application of this material is limited by its poor sinterability and grain growth. Thus, minor additions of oxides of zinc, phosphorous and boron were studied as possible sintering additives. The introduction of ZnO can produce substantially enhanced densification, compared to the un-doped material, lowering the sintering temperature from 1600ºC to 1300ºC. Thus, the current work discusses the best solid solution mechanism to accommodate this sintering additive. Maximum proton conductivity was shown to be obtained in materials where the Zn additive is intentionally adopted into the base perovskite composition. P2O5 additions were shown to be less effective as a sintering additive. The presence of P2O5 was shown to impair grain growth, despite improving densification of BZY for intermediate concentrations in the range 4 – 8 mol%. Interreaction of BZY with P was also shown to have a highly detrimental effect on its electrical transport properties, decreasing both bulk and grain boundary conductivities. The densification behavior of H3BO3 added BaZrO3 (BZO) shows boron to be a very effective sintering aid. Nonetheless, in the yttrium containing analogue, BaZr0.85Y0.15O3- (BZY) the densification behavior with boron additives was shown to be less successful, yielding impaired levels of densification compared to the plain BZY. This phenomenon was shown to be related to the undesirable formation of barium borate compositions of high melting temperatures. In the last section of the work, the emerging oxide-ion conducting materials, (Ba,Sr)GeO3 doped with K, were studied. Work assessed if these materials could be formed by mechanochemical process and the role of the ionic radius of the alkaline earth metal cation on the crystallographic structure, compositional homogeneity and ionic transport. An abrupt jump in oxide-ion conductivity was shown on increasing operation temperature in both the Sr and Ba analogues.

Existence and weak-strong uniqueness for the Navier-Stokes-Smoluchowski system over moving domains

This dissertation concerns the well-posedness of the Navier-Stokes-Smoluchowski system. The system models a mixture of fluid and particles in the so-called bubbling regime. The compressible Navier-Stokes equations governing the evolution of the fluid are coupled to the Smoluchowski equation for the particle density at a continuum level. First, working on fixed domains, the existence of weak solutions is established using a three-level approximation scheme and based largely on the Lions-Feireisl theory of compressible fluids. The system is then posed over a moving domain. By utilizing a Brinkman-type penalization as well as penalization of the viscosity, the existence of weak solutions of the Navier-Stokes-Smoluchowski system is proved over moving domains. As a corollary the convergence of the Brinkman penalization is proved. Finally, a suitable relative entropy is defined. This relative entropy is used to establish a weak-strong uniqueness result for the Navier-Stokes-Smoluchowski system over moving domains, ensuring that strong solutions are unique in the class of weak solutions.

Kinetic study of solid phase demineralization by weak acids in one-step enzymatic bio-refinery of shrimp cuticles

We describe a one-step bio-refinery process for shrimp composites by-products. Its originality lies in a simple rapid (6 h) biotechnological cuticle fragmentation process that recovers all major compounds (chitins, peptides and minerals in particular calcium). The process consists of a controlled exogenous enzymatic proteolysis in a food-grade acidic medium allowing chitin purification (solid phase), and recovery of peptides and minerals (liquid phase). At a pH of between 3.5 and 4, protease activity is effective, and peptides are preserved. Solid phase demineralization kinetics were followed for phosphoric, hydrochloric, acetic, formic and citric acids with pKa ranging from 2.1 to 4.76. Formic acid met the initial aim of (i) 99 % of demineralization yield and (ii) 95 % deproteinization yield at a pH close to 3.5 and a molar ratio of 1.5. The proposed one-step process is proven to be efficient. To formalize the necessary elements for the future optimization of the process, two models to predict shell demineralization kinetics were studied, one based on simplified physical considerations and a second empirical one. The first model did not accurately describe the kinetics for times exceeding 30 minutes, the empirical one performed adequately.

Effects of synthetic conditions on the structural, stability and ion conducting properties of Li0.30(La0.50Ln0.50)0.567TiO3 (Ln= La, Pr, Nd) solid electrolytes for rechargeable lithium batteries

The structure, thermal stability, morphology and ion conductivity of titanium perovskites with the general formula Li3xLn2/3−xTiO3 (Ln = rare earth element; 3x= 0.30) are studied in the context of their possible use as solid electrolyte materials for lithium ion batteries. Materials are prepared by a glycine-nitrate method using different sintering treatments, with a cation-disorder-induced structural transition from tetragonal to cubic symmetry, detected as quenching temperature increases. SEM images show that the average grain size increases with increasing sintering temperature and time. Slightly higher bulk conductivity values have been observed for quenched samples sintered at high temperature. Bulk conductivity decreases with the lanthanide ion size. A slight conductivity enhancement, always limited by grain boundaries, is observed for longer sintering times. TDX measurements of the electrolyte/cathode mixtures also show a good stability of the electrolytes in the temperature range of 30-1100ºC.

WEAK ISOMETRIES OF HAMMING SPACES

In this thesis we study weak isometries of Hamming spaces. These are permutations of a Hamming space that preserve some but not necessarily all distances. We wish to find conditions under which a weak isometry is in fact an isometry. This type of problem was first posed by Beckman and Quarles for Rn. In chapter 2 we give definitions pertinent to our research. The 3rd chapter focuses on some known results in this area with special emphasis on papers by V. Krasin as well as S. De Winter and M. Korb who solved this problem for the Boolean cube, that is, the binary Hamming space. We attempted to generalize some of their methods to the non-boolean case. The 4th chapter has our new results and is split into two major contributions. Our first contribution shows if n=p or p < n2, then every weak isometry of Hnq that preserves distance p is an isometry. Our second contribution gives a possible method to check if a weak isometry is an isometry using linear algebra and graph theory.

Trace elements and electrolytes in human resting mixed saliva after exercise

Objectives—Exercise is known to cause changes in the concentration of salivary components such as amylase, Na, and Cl. The aim of this investigation was to evaluate the eVect of physical exercise on the levels of trace elements and electrolytes in whole (mixed) saliva. Methods—Forty subjects performed a maximal exercise test on a cycle ergometer. Samples of saliva were obtained before and immediately after the exercise test. Sample concentrations of Fe, Mg, Sc, Cr, Mn, Co, Cu, Zn, Se, Sr, Ag, Sb, Cs, and Hg were determined by inductively coupled plasma mass spectrometry and concentrations of Ca and Na by atomic absorption spectrometry. Results—After exercise, Mg and Na levels showed a significant increase (p<0.05) while Mn levels fell (p<0.05). Zn/Cu molar ratios were unaVected by exercise. Conclusions—Intense physical exercise induced changes in the concentrations of only three (Na, Mg, and Mn) of the 16 elements analysed in the saliva samples. Further research is needed to assess the clinical implications of these findings.