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Mechanical and electrical properties of carbon nanofiber–ceramic nanoparticle–polymer composites
(2010)

The present research is focused on the manufacturing and analysis of composites consisting of a thermosetting polymer reinforced with fillers of nanometric dimensions. The materials were chosen to be an epoxy resin matrix and two different kinds of fillers: electrically conductive carbon nanofibers (CNFs) and ceramic titanium dioxide (TiO2) and aluminium dioxide (Al2O3) nanoparticles. In an initial step of the work, in order to understand the effect that each kind of filler had when added separately to the polymer matrix, CNF–EP and ceramic nanoparticle–EP composites were manufactured and tested. Each type of filler was dispersed in the polymer matrix using two different dispersion technologies. CNFs were dispersed in the resin with the aid of a three roll calender (TRC) whereas a torus bead mill (TML) was used in the ceramic nanoparticle case. Calendering proved to be an efficient method to disperse the untreated CNFs in the polymer matrix. The study of the physical properties of undispersed CNF composites showed that the tensile strength and the maximum sustained strain, were more sensitive to the state of dispersion of the nanofibers than the elastic modulus, fracture toughness, impact energy and electrical conductivity (for filler loadings above the percolation threshold of the system). Rheological investigation of the uncured CNF–epoxy mixture at different stages of dispersion indicated the formation of an interconnected nanofiber network within the matrix after the initial steps of calendering. CNF–EP composites showed better mechanical performance than the unmodified polymer matrix. However, the tensile modulus and strength of the CNF composites accused the presence of remaining nanofiber clusters and did not reach theoretically predicted values. Fracture toughness and resistance against impact did not seem to be so sensitive to the state of nanofiber dispersion and improved consistently with the incorporation of the CNFs. The electrical conductivity of the CNF composites saw an eight orders of magnitude percolative enhancement with increasing nanofiber content. The percolation threshold for the achieved level of CNF dispersion was found to be 0.14 vol. %. It was also determined that, for these composites, the main mechanism of electrical transmission was the electron tunnelling mechanism. Ceramic nanoparticle–EP composites were manufactured using TiO2 and Al2O3 particles as fillers in the epoxy matrix. Mechanical dispersion of the nanoparticles in the liquid polymer by means of a torus bead mill dissolver led to homogeneous distributions of particles in the matrix. Remaining particle agglomerates had a mean value of 80 nm. However, micrometer sized agglomerates could clearly be observed in the microscopical analysis of the composites, especially in the TiO2 case. The inclusion of the nanoparticles in the epoxy resin resulted in a general improvement of the modulus, strength, maximum sustained strain, fracture toughness and impact energy of the polymer matrix. Nanoparticles were able to overcome the stiffness/toughness problem. On the other hand, nanoparticle–EP composites showed lower electrical conductivity than the neat epoxy. In general, there were no significant differences between the incorporation of TiO2 or Al2O3 particles. Based on the previous results, CNFs and nanoparticles were combined as fillers to create a nanocomposite that could benefit from the electrical properties provided by the conductive CNFs and, at the same time, have improved mechanical performance thanks to the presence of the well dispersed ceramic nanoparticles. Nanoparticles and CNFs were dispersed separately to create two batches which were blended together in a dissolver mixer. This method proved effective to create well dispersed CNF–nanoparticle–epoxy composites which showed improved electrical and mechanical properties compared with the neat polymer matrix. The well dispersed ceramic nanofillers were able to introduce additional energy dissipating mechanisms in the CNF–EP composites that resulted in an improvement of their mechanical performance. With high volume loadings of nanoparticles most of the reinforcement came from the presence of the nanoparticles in the polymer matrix. Therefore, the observed trends were, in essence, similar to the ones observed in the ceramic nanoparticle–EP composites. The enhancement in the mechanical performance of the CNF composites with the inclusion of ceramic nanoparticles came at the price of an increase in the percolation threshold and a reduction of the electrical conductivity of the CNF–nanoparticle–EP composites compared with the CNF–EP materials. A modified Weber and Kamal’s fiber contact model (FCM) was used to explain the electrical behaviour of the CNF–nanoparticle–EP composites once percolation was achieved. This model was able to fit rather accurately the experimentally measured conductivity of these composites.

Tropical intersection theory
(2010)

This thesis consists of five chapters: Chapter 1 contains the basics of the theory and is essential for the rest of the thesis. Chapters 2-5 are to a large extent independent of each other and can be read separately. - Chapter 1: Foundations of tropical intersection theory In this first chapter we set up the foundations of a tropical intersection theory covering many concepts and tools of its counterpart in algebraic geometry such as affine tropical cycles, Cartier divisors, morphisms of tropical cycles, pull-backs of Cartier divisors, push-forwards of cycles and an intersection product of Cartier divisors and cycles. Afterwards, we generalize these concepts to abstract tropical cycles and introduce a concept of rational equivalence. Finally, we set up an intersection product of cycles and prove that every cycle is rationally equivalent to some affine cycle in the special case that our ambient cycle is R^n. We use this result to show that rational and numerical equivalence agree in this case and prove a tropical Bézout's theorem. - Chapter 2: Tropical cycles with real slopes and numerical equivalence In this chapter we generalize our definitions of tropical cycles to polyhedral complexes with non-rational slopes. We use this new definition to show that if our ambient cycle is a fan then every subcycle is numerically equivalent to some affine cycle. Finally, we restrict ourselves to cycles in R^n that are "generic" in some sense and study the concept of numerical equivalence in more detail. - Chapter 3: Tropical intersection products on smooth varieties We define an intersection product of tropical cycles on tropical linear spaces L^n_k and on other, related fans. Then, we use this result to obtain an intersection product of cycles on any "smooth" tropical variety. Finally, we use the intersection product to introduce a concept of pull-backs of cycles along morphisms of smooth tropical varieties and prove that this pull-back has all expected properties. - Chapter 4: Weil and Cartier divisors under tropical modifications First, we introduce "modifications" and "contractions" and study their basic properties. After that, we prove that under some further assumptions a one-to-one correspondence of Weil and Cartier divisors is preserved by modifications. In particular we can prove that on any smooth tropical variety we have a one-to-one correspondence of Weil and Cartier divisors. - Chapter 5: Chern classes of tropical vector bundles We give definitions of tropical vector bundles and rational sections of tropical vector bundles. We use these rational sections to define the Chern classes of such a tropical vector bundle. Moreover, we prove that these Chern classes have all expected properties. Finally, we classify all tropical vector bundles on an elliptic curve up to isomorphisms.