Crystallization characteristics of bioactive glasses

Bioactive glasses are excellent candidates for implant materials, because they can form a chemical bond to bone or guide bone growth, depending on the glass composition. Some compositions have even shown soft tissue attachment and antimicrobial effects. So far, most clinical applications are based on monoliths, plates and particulates of different grain sizes. There is a growing interest in special products such as porous implants sintered from microspheres and fibers drawn from preforms or glass melts. The viscosity range at which these are formed coincides with the crystallization temperature range for most bioactive glasses, thus complicating the manufacturing process. In this work, the crystallization tendency and its kinetics for a series of glasses with their compositions within the range of bioactivity were investigated. The factors affecting crystallization and how it is related to composition were studied by means of thermal analysis and hot stage microscopy. The crystal compositions formed during isothermal and non-isothermal heat treatments were analyzed with SEM-EDXA and X-ray diffraction analysis. The temperatures at which sintering and fiber drawing can take place without interfering with crystallization were determined and glass compositions which are suitable for these purposes were established. The bioactivity of glass fibers and partly crystallized glass plates was studied by soaking them in simulated body fluid (SBF). The thickness of silica, calcium and phosphate rich reaction layers on the glass surface after soaking was used as an indication of the bioactivity. The results indicated that the crystallization tendencies of the experimental glasses are strongly dependent on composition. The main factor affecting the crystallization was found to be the alkali oxide content: the higher the alkali oxide content the lower the crystallization temperature. The primary crystalline phase formed at low temperatures in these glasses was sodium calcium silicate. The crystals were found to form through internal nucleation, leading to bulk crystallization. These glasses had high bioactivity in vitro. Even when partially crystalline, they formed typical reaction layers, indicating bioactivity. In fact, sodium calcium silicate crystals were shown to transform in vitro into hydroxyapatite during soaking. However, crystallization should be avoided because it was shown to retard dissolution, bioactivity reactions and complicate fiber drawing process. Glass compositions having low alkali oxide content showed formation of wollastonite crystals on the surface, at about 300°C above the glass transition temperature. The wide range between glass transition and crystallization allowed viscous flow sintering of these compositions. These glasses also withstood the thermal treatments required for fiber drawing processing. Precipitation of calcium and phosphate on fibers of these glasses in SBF suggested that they were osteoconductive. Glasses showing bioactivity crystallize easily, making their hot working challenging. Undesired crystallization can be avoided by choosing suitable compositions and heat treatment parameters, allowing desired product forms to be attained. Small changes in the oxide composition of the glass can have large effects and therefore a thorough understanding of glass crystallization behavior is a necessity for a successful outcome, when designing and manufacturing implants containing bioactive glasses.

Mössbauer spectra of iron oxides in the bulk and nanocrystalline states

Magnetic nanoparticles are very important in modern industry. These particles are used in many different spheres of life. Nanoparticles have unusual physical and chemical properties connected both with quantum dimensional effects and with the increased role of the surface atoms. Most clearly the difference between the properties of bulk materials and nanoparticles can be seen in the magnetic properties of these materials. The most typical magnetic properties of nanomaterials are superparamagnetism with the size of the cluster from 1 to 10 nm; single-domain magnetic state of nanoclusters and nanostructures up to 20 nm; magnetization processes connected with magnetic cluster ordering and with its forms and sizes; quantum magnetic tunneling effects when magnetization changes by jumps and giant magnetoresistance effects. For research of the magnetic properties of iron-containing nanostructures, it is convenient to apply Mӧssbauer spectroscopy. In this work a number of nano-sized samples of iron oxides were examined by Mössbauer spectroscopy. The Mössbauer spectra of nanoparticles with various sizes were obtained. Mössbauer spectra of iron oxide nanoparticles were compared with the spectra of bulk samples. It was shown how the spectra of iron oxide nanoparticles change depending on the particle sizes.

Ferromagnetic properties of pyrolytic nanocarbon

The work reported in this thesis is dedicated to irreversible magnetic properties in pyrolytic nanocarbon samples. Based on atomic force microscope images, the samples consist of carbon clusters with radius 30..120 nm. These are treated as single-domain nanoparticles. Magnetic hysteresis, field cooled, zero field cooled and thermoremanent magnetization measurements were performed using an RF SQUID magnetometer and ferromagnetic behaviour was observed. Analysis suggests that the ferromagnetic ordering is associated with defects in a thin surface layer, whose thickness is independent of particle size. Critical radius for single-domain particles, critical radius for coherent rotation, magnetic layer thickness, distance between elementary magnetic moments, saturation magnetization, exchange stiffness constant and anisotropy energy density are also presented.

Growth, magnetic and transport properties of InSb and II-IV-As2 semiconductors doped with manganese

This thesis is devoted to growth and investigations of Mn-doped InSb and II-IV-As2 semiconductors, including Cd1-xZnxGeAs2:Mn, ZnSiAs2:Mn bulk crystals, ZnSiAs2:Mn/Si heterostructures. Bulk crystals were grown by direct melting of starting components followed by fast cooling. Mn-doped ZnSiAs2/Si heterostructures were grown by vacuum-thermal deposition of ZnAs2 and Mn layers on Si substrates followed by annealing. The compositional and structural properties of samples were investigated by different methods. The samples consist of micro- and nano- sizes clusters of an additional ferromagnetic Mn-X phases (X = Sb or As). Influence of magnetic precipitations on magnetic and electrical properties of the investigated materials was examined. With relatively high Mn concentration the main contribution to magnetization of samples is by MnSb or MnAs clusters. These clusters are responsible for high temperature behavior of magnetization and relatively high Curie temperature: up to 350 K for Mn-doped II-IV-As2 and about 600 K for InMnSb. The low-field magnetic properties of Mn-doped II-IV-As2 semiconductors and ZnSiAs2:Mn/Si heterostructures are connected to the nanosize MnAs particles. Also influence of nanosized MnSb clusters on low-field magnetic properties of InMnSb have been observed. The contribution of paramagnetic phase to magnetization rises at low temperatures or in samples with low Mn concentration. Source of this contribution is not only isolated Mn ions, but also small complexes, mainly dimmers and trimmers formed by Mn ions, substituting cation positions in crystal lattice. Resistivity, magnetoresistance and Hall resistivity properties in bulk Mn-doped II-IV-As2 and InSb crystals was analyzed. The interaction between delocalized holes and 3d shells of the Mn ions together with giant Zeeman splitting near the cluster interface are respond for negative magnetoresistance. Additionally to high temperature critical pointthe low-temperature ferromagnetic transition was observed Anomalous Hall effect was observed in Mn doped samples and analyzed for InMnSb. It was found that MnX clusters influence significantly on magnetic scattering of carriers.

Oxidation rates of carbon and nitrogen in char residues from solid fuels

Computational fluid dynamics (CFD) modeling is an important tool in designing new combustion systems. By using CFD modeling, entire combustion systems can be modeled and the emissions and the performance can be predicted. CFD modeling can also be used to develop new and better combustion systems from an economical and environmental point of view. In CFD modeling of solid fuel combustion, the combustible fuel is generally treated as single fuel particles. One of the limitations with the CFD modeling concerns the sub-models describing the combustion of single fuel particles. Available models in the scientific literature are in many cases not suitable as submodels for CFD modeling since they depend on a large number of input parameters and are computationally heavy. In this thesis CFD-applicable models are developed for the combustion of single fuel particles. The single particle models can be used to improve the combustion performance in various combustion devices or develop completely new technologies. The investigated fields are oxidation of carbon (C) and nitrogen (N) in char residues from solid fuels. Modeled char-C oxidation rates are compared to experimental oxidation rates for a large number of pulverized solid fuel chars under relevant combustion conditions. The experiments have been performed in an isothermal plug flow reactor operating at 1123-1673 K and 3-15 vol.% O2. In the single particle model, the char oxidation is based on apparent kinetics and depends on three fuel specific parameters: apparent pre-exponential factor, apparent activation energy, and apparent reaction order. The single particle model can be incorporated as a sub-model into a CFD code. The results show that the modeled char oxidation rates are in good agreement with experimental char oxidation rates up to around 70% of burnout. Moreover, the results show that the activation energy and the reaction order can be assumed to be constant for a large number of bituminous coal chars under conditions limited by the combined effects of chemical kinetics and pore diffusion. Based on this, a new model based on only one fuel specific parameter is developed (Paper III). The results also show that reaction orders of bituminous coal chars and anthracite chars differ under similar conditions (Paper I and Paper II); reaction orders of bituminous coal chars were found to be one, while reaction orders of anthracite chars were determined to be zero. This difference in reaction orders has not previously been observed in the literature and should be considered in future char oxidation models. One of the most frequently used comprehensive char oxidation models could not explain the difference in the reaction orders. In the thesis (Paper II), a modification to the model is suggested in order to explain the difference in reaction orders between anthracite chars and bituminous coal chars. Two single particle models are also developed for the NO formation and reduction during the oxidation of single biomass char particles. In the models the char-N is assumed to be oxidized to NO and the NO is partly reduced inside the particle. The first model (Paper IV) is based on the concentration gradients of NO inside and outside the particle and the second model is simplified to such an extent that it is based on apparent kinetics and can be incorporated as a sub-model into a CFD code (Paper V). Modeled NO release rates from both models were in good agreement with experimental measurements from a single particle reactor of quartz glass operating at 1173-1323 K and 3-19 vol.% O2. In the future, the models can be used to reduce NO emissions in new combustion systems.

Magnetic properties of multi-walled nanotubes on polysterene substrate

Nanotubes are one of the most perspective materials in modern nanotechologies. It makes present investigation very actual. In this work magnetic properties of multi-walled nanotubes on polystyrene substrate are investigated by using quantum magnetometer SQUID. Main purpose was to obtain magnetic field and temperature dependences of magnetization and to compare them to existing theoretical models of magnetism in carbon-bases structures. During data analysis a mathematical algorithm for obtained data filtration was developed because measurement with quantum magnetometer assume big missives of number data, which contain accidental errors. Nature of errors is drift of SQUID signal, errors of different parts of measurement station. Nanotube samples on polystyrene substrate were studied with help of atomic force microscope. On the surface traces of nanotube were found contours, which were oriented in horizontal plane. This feature was caused by rolling method for samples. Detailed comparison of obtained dependences with information of other researches on this topic allows to obtain some conclusions about nature of magnetism in the samples. It emphasizes importance and actuality of this scientific work.

Cost Reduction of Permanent Magnet Synchronous Machines

Electrical machine drives are the most electrical energy-consuming systems worldwide. The largest proportion of drives is found in industrial applications. There are, however many other applications that are also based on the use of electrical machines, because they have a relatively high efficiency, a low noise level, and do not produce local pollution. Electrical machines can be classified into several categories. One of the most commonly used electrical machine types (especially in the industry) is induction motors, also known as asynchronous machines. They have a mature production process and a robust rotor construction. However, in the world pursuing higher energy efficiency with reasonable investments not every application receives the advantage of using this type of motor drives. The main drawback of induction motors is the fact that they need slipcaused and thus loss-generating current in the rotor, and additional stator current for magnetic field production along with the torque-producing current. This can reduce the electric motor drive efficiency, especially in low-speed, low-power applications. Often, when high torque density is required together with low losses, it is desirable to apply permanent magnet technology, because in this case there is no need to use current to produce the basic excitation of the machine. This promotes the effectiveness of copper use in the stator, and further, there is no rotor current in these machines. Again, if permanent magnets with a high remanent flux density are used, the air gap flux density can be higher than in conventional induction motors. These advantages have raised the popularity of PMSMs in some challenging applications, such as hybrid electric vehicles (HEV), wind turbines, and home appliances. Usually, a correctly designed PMSM has a higher efficiency and consequently lower losses than its induction machine counterparts. Therefore, the use of these electrical machines reduces the energy consumption of the whole system to some extent, which can provide good motivation to apply permanent magnet technology to electrical machines. However, the cost of high performance rare earth permanent magnets in these machines may not be affordable in many industrial applications, because the tight competition between the manufacturers dictates the rules of low-cost and highly robust solutions, where asynchronous machines seem to be more feasible at the moment. Two main electromagnetic components of an electrical machine are the stator and the rotor. In the case of a conventional radial flux PMSM, the stator contains magnetic circuit lamination and stator winding, and the rotor consists of rotor steel (laminated or solid) and permanent magnets. The lamination itself does not significantly influence the total cost of the machine, even though it can considerably increase the construction complexity, as it requires a special assembly arrangement. However, thin metal sheet processing methods are very effective and economically feasible. Therefore, the cost of the machine is mainly affected by the stator winding and the permanent magnets. The work proposed in this doctoral dissertation comprises a description and analysis of two approaches of PMSM cost reduction: one on the rotor side and the other on the stator side. The first approach on the rotor side includes the use of low-cost and abundant ferrite magnets together with a tooth-coil winding topology and an outer rotor construction. The second approach on the stator side exploits the use of a modular stator structure instead of a monolithic one. PMSMs with the proposed structures were thoroughly analysed by finite element method based tools (FEM). It was found out that by implementing the described principles, some favourable characteristics of the machine (mainly concerning the machine size) will inevitable be compromised. However, the main target of the proposed approaches is not to compete with conventional rare earth PMSMs, but to reduce the price at which they can be implemented in industrial applications, keeping their dimensions at the same level or lower than those of a typical electrical machine used in the industry at the moment. The measurement results of the prototypes show that the main performance characteristics of these machines are at an acceptable level. It is shown that with certain specific actions it is possible to achieve a desirable efficiency level of the machine with the proposed cost reduction methods.

The Role of Structural Imperfections in Sr2FeMoO6 Thin Films

In this work, Sr2FeMoO6 (SFMO) thin films were studied with the main focus on their magnetic and magneto-transport properties. The fabrication process of pulsed laser deposited SFMO films was first optimized. Then the effects of strain, film thickness and substrate were thoroughly investigated. In addition to these external factors, the effect of intrinsic defects on the magnetic properties of SFMO were also clarified. Secondly, the magnetoresistivity mechanims of SFMO films were studied and a semiempirical model of the temperature dependence of resistivity was introduced. The films were grown on single crystal substrates using a ceramic target made with sol-gel method. The structural characterization of the films were carried out with X-ray diffraction, atomic force microscopy, transmission electron microscopy and high kinetic energy photoelectron spectroscopy. The magnetic properties were measured with SQUID magnetometer and the magneto-transport properties by magnetometer with a resistivity option. SFMO films with the best combination of structural and magnetic properties were grown in Ar atmosphere at 1050 °C . Their magnetic properties could not be improved by the ex situ post-annealing treatments aside from the treatments in ultra-high vacuum conditions. The optimal film thickness was found to be around 150 nm and only small improvement in the magnetic properties with decreasing strain was observed. Instead, the magnetic properties were observed to be highly dependent on the choice of the substrate due to the lattice mismatch induced defects, which are best avoided by using the SrTiO3 substrate. The large difference in the Curie temperature and the saturation magnetization between the SFMO thin film and polycrystalline bulk samples was connected to the antisite disorder and oxygen vacancies. Thus, the Curie temperature of SFMO thin films could be improved by increasing the amount of oxygen vacancies for example with ultra-high vacuum treatments or improving the B-site ordering by further optimization of the deposition parameters. The magneto-transport properties of SFMO thin films do not follow any conventional models, but the temperature dependence of resistivity was succesfully described with a model of two spin channel system. Also, evidences that the resistivity-temperature behaviour of SFMO thin films is dominated by the structural defects, which reduce the band gap in the majority spin band were found. Moreover, the magnetic field response of the resistivity in SFMO thin films were found to be superposition of different mechanisms that seems to be related to the structural changes in the film.