1. Infrared spectra in amorphous alumina : a combined ab initio and experimental studyLuigi Giacomazzi, Nikita S. Shcheblanov, Mikhail E. Povarnitsyn, Yanbo Li, Andraž Mavrič, Barbara Zupančič, Jože Grdadolnik, Alfredo Pasquarello, 2023, original scientific article Abstract: We present a combined study based on the experimental measurements of an infrared (IR) dielectric function and first-principles calculations of IR spectra and the vibrational density of states (VDOS) of amorphous alumina (am−Al2O3). In particular, we show that the main features of the imaginary part of the dielectric function ε2(ω) at ∼380 and 630 cm−1 are related to the motions of threefold-coordinated oxygen atoms, which are the vast majority of oxygen atoms in am-Al2O3. Our analysis provides an alternative point of view with respect to an earlier suggested assignment of the vibrational modes, which relates them to the stretching and bending vibrational modes of AlOn (n=4, 5, and 6) polyhedra. Our assignment is based on the additive decomposition of the VDOS and ε2(ω) spectra, which shows that (i) the band at ∼380cm−1 features oxygen motions occurring in a direction normal to the plane defined by the three nearest-neighbor aluminum atoms, i.e., out-of-plane motions of oxygen atoms; (ii) Al-O stretching vibrations (i.e., in-plane motions of oxygen atoms) appear at frequencies above ∼500cm−1, which characterize the vibrational modes underlying the band at ∼630cm−1. Aluminum and fourfold-coordinated oxygen atoms contribute uniformly to the VDOS and ε2(ω) spectra in the frequency region ∼350–650 cm−1 without causing specific features. Our numerical results are in good agreement with the previous and presently obtained experimental data on the IR dielectric function of am−Al2O3 films. Finally, we show that the IR spectrum can be modeled successfully by assuming isotropic Born charges for aluminum atoms and fourfold-coordinated oxygen atoms, while requiring the use of three parameters, defined in a local reference frame, for the anisotropic Born charges of threefold-coordinated oxygen atoms.
Keywords: dielectric properties, microstructure, amorphous materials, density functional calculations, infrared techniques, aluminium oxide
Published in RUNG: 10.05.2023; Views: 1182; Downloads: 7
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4. Modelling of Macrosegregation of a Low-Frequency Electromagnetic Direct Chill Casting by a Meshless MethodVanja Hatić, 2019, doctoral dissertation Abstract: The main aim of the dissertation is to develop a meshless model that describes the solidification and macrosegregation phenomena during the direct chill casting (DCC) of aluminium alloys under the influence of a low-frequency electromagnetic field. Macrosegregation is an undesired consequence of alloy solidification. It represents one of the major casting defects and substantially reduces the quality of the finished product. On the other hand, low-frequency electromagnetic casting (LFEC) is a process that promises to increase greatly the product quality, including the reduction of macrosegregation. The modelling of both processes is of tremendous importance to the metallurgical industry, due to the high costs of experiments during production.
The volume-averaging formulation is used for the modelling of the solid-liquid interaction. The conservation equations for mass, energy, momentum, and species are used to model the solidification of aluminium-alloy billets in axysimmetry. The electromagnetic-induction equation is coupled with the melt flow. It is used to calculate the magnetic vector potential and the Lorentz force. The Lorentz force is time-averaged and included in the momentum-conservation equation, which intensifies the melt flow. The effect of Joule heating is neglected in the energy conservation due to its insignificant contribution. The semi-continuous casting process is modelled with the Eulerian approach. This implies that the global computational domain is fixed in space. The inflow of the liquid melt is assumed at the top boundary and the outflow of the solid metal is assumed at the bottom. It is assumed that the whole mushy area is a rigid porous media, which is modelled with the Darcy law. The Kozeny-Carman relation is used for the permeability definition. The incompressible mass conservation is ensured by the pressure correction, which is performed with the fractional step method. The conservation equations and the induction equation are posed in the cylindrical coordinate system. A linearised eutectic binary phase diagram is used to predict the solute redistribution in the solid and liquid phases. The micro model uses the lever rule to determine the temperature and the liquid fraction field from the transport equations.
The partial differential equations are solved with the meshless-diffuse-approximate method (DAM). The DAM uses weighted least squares to determine a locally smooth approximation from a discrete set of data. The second-order polynomials are used as the trial functions, while the Gaussian function is used as the weight function. The method is localised by defining a smooth approximation for each computational node separately. This is performed by associating each node with a unique local neighbourhood, which is used for the minimisation. There are 14 nodes included in the local subdomains for the DCC and LFEC simulations. The stability of the advective term is achieved with a shift of the Gaussian weight in the upwind direction. This approach is called the adaptive upwind weight function and is used in the DAM for the first time. The Explicit-Euler scheme is used for temporal discretisation.
The use of a meshless method and the automatic node-arrangement generation makes it possible to investigate the complicated flow structures, which are formed in geometrically complex inflow conditions in a straightforward way. A realistic inflow geometry and mould can therefore be included in the model. The number of computational nodes is increased in the mushy zone and decreased in the solid phase, due to the optimisation of the computational time and memory. The computational node arrangement is automatically adapted with time, as the position of the mushy zone is changed in shape and position.
Keywords: low-frequency electromagnetic casting, direct chill casting, macrosegregation, electromagnetic stirring, aluminium alloys, meshless methods, diffuse-approximate method, multiphysics model, solidification
Published in RUNG: 25.04.2019; Views: 3903; Downloads: 148
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5. High-temperature stabilization of bulk amorphous Al2O3Andraž Mavrič, Mattia Fanetti, Gregor Mali, Matjaž Valant, 2018, original scientific article Abstract: We present a method for high temperature stabilization of bulk amorphous aluminium oxide. The stabilization is achieved by dispersing polysilane dendritic molecules in aluminium hydroxide gel, which upon thermal treatment gives amorphous aluminium oxide stable up to 900 °C. The dispersed macromolecules covalently bind to the alumina matrix and induce homogeneously distributed strain fields that keep the alumina amorphous. The thermal conversion of the precursor system was followed by thermogravimetry with an evolved gas analysis, infrared spectroscopy and 29Si NMR. The amorphous structure of aluminium oxide was confirmed with an X-ray and electron diffraction. Additionally, the amorphous state was supported by presence of penta-coordinated aluminium detected by 27Al NMR and a low bandgap measured by a UV–visible absorption spectroscopy.
Keywords: Amorphous aluminium oxide, Polysilane, Nanocomposite, Stabilization
Published in RUNG: 30.07.2018; Views: 4295; Downloads: 16
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6. Amorphous nanocomposite of polycarbosilanes and aluminum oxideAndraž Mavrič, 2018, doctoral dissertation Abstract: This work presents a paradigm for high temperature stabilization of bulk amorphous aluminium oxide. The thermodynamic stabilization is achieved by preparing a nanocomposite, where polymethylsilane dendritic molecules are dispersed in an aluminium hydroxide gel. Upon heat-treatment the gel transforms to the amorphous aluminium oxide that is stable up to 900°C. The dispersion of the macromolecules and their covalent bonding to the alumina matrix induce homogeneously distributed strain fields that keep the alumina amorphous.
The first part of the thesis focuses on the synthesis, characterization and solubility properties of the dendritic polymethylsilane. The polymethylsilane is synthetized by electrochemical polymerization from trichloromethylsilane monomer. The polymerization mechanism, involving a single polymerization pathway, is identified. The polymer growth proceeds through reduction of the monomers to the silyl anions and their addition to the growing polymer.
The solubility of three chemically related but topologically different polysilanes (linear, dendritic and network) were studied by dynamic light scattering. At room temperature the agglomerates in a range from 500 to 1300 nm are present. They undergo de-agglomeration at slightly elevated temperatures of around 40°C. The de-agglomeration results in formation of stable solutions, where a hydrodynamic diameter of the individual polymer molecules was measured to be in a range from 20 to 40 nm.
The obtained diameters of two dendritic polymethylsilane macromolecules, synthesized under different electrolysis conditions, are much larger than the theoretical size estimated for an ideal dendrimer. We determined by 29Si NMR that the reason for this is in a large number of branching irregularities (defects) contained in the molecular structure. Combining the experimental values obtained by DLS and density measurements with a structural model that considers the branching irregularities, it is shown that the inclusion of the defects allows the dendritic polymer to exceed the sterical limitations and form the hyperbranched dendritic structure. The final size depends on a relative amount of the branching defects.
In the second part, the synthetized polymethylsilane molecules were successfully used for the nanocomposite formation. The aluminium hydroxide gel with the dispersed polymethylsilane molecules was prepared as a precursor. Upon heat-treatment it gives the amorphous aluminium oxide stable up to 900°C. The dispersed macromolecules induce homogeneously distributed strain fields that keep the aluminium oxide amorphous during the thermal treatment the dispersed macromolecules covalently bind to the matrix, inducing the interface strain. The amorphous state was confirmed by the presence of penta-coordinated aluminium detected by 27Al NMR and a low bandgap measured by UV-vis absorption spectroscopy.
Keywords: amorphous aluminium oxide, polymethylsilane, nanocomposite, electropolymerization, solubility, agglomeration, de-agglomeration, dendrimer, hyperbranched dendritic structure, dynamic light scattering, thermal analysis, transmission electron microscopy, scanning electron microscopy, X-ray diffraction, infrared spectroscopy, UV-Vis spectroscopy
Published in RUNG: 19.07.2018; Views: 6073; Downloads: 210
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7. Meshless modeling of thermo-mechanics of low-frequency electromagnetic direct chill castingBoštjan Mavrič, 2017, doctoral dissertation Abstract: The aim of this dissertation is to devise a meshless model describing the thermomechanical phenomena, which occur during DC casting of aluminium alloys under the influence of electromagnetic stirring. The thermoemchanical phenomena are important, because they can cause several type of defects, which can significantly deteriorate the quality of the resulting billet. The two most important of them are the hot tearing, which causes cracks to appear in the mushy zone, and the porosity, which demonstrates itself as micrometer sized voids in the microstructure of the billet.
To calculate the stresses and strains, a computational model of the stationary state of the process, stated in axial symmetry, is formulated. It uses Eulerian formulation by fixing the computational domain to the mold of the casting device allowing the material to move through the computational domain. The stresses are calculated from the stress equilibrium equations. The small strain approximation is used to consider the three contributions to strain. The strain consists of the thermal strain, which is caused by the inhomogeneous thermal profile in the billet, the viscoplastic strain, which is caused by the irreversible deformation because of the large stresses occurring in the billet, and the elastic strain.
The spatial discretization of the governing equations is performed by local radial basis function collocation method (LRBFCM) and the temporal discretization is achieved by the method of lines with implicit Euler formula. The method used for spatial discretization uses radial basis functions augmented by monomials to approximate the solution values on localized stencils. This approximation is used to construct the discretization coefficients of the differential operators present in the model. A flexible framework for formulation of multiphysics problems is developed to use the obtained discretization coefficients to construct the temporal discretization of the governing equations. The node arrangement, on which the spatial discretization is performed, was generated by a point-repel algorithm.
The performance of the method is tested on several benchmark test cases. The accuracy of the discretization is estimated by comparing the analytic and the numerical solution to several stationary problems in thermomechancis. Of special interest is the performance of the method with respect to the choice of the shape parameter, which determines the spatial scale of the radial basis functions. Besides this, the dependence of the condition number of the interpolation matrix on the shape parameter is studied. The condition number is found fit to replace the condition number as the shape-determining free parameter of the method.
The implementation of the solver of time dependent problems is tested on problem of thermoelasticity, which couples the thermal transport with the elastic waves. The results of the problem are compared with the finite element method, showing good agreement of the two methods. The results are also compared with the results obtained by meshless local Petrov-Galerkin method and the proposed local collocation method demonstrated significantly better solution quality in the studied case.
The performance of the solver used to solve the system of nonlinear equations given by the viscoplastic constitutive equations is estimated on a quasi zero-dimensional problem. The results are found to match perfectly. Solution of a more complicated problem is obtained with the proposed method and the finite-element method, both methods giving practically the same solution, although some serious limitations of the chosen finite element solver are exposed during the selection of the problem parameters.
Finally, the devised method is applied to the problem of DC casting of aluminium alloys. The thermomechanical model relies on a model of heat and mass transfer to obtain the input fields needed in the solver. The required fields are: temperature, pressure, liquid
Keywords: thermomechanics, viscoplasticity, aluminium alloys, direct-chill casting, electromagnetic stirring, hot tearing, porosity, meshless methods, local collocation method, radial basis functions, shape parameter
Published in RUNG: 28.06.2017; Views: 5803; Downloads: 255
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8. Developments of a new mirror technology for the Cherenkov Telescope ArrayJerzy Michałowski, Andrej Filipčič, Gašper Kukec Mezek, Samo Stanič, Serguei Vorobiov, Lili Yang, Gabrijela Zaharijas, Danilo Zavrtanik, Marko Zavrtanik, 2015, published scientific conference contribution Keywords: Cherenkov Telescope Array (CTA), mirror technology for CTA, cold-slumping, front reflecting aluminium-coated panel
Published in RUNG: 16.01.2017; Views: 3788; Downloads: 249
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