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Core-Shell Ceramic Structures Prepared by Thermoplastic Co-Extrusion Method
Kaštyl, Jaroslav ; Pabst, Willi (referee) ; Hadraba, Hynek (referee) ; Trunec, Martin (advisor)
In the doctoral thesis, the bi-layer ceramic bodies with core-shell geometry were prepared by thermoplastic co-extrusion method and for these composite bodies the mechanical properties were studied. For study of co-extrusion and mechanical properties were designed two composite systems. First system ZTA-A combined the dense core ZTA (zirconia-toughened alumina) and the dense shell Al2O3. Second system ZST-Z consisted of porous core and dense shell made from ZrO2 for both cases. In the thesis, the rheology of ceramic thermoplastic suspensions and their mutual influence during co-extrusion was studied. Subsequently, the debinding process and sintering were studied, and based on the optimization of all process steps were obtained defect-free bodies with core-shell geometry. The mechanical properties (elastic modulus, hardness and bending strength) were determined for sintered bodies. To estimate the stress path in the core shell bodies loaded in bending, the relationship considering different elastic moduli of the core and the shell was used. For bodies of ZTA-A system was increased the strength in comparison with monolithic bodies of the individual components. Thus, bodies with high surface hardness of shell from Al2O3 and moreover having high fracture strength in bending were obtained. The effective elastic modulus was decreased for bodies of ZST-Z system up to 25 % in comparison with the elastic modulus of dense monolithic samples. The same effective modulus of elasticity was possible to achieve with core-shell bodies while maintaining significantly higher fracture strength than monolithic porous bodies or pipes.
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Utilization of flow-coulometry in study of transport metal ions in humic gels
Kalina, Michal ; Pabst, Willi (referee) ; Klučáková, Martina (advisor)
This diploma thesis deals with the study of non-stationary diffusion of cupric ions in humic gels. The main objective of the work was the optimalization of conditions for using the electrochemical analyzer EcaFlow 150 GLP for the study of diffusion experiments. Next part was focused on reaching of constant concentration profiles of cupric ions in humic gel. Last aim of the study was the bond strength between cupric ions and humic acids. Diffusion was characterized by the values of the diffusion flux and cupric ions concentration profiles in humic gel. The data necessary for calculation were obtained by the electrochemical analyses of the extracts of each slice after diffusion on the EcaFlow 150 GLP. It has been proved that after application of several adjustment is this method suitable for the study of diffusion experiments. By using of different extraction agents was obtained the fractionalization of cupric ions according to the bond strength to humic acids.
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Behaviour of the Interface of Low Toughness Materials
Halasová, Martina ; Pabst, Willi (referee) ; Tatarko, Peter (referee) ; Fintová, Stanislava (referee) ; Chlup, Zdeněk (advisor)
The work is focused on evaluation of factors influencing behaviour of interface in low toughness ceramic materials reinforced with fibres. The main aim was to characterise processing effects influencing the quality of fibre-matrix interface, with respect to final behaviour of composites at various loading type. The partial goal was to map the possibility of influencing the composite material by choice of matrix material, eventually by change of its processing, leading to change of interfacial properties without need of modification of reinforcement surface. The materials used in studied composites as a matrix were based on thermal transformation of polymer precursors, thus, the resulting materials were characterised in partially as well as in fully pyrolyzed state. Behaviour of interface in cpomposite materials was first evaluated from the global behaviour (i.e., change of mechanical properties) and in chosen representative composites also from the point of local changes in close surrounding of the interface (i.e., microstructure, chemical processes, fracture-mechanic processes, etc.) due to thermal exposition. In experiment were used particularly composite materials prepared by pyrolysis of polysiloxane resins reinforced by basalt fibres or Nextel™720 fibres. With respect to thermal resistance of the reinforcement, the basalt reinforced composites contained only partially pyrolyzed matrix (i.e., to temperature of 800°C), and in composites with Nextel™720 reinforcement was the matrix in form of fully pyrolyzed polymer into ceramic (SiOC). At partial pyrolysis of polysiloxane resin occurs rapid change of behaviour at temperature of 600°C. It was demonstrated, that around this temperature the formed interface with basalt fibre exhibits optimum adhesion/strength, allowing to reach sufficient level of composite strength at acceptable fracture toughness. Above temperature of 750°C occur significant difusion processes in the area of the interface and formation of new crystalline phases in the fibre, what deteriorates the fibre strength, and on the contrary, strengthen the interface cohesion, what leads to degradation of properties of the whole composite. At composite materials determined for high temperatures, reinforced by Nextel™720 fibres, was detected significant resistivity against oxidation caused especially by fully pyrolyzed matrix. As similarly important factor was observed the formation of mullite interphase in surface area of the fibre. Volume changes caused by formation of the interphase, difusional transport of the matter and thermal exposition led to formation of thermally and stress-induced micro-cracks, weakening interfacial surrounding in matrix as well as in fibre. This mechanism in contrast to amplifying chemical bond between fibre and matrix led to preserving of the composite properties also at high temperatures up to 1500°C. The work also dealed with effects of loading rate, where in contrast to static loading were observed different failure mechanisms. Realized research led to description and explanation of the influence of the fibre-matrix interface by change of matrix material processing parameters, which allow processing of economically advantageous and thermally stable composite.
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Diffusion of cupric ions in humic hydrogels
Grunt, Jakub ; Pabst, Willi (referee) ; Klučáková, Martina (advisor)
Presented diploma thesis focuses on the study of diffusion of cupric ions in humic acid hydrogels. A total of eight different hydrogels were prepared by dissolving the humic acids with sodium hydroxide and sodium triphosphate. For the purpose of precipitation and cross linking, hydrochloric acid and chlorides of magnesium, calcium and iron were used during a modified preparation of gels. Different gel-forming interactions were achieved by modifying the preparation of hydrogel systems. The aim of the thesis was to assess the effect of gel preparation procedure on the transport properties of the gels. Therefore, diffusion coeficients were determined for all samples. Two different methods - constant-source diffusion and instantaneous planar source diffusion - were used to assign the diffusion coefficients. Methods differ in source concentrations of cupric ions and are suitable for assessing the impact of the concentration on the diffusion coefficient. Both these methods were based on monitoring temporal evolution of diffusion profiles of cupric ions and on assigning the overall diffusion flow. Copper ions were elected as diffusing medium because of their high affinity and strong binding to humic acids. Measurements show that gels prepared using polyphosphate allow slightly faster diffusion of cupric ions and that the constant-source method provides higher diffusion coefficients in comparison to instantaneous planar source method.
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Mechanical Reinforcement of Bioglass®-Based Scaffolds
Bertolla, Luca ; Prof. Dr.-Ing. habil. Aldo R. Boccaccini (referee) ; Kotoul, Michal (referee) ; Pabst, Willi (referee) ; Dlouhý, Ivo (advisor)
Bioactive glasses exhibit unique characteristics as a material for bone tissue engineering. Unfortunately, their extensive application for the repair of load-bearing bone defects is still limited by low mechanical strength and fracture toughness. The main aim of this work was two-fold: the reinforcement of brittle Bioglass®-based porous scaffolds and the production of bulk Bioglass® samples exhibiting enhanced mechanical properties. For the first task, scaffolds were coated by composite coating constituted by polyvinyl alcohol (PVA) and microfibrillated cellulose (MFC). The addition of PVA/MFC coating led to a 10 fold increase of compressive strength and a 20 fold increase of tensile strength in comparison with non-coated scaffolds. SEM observations of broken struts surfaces proved the reinforcing and toughening mechanism of the composite coating which was ascribed to crack bridging and fracture of cellulose fibrils. The mechanical properties of the coating material were investigated by tensile testing of PVA/MFC stand–alone specimens. The stirring time of the PVA/MFC solution came out as a crucial parameter in order to achieve a more homogeneous dispersion of the fibres and consequently enhanced strength and stiffness. Numerical simulation of a PVA coated Bioglass® strut revealed the infiltration depth of the coating until the crack tip as the most effective criterion for the struts strengthening. Contact angle and linear viscosity measurements of PVA/MFC solutions showed that MFC causes a reduction in contact angle and a drastic increase in viscosity, indicating that a balance between these opposing effects must be achieved. Concerning the production of bulk samples, conventional furnace and spark plasma sintering technique was used. Spark plasma sintering performed without the assistance of mechanical pressure and at heating rates ranging from 100 to 300°C /min led to a material having density close to theoretical one and fracture toughness nearly 4 times higher in comparison with conventional sintering. Fractographic analysis revealed the crack deflection as the main toughening mechanisms acting in the bulk Bioglass®. Time–dependent crack healing process was also observed. The further investigation on the non-equilibrium phases crystallized is required. All obtained results are discussed in detail and general recommendations for scaffolds with enhanced mechanical resistance are served.
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New Methods of Study of Reactivity and Transport Properties of Biocolloids
Smilek, Jiří ; Weidlich,, Tomáš (referee) ; Pabst, Willi (referee) ; Klučáková, Martina (advisor)
The main aim of doctoral thesis was the study on reactivity, transport and barrier properties of biocolloidal and synthetic polymeric substances by simple diffusion techniques. It was studied mainly the influence of basic physic-chemical parameters (temperature, concentration, pH and modification of material) on the reactivity and barrier ability of chosen compounds. Further substances were chosen as a model compounds: biocolloids (humic acids, alginate, chitosan, hyaluronate) and synthetic polymer (polystyrenesulfonate). Reactivity, barrier and transport properties of chosen substances were studied by interactions with oppositely charged basic organic dyes (methylene blue, rhodamine 6G, amido black 10B respectively) in hydrogels medium based on linear polysaccharide (agarose). The attention was also paid to basic physic-chemical characterisation (infrared spectroscopy, rheology, elemental analysis, thermogravimetry and scanning electron microscopy) of chosen materials and also hydrogels. Key part of the whole doctoral thesis was the optimization of selected diffusion techniques (diffusion cell technique and non-stationary diffusion in cuvettes) designated for the study on reactivity and barrier properties of wide range compounds (optimized method should be used as an universal method for simple and fast determination of reactivity of different compounds at given or changing conditions). The rate of reactivity, transport and barrier properties was determined based on fundamental diffusion parameters such as diffusion coefficients, break-through time so called lag time, interfacial concentration of chosen organic dye, apparent equilibrium constant, tortuosity factor, partition coefficient.
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influence of physical conditions on diffusion processes in humic gels
Marvan, Jan ; Pabst, Willi (referee) ; Klučáková, Martina (advisor)
Diploma thesis is based on diffusion processes of copper (II) ions to humic gels obtained from lignite. Solutions with various concentrations and acidity were exposed to diffusion for exact time 24 hours. After the diffusion was ended the copper (II) ionic concentration profiles of tubular gels were create and calculated total diffusion flux. The experiment showed that the higher acidity of copper (II) solution decrease an amount of immobilized Cu2+ ions to the humic gels. In comparison concentration/pH: concentration of the solution has higher influence on sorption metal ions than change of the pH.
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Influence of reactivity on transport of metal ions in humic gels
Smitalová, Michaela ; Pabst, Willi (referee) ; Klučáková, Martina (advisor)
This diploma thesis deals with copper(II) ions diffusion in the humic hydrogels. The hydrogels were prepared from several samples of humic acids using different method and their isolation conditions from the original matrix. A selective blocking of functional groups (COOH, OH) was performed in the selected samples of humic acids. These reactive groups were selectively blocked using methylation agent trimethylsilyl-diazomethane. The success of performed methylation and functional groups blocking was verified using a FT-IR spectroscopy. There was carried out the set of diffusion experiments. The experimental arrangement was selected to enable an instantaneous planar source met-hod for data processing. The basis of this method was to determine the copper(II) ions con-centration distribution in the hydrogels. The method consists of slicing of the hydrogels after the diffusion experiments, extraction of the copper ions in the solution and determina-tion of concentration in the extracts from individual slices using UV-VIS spectroscopy. Based on the experimental data the effective diffusion coefficients were determined. The resulting values include both the effect of hydrogels structure and the effect of the reaction between Cu(II) ions and humic acids. There were prepared gels with defined portion of blocked functional groups for selected samples, which allowed to investigate the effect of reactivity on the copper ions diffusion without the significant changes in the gel structure (porosity). The blocking of functional groups reflected in a lower values of diffusion coefficients in comparison to the gels prepared from unmodified humic acids as follows. There was also confirmed the effect of humic acids isolation procedure and their properties on the diffusivity.
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Customized hybrid bioscaffolds for bone regeneration
Šťastný, Přemysl ; Šupová,, Monika (referee) ; Pabst, Willi (referee) ; Trunec, Martin (advisor)
Doktorská práce s názvem Individualizované hybridní podpůrné struktury pro regeneraci kostní tkáně je rozdělena do dvou částí. První část si klade za cíl ukázat vzájemný vztah mezi implantovaným materiálem a kostní tkání a současný stav poznání v oblasti vývoje matriálů na bázi fosforečnanů vápenatých a z nich vyráběných implantátů pro regeneraci kostní tkáně. Koncept individualizace a pečlivého výběru fázového složení implantátu představuje stěžejní body druhé části práce. Individualizace v této práci není chápána jako pouhé dosažení tvarové a rozměrové přesnosti implantátu. Velká pozornost byla věnována mikrostrukturním detailům, fázovému složení a distribuci jednotlivých fází, což umožňuje připravit specifický materiál na základě zamýšlené aplikace. Biologická odezva na připravené materiály byla vyhodnocena pomocí in-vitro a in-vivo testů. Doktorská práce ukazuje jak pochopení základních chemických a fyzikálních vlastností materiálu může pomoc při návrhu implantátu s vynikající biologickou odezvou. In-vivo aplikace navrženého materiálu a jeho srovnání s autograftním kostním štěpem, současným zlatým standardem, je jedinečným a cenným výstupem předložené práce.
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Behaviour of the Interface of Low Toughness Materials
Halasová, Martina ; Pabst, Willi (referee) ; Tatarko, Peter (referee) ; Fintová, Stanislava (referee) ; Chlup, Zdeněk (advisor)
The work is focused on evaluation of factors influencing behaviour of interface in low toughness ceramic materials reinforced with fibres. The main aim was to characterise processing effects influencing the quality of fibre-matrix interface, with respect to final behaviour of composites at various loading type. The partial goal was to map the possibility of influencing the composite material by choice of matrix material, eventually by change of its processing, leading to change of interfacial properties without need of modification of reinforcement surface. The materials used in studied composites as a matrix were based on thermal transformation of polymer precursors, thus, the resulting materials were characterised in partially as well as in fully pyrolyzed state. Behaviour of interface in cpomposite materials was first evaluated from the global behaviour (i.e., change of mechanical properties) and in chosen representative composites also from the point of local changes in close surrounding of the interface (i.e., microstructure, chemical processes, fracture-mechanic processes, etc.) due to thermal exposition. In experiment were used particularly composite materials prepared by pyrolysis of polysiloxane resins reinforced by basalt fibres or Nextel™720 fibres. With respect to thermal resistance of the reinforcement, the basalt reinforced composites contained only partially pyrolyzed matrix (i.e., to temperature of 800°C), and in composites with Nextel™720 reinforcement was the matrix in form of fully pyrolyzed polymer into ceramic (SiOC). At partial pyrolysis of polysiloxane resin occurs rapid change of behaviour at temperature of 600°C. It was demonstrated, that around this temperature the formed interface with basalt fibre exhibits optimum adhesion/strength, allowing to reach sufficient level of composite strength at acceptable fracture toughness. Above temperature of 750°C occur significant difusion processes in the area of the interface and formation of new crystalline phases in the fibre, what deteriorates the fibre strength, and on the contrary, strengthen the interface cohesion, what leads to degradation of properties of the whole composite. At composite materials determined for high temperatures, reinforced by Nextel™720 fibres, was detected significant resistivity against oxidation caused especially by fully pyrolyzed matrix. As similarly important factor was observed the formation of mullite interphase in surface area of the fibre. Volume changes caused by formation of the interphase, difusional transport of the matter and thermal exposition led to formation of thermally and stress-induced micro-cracks, weakening interfacial surrounding in matrix as well as in fibre. This mechanism in contrast to amplifying chemical bond between fibre and matrix led to preserving of the composite properties also at high temperatures up to 1500°C. The work also dealed with effects of loading rate, where in contrast to static loading were observed different failure mechanisms. Realized research led to description and explanation of the influence of the fibre-matrix interface by change of matrix material processing parameters, which allow processing of economically advantageous and thermally stable composite.
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