Dissertations / Theses on the topic 'Glass extrusion'

A thermodynamical framework is presented that describes the solidification of molten polymers to an amorphous as well as to a semicrystalline solid-like state. This framework fits into a general structure developed for materials undergoing a large class of entropy producing processes. The molten polymers are usually isotropic in nature and certain polymers crystallize, with the exception of largely atactic polymers, which solidify to an amorphous solid, to an anisotropic solid. The symmetry of the crystalline structures in the semicrystalline polymers is dependent upon the thermomechanical process to which the polymer is subjected to. The framework presented takes into account that the natural configurations associated with the polymer melt (associated with the breaking and reforming of the polymer network) and the solid evolve in addition to the evolving material symmetry associated with these natural configurations. The functional form of the various primitives such as how the material stores, dissipates energy and produces entropy are prescribed. Entropy may be produced by a variety of mechanisms such as conduction, dissipation, solidification, rearragement of crystalline structures due to annealing and so forth. The manner in which the natural configurations evolve is dictated by the maximization of the rate of dissipation. Similarly, the crystallization and glass transition kinetics may be obtained by maximization of their corresponding entropy productions. The restrictions placed by the second law of thermodynamics, frame indiference, material symmetry and incompressibility allows for a class of constitutive equations and the maximization of the rate of entropy production is invoked to select a constitutive equation from an allowable class of constitutive equations. Using such an unified thermodynamic approach, the popular crystallization equations such as Avrami equation and its various modifications such as Nakamura and Hillier and Price equations are obtained. The predictions of the model obtained using this framework are compared with the spinline data for amorphous and semicrystalline polymers.

Field Assisted Sintering Technique (FAST) was used for the crystallisation of ionomer glasses and the production of the relevant glass ceramics. Extrusion was also used as an alternative processing method to produce honeycomb glass ceramics derived from similar glass compositions. Apatite-mullite glass ceramics derived from the general glass composition 4.5SiO\(_2\)-3A1\(_2\)O\(_3\)- 1.5P\(_2\)O\(_5\)-(5-x)CaO-xCaF\(_2\) can be produced by a lost wax method. However, Field Assisted Sintering Technique and Honeycomb Extrusion Technique are never used before and this present work presents the first data on the use of both of the above mentioned techniques. Calcium (Ca), Strontium (Sr) and Magnisium (Mg) containing glass powder compositions were produced and processed by FAST and Extrusion technique. X-ray diffraction of the materials produced by FAST showed the formation of a fluorapatite, mulite and a minor A1PO\(_4\) phase for the calcium glass. Sr-fluorapatite and Sr-aluminium silicate were formed in Sr glass and mullite and wagnerite were formed in Mg glasses. All the crystal phases formed were in good agreement with previous conventional crystallization studies. The FAST sintered glass ceramic properties were improved when compared with conventional sintering. In extrusion technique, the rheological properties were studied using Benow/Bridgwater model for paste parameters. Honeycomb extrusion pressure drop was also studied using a model developed by Blackburn and Bohm. In this study, we used waste glass to model the binder rehology of glass powder and modelled binder rheology in the apatite mullite glass. The measured paste parameters were in good agreement when compared with the experimental results. The produced honeycomb structure was sintered conventionally using a furnace. Microstructural studies and X-ray diffraction were carried out. The results of this studies show a well-defined porous structure and formation of crystal phases similar to the phases observed during conventional sintering.

Glass fiber reinforced poly(ethylene terephthalate), GF/PET has excellent potential for future structural applications of composite materials. PET as a semi-crystalline thermoplastic polyester has high wear resistance, low coefficient of friction, high flexural modulus and superior dimensional stability make it a versatile material for designing mechanical and electromechanical parts. Glass fibers are currently used as strength giving material in structural composites because of their high strength and high performance capabilities. In order to obtain high interfacial adhesion between glass fiber and polymer, glass fibers are treated with silane coupling agents. The objective of this study is to produce GF/PET composites with varying glass fiber concentration at constant process parameters in a twin screw extruder. Also, by keeping GF content constant, it is aimed to observe the effects of process parameters such as screw speed and feed rate on structural properties of the composites. Another objective of the study is to investigate the influence of different coupling agents on the morphological, thermal and mechanical properties and on fiber length distributions of the composites. Tensile strength and tensile moduli of the GF/PET composites increased with increasing GF loading. There was not a direct relation between strain at break values and GF content. The interfacial adhesion between glass fiber received from the manufacturer and PET was good as observed in the SEM photograps. Degree of crystallinity values increased with the addition of GF. Increasing the screw speed did not affect the tensile strength of the material significantly. While increasing the feed rate the tensile strength decreased. The coupling agent, 3-APME which has less effective functional groups than the others showed poor adhesion between glass fiber and PET. Therefore, lower tensile properties were obtained for the composite with 3-APME than those of other silane coupling agents treated composites. Number average fiber length values were reduced to approximately 300&
#61549
m for almost all composites prepared in this study.

Metallic glasses exhibit many attractive attributes such as outstanding mechanical, magnetic, and chemical properties. Due to the absence of crystal defects, metallic glasses display remarkable mechanical properties including higher specific strength than crystalline alloys, high hardness and larger fracture resistance than ceramics. The technological breakthrough of metallic glasses, however, has been greatly hindered by the limited plastic strain to failure. Thus, several strategies have been employed to improve the intrinsic and extrinsic effects on the flow behavior of metallic glasses with respect to their fracture toughness and overall plastic strain. One of the suggested strategies is the production of a composite consisting of the brittle metallic glass along with a ductile second phase that either acts as an active carrier of plastic strain or passively enhances the multiplication of shear bands via shear-band splitting . Another approach for increasing plastic deformation consists of introducing pores as a gaseous second phase into the material. The pores are similarly effective in delaying catastrophic failure resulting from shear band localization. In metallic glasses with high porosity, propagation of shear bands can even become stable, enabling macroscopic compressive strains of more than 80 % without fracture. In this thesis, Ni59Zr20Ti16Si2Sn3 glass and its composites have been fabricated using mechanical milling and consolidation by hot pressing followed by extrusion of Ni59Zr20Ti16Si2Sn3 metallic glass powder or Ni59Zr20Ti16Si2Sn3 metallic glass powder reinforced with 40 vol.% of brass particles to obtained bulk composite materials with high strength and enhanced compressive plasticity and to generate porous structure in Ni59Zr20Ti16Si2Sn3 metallic glass using selective dissolution. The brass–glass powder mixtures to be consolidated were prepared using two different approaches: manual blending and ball milling to properly vary size and morphology of the second phase in the composites. Powder consolidation was carried out at temperatures within the supercooled Liquid (SCL) region, where the glassy phase displays a strong decrease of viscosity, with using the sintering parameters which were chosen after analysis of the crystallization behavior of the glassy phase to avoid its crystallization during consolidation. Ball milling has a significant effect on the microstructure of the powder mixtures: a refined layered structure consisting of alternating layer of glass and brass is formed as a result of the mechanical deformation. However, ball milling reduces the amorphous content of the composite powders due to mechanically induced crystallization and reaction of the glass and brass phases during heating. In addition, the milling of the composite powders and the following consolidation step reduces the amorphous content by about 50 %. The bulk amorphous Ni59Zr20Ti16Si2Sn3 alloy synthesized by hot pressing exhibits higher strength (2.28 GPa) than that of the as-cast bulk amorphous Ni59Zr20Ti16Si2Sn3 alloy (2.2 GPa). The mechanical behavior of the glass-brass composites is significantly affected by the control of the microstructure between the reinforcement and the nano-grained matrix phase through the different methods used for the preparation of the powder mixtures. The strength of the composites increases from 500 MPa for pure brass to 740 and 925 MPa for the composites with 40 and 60 vol.% glass reinforcement prepared by manual blending. The strength further increases to 1240 and 1640 MPa for the corresponding composites produced by ball milling caused by the remarkable effect of the matrix ligament size on the strengthening of the composites. The porous metallic glass was obtained by the selective dissolution in a HNO3 solution of the fugitive brass phase in the Ni59Zr20Ti16Si2Sn3 composite. The microstructure of the porous samples consists of highly elongated layered pore structures and/or irregularly shaped pores. The average size of the pores depends on the processing parameters and can be varied in the range of 0.4–15 µm. Additional porous samples were prepared from different extruded composite precursors of blended and milled powder mixtures. This leads to customized hybrid porous structures consisting of a combination of large and small pores. The specific surface area of the porous Ni-based metallic glass powder measured by the BET method is 16 m2/g, while the as-atomized Ni59Zr20Ti16Si2Sn3 powder has a specific surface area of 0.29 m2/g. This indicates a mechanical milling induced enhancement in surface area by refinement of the fugitive brass phase. However the specific surface area of the porous Ni-based metallic glass obtained from as-extruded precursors is 10 m2/g caused by a breakdown of the porous structure during selective dissolution of the nano-scale fugitive phase. Although milling of the present composite powders and the following consolidation step reduces the amorphous content by about 50 %, through the use of glassy phases with improved stability against mechanically induced crystallization along with reduced affinity with the fugitive phase to avoid unwanted reactions during processing, this approach using powder metallurgical offers the possibility to produce highly active porous bulk materials for functional applications, such as catalysis, which require the fast transport of reactants and products provided by the large pores along with high catalytic activity ensured by the large surface area characterizing the small pores. Accordingly, gas absorption ability tests of porous Ni-based metallic glass powders have been performed in order to evaluate the possibility of replacement of conventional support materials. From these first tests it can be conclude that additional opportunities should exist for nano-porous MGs with designed architecture of porous structures that are tailored to specific functional applications
Metallische Gläser weisen viele attraktive mechanische, magnetische und chemische Eigenschaften auf. Aufgrund der fehlenden Kristallstruktur zeigen metallische Gläser bemerkenswerte mechanische Eigenschaften, einschließlich höherer spezifischer Festigkeit, höherer Härte und größerer Bruchfestigkeit als Keramik. Der technologischen Durchbruch metallischer Gläser wird jedoch bis heute stark von ihremspröden Bruchverhalten behindert. Deshalb wurden verschiedene Herstellungsverfahren entwirkt, um sowohl die plastische Verformung der metallischer Massivgläser zu erhöhen, als auch um die mechanischen Eigenschaften generell zu verbessern. Eine mögliche Methode, zur Erhöhung der Plastizität und zur Beeinflussung der mechanischen Eigenschaften der metallischen Gläser ist der Einbau zweiter Phasen, wie z.B. durch Fremdpartikel Verstärkung oder Poren in Kompositen. Die Scherband bewegung wird durch die Wechselwirkung mit zweiten Phasen behindert, und gleichzeitig werden durch die in den Grenzflächen entstehenden Spannungsspitzen zwischen der zweiten Phase und der Matrix neue Scherbänder initiert. Dies führt zur Bildung einer Vielzahl von Scherbändern, was eine höhere plastische Dehnung zur Folge hat, da die Deformationsenergie auf ein größeres Volumen verteilt wird. In der vorliegenden Arbeit wurden Ni59Zr20Ti16Si2Sn3 Massivglas und mit Messing- verstärkte Komposite durch Kugelmahlen und Heißpressen mit anschließender Extrusion von Ni59Zr20Ti16Si2Sn3 Pulver oder Ni59Zr20Ti16Si2Sn3 Pulver mit 40 vol.% Messing Partikeln hergestellt. Neben der Herstellung der Ni59Zr20Ti16Si2Sn3 Komposite mit Messing Partikeln, wurden auch Ni59Zr20Ti16Si2Sn3 Komposite mit definierter Porösität durch die selektive Auflösung der zweiten Phase erzeugt. Die verwendete Mischung von Messing und metallischem Glaspulver wurde über zwei verschiedene Ansätzen hergestellt: die Pulver wurden manuell gemischt oder gemahlen, um die optimale Größe und Morphologie der zweiten Phase in den Komositen zu erzeugen. Das Sintern der Pulver erfolgte bei Temperaturen im Bereich der unterkühlten Schmelze, wobei die Legierung eine starke Abnahme der Viskosität zeigte, mit Hilfe optimierter Sinterparameter, die nach der Analyse des Kristallisationsverhaltens der gläsernen Phase ausgewählt wurden, um deren Kristallisation während der Konsolidierung zu vermeiden. Kugelmahlen hat einen signifikanten Einfluss auf die Mikrostruktur der gemahlenen Pulver: Eine verfeinerte Lamellare Struktur, teils bestehend aus Glas und teils aus Messing, wird durch mechanische Verformung gebildet. Kugelmahlen reduziert jedoch den amorphen Anteil der Komposite durch mechanische induzierte Kristallisation und die Reaktion der Glas- und Messing- Phasen durch Erwärmung. Das Kugelmahlen der Komposite (Pulver) und das darauf folgende Sintern führte zur eine Absenkung der freien Enthalpie der amorphen Phase um ca. 50%. Ni59Zr20Ti16Si2Sn3 metallische Massivgläser, welche durch Heißpressen hergestellt werden, weisen eine höhere Streckgrenze von 2.28 GPa als das gegossene Ni59Zr20Ti16Si2Sn3 Massivglas (2.2 GPa) auf. Die mechanischen Eigenschaften der mit Messing Ni59Zr20 Ti16Si2Sn3 verstärkten Komposite sind abhängig von der Kontrolle der Mikrostruktur zwischen den zweiten Phasen und der Matrixphase durch die verschiedenen Verfahren zur Herstellung von Pulvermischungen. Die Festigkeiten der Komposite, welche durch Handmischen und Heißpressen mit nachfolgender Extrusion hergestellt wurden, erhöhten sich von 500 MPa für reines Messing bis auf 740 und 925 MPa für die Komposite mit 40 und 60 Vol. % Glaspartikel- Verstärkung durch Handmischen. Die Festigkeiten erhöhten sich nochmals auf 1240 und 1640 MPa für die Komposite mit 40 und 60 Vol. % an Glaspartikel-Verstärkung mit lamellare Stuktur, die durch Kugelmahlen hergestellt würden. Die Ursache hier für liegt in der Wirkung der Ligamentabmessungen zwischen den Matrixbestandteilen hinsichtlich der Verfestigung der Komposite. Die Porösität im metallischen Glas wurde durch die selektive Auflösung der flüchtigen Messingphasen in den Kompositen mit Salpetersäure-Lösung erhalten. Die Mikrostuktur der porösen metallischen Gläser besteht aus stark elongiert geschichteten Porenstrukturen und/oder unregelmäßig geformten Poren. Die durchschnittliche Größe einer Pore hängt von den behandelnden Parametern ab und kann von 0.4–15 µm variieren. Weitere poröse Proben wurden ausgehend von verschiedenen extrudierten Komposit-Precursoren aus handgemischten und kugelgemahlenen Pulvermixturen erzeugt. Dies führte zu angepassten hybrid-porösen Strukturen bestehend aus einer Kombination von großen und kleinen Poren. Die spezifische Oberfläche des porösen Glaspulvers gemessen mit Hilfe der BET- Methode, beträgt 16m2/g, wohingegen das atomisierte Ni59Zr20Ti16Si2Sn3 MG Ausgangspulver eine spezifische Oberfläche von 0.29 m2/g besitzt. Dies weist darauf hin, dass das Mahlen eine Vergrößerung der Oberfläche durch die Verfeinerung der flüchtigen Messingphase induziert. Die spezifische Oberfläche der porösen-metallischen Gläser beträgt 10 m2/g und entsteht durch die Zerstörung der porösen Struktur während der selektiven Auflösung der nanoskaligen flüchtigen Phase. Obwohl das Kugelmahlen der Komposite (Pulver) und die darauf folgende Konsolidierung zwar den amorphen Anteil um etwa 50% reduziert, bietet die Pulvermetallurgische Herstellung durch die Verwendung von gläsernen Phasen mit verbesserter Stabilität gegenüber mechanisch induzierter Kristallisation, sowie einer reduzierten Affinität mit der flüchtigen Messingphase zur Vermeidung von unerwünschten Reaktionen während des Prozesses eine Möglichkeit, hochaktive poröse metallische Gläser für funktionelle Anwendungen, wie z.B. Katalyse, zu entwickeln. Hier ist eine schnelle Transport von Reaktanten und Produkten, welcher von den großen Poren, sowie eine hohe katalytische Aktivität, die von kleinen Poren und einer großen Oberfläche sichergestellt wird wesentlich. Daher wurden Untersuchungen zur Gasabsorptionsfähigkeit von porösem metallischen Glaspulver durchgeführt, um die Möglichkeit der Ersetzung von konventionellen Trägermaterialen bewerten zu können. Diese ersten Versuche zeigen die grundsäLzliche Eignung nano poröse metallischer Gläser zur Herstellung von porösen Strukturen mit einstellbarer Porenarchitektur auf die Langfristig für spezifische funktionelle Anwendungen von Interesse sein könnten

Metallic glasses exhibit many attractive attributes such as outstanding mechanical, magnetic, and chemical properties. Due to the absence of crystal defects, metallic glasses display remarkable mechanical properties including higher specific strength than crystalline alloys, high hardness and larger fracture resistance than ceramics. The technological breakthrough of metallic glasses, however, has been greatly hindered by the limited plastic strain to failure. Thus, several strategies have been employed to improve the intrinsic and extrinsic effects on the flow behavior of metallic glasses with respect to their fracture toughness and overall plastic strain. One of the suggested strategies is the production of a composite consisting of the brittle metallic glass along with a ductile second phase that either acts as an active carrier of plastic strain or passively enhances the multiplication of shear bands via shear-band splitting . Another approach for increasing plastic deformation consists of introducing pores as a gaseous second phase into the material. The pores are similarly effective in delaying catastrophic failure resulting from shear band localization. In metallic glasses with high porosity, propagation of shear bands can even become stable, enabling macroscopic compressive strains of more than 80 % without fracture. In this thesis, Ni59Zr20Ti16Si2Sn3 glass and its composites have been fabricated using mechanical milling and consolidation by hot pressing followed by extrusion of Ni59Zr20Ti16Si2Sn3 metallic glass powder or Ni59Zr20Ti16Si2Sn3 metallic glass powder reinforced with 40 vol.% of brass particles to obtained bulk composite materials with high strength and enhanced compressive plasticity and to generate porous structure in Ni59Zr20Ti16Si2Sn3 metallic glass using selective dissolution. The brass–glass powder mixtures to be consolidated were prepared using two different approaches: manual blending and ball milling to properly vary size and morphology of the second phase in the composites. Powder consolidation was carried out at temperatures within the supercooled Liquid (SCL) region, where the glassy phase displays a strong decrease of viscosity, with using the sintering parameters which were chosen after analysis of the crystallization behavior of the glassy phase to avoid its crystallization during consolidation. Ball milling has a significant effect on the microstructure of the powder mixtures: a refined layered structure consisting of alternating layer of glass and brass is formed as a result of the mechanical deformation. However, ball milling reduces the amorphous content of the composite powders due to mechanically induced crystallization and reaction of the glass and brass phases during heating. In addition, the milling of the composite powders and the following consolidation step reduces the amorphous content by about 50 %. The bulk amorphous Ni59Zr20Ti16Si2Sn3 alloy synthesized by hot pressing exhibits higher strength (2.28 GPa) than that of the as-cast bulk amorphous Ni59Zr20Ti16Si2Sn3 alloy (2.2 GPa). The mechanical behavior of the glass-brass composites is significantly affected by the control of the microstructure between the reinforcement and the nano-grained matrix phase through the different methods used for the preparation of the powder mixtures. The strength of the composites increases from 500 MPa for pure brass to 740 and 925 MPa for the composites with 40 and 60 vol.% glass reinforcement prepared by manual blending. The strength further increases to 1240 and 1640 MPa for the corresponding composites produced by ball milling caused by the remarkable effect of the matrix ligament size on the strengthening of the composites. The porous metallic glass was obtained by the selective dissolution in a HNO3 solution of the fugitive brass phase in the Ni59Zr20Ti16Si2Sn3 composite. The microstructure of the porous samples consists of highly elongated layered pore structures and/or irregularly shaped pores. The average size of the pores depends on the processing parameters and can be varied in the range of 0.4–15 µm. Additional porous samples were prepared from different extruded composite precursors of blended and milled powder mixtures. This leads to customized hybrid porous structures consisting of a combination of large and small pores. The specific surface area of the porous Ni-based metallic glass powder measured by the BET method is 16 m2/g, while the as-atomized Ni59Zr20Ti16Si2Sn3 powder has a specific surface area of 0.29 m2/g. This indicates a mechanical milling induced enhancement in surface area by refinement of the fugitive brass phase. However the specific surface area of the porous Ni-based metallic glass obtained from as-extruded precursors is 10 m2/g caused by a breakdown of the porous structure during selective dissolution of the nano-scale fugitive phase. Although milling of the present composite powders and the following consolidation step reduces the amorphous content by about 50 %, through the use of glassy phases with improved stability against mechanically induced crystallization along with reduced affinity with the fugitive phase to avoid unwanted reactions during processing, this approach using powder metallurgical offers the possibility to produce highly active porous bulk materials for functional applications, such as catalysis, which require the fast transport of reactants and products provided by the large pores along with high catalytic activity ensured by the large surface area characterizing the small pores. Accordingly, gas absorption ability tests of porous Ni-based metallic glass powders have been performed in order to evaluate the possibility of replacement of conventional support materials. From these first tests it can be conclude that additional opportunities should exist for nano-porous MGs with designed architecture of porous structures that are tailored to specific functional applications.
Metallische Gläser weisen viele attraktive mechanische, magnetische und chemische Eigenschaften auf. Aufgrund der fehlenden Kristallstruktur zeigen metallische Gläser bemerkenswerte mechanische Eigenschaften, einschließlich höherer spezifischer Festigkeit, höherer Härte und größerer Bruchfestigkeit als Keramik. Der technologischen Durchbruch metallischer Gläser wird jedoch bis heute stark von ihremspröden Bruchverhalten behindert. Deshalb wurden verschiedene Herstellungsverfahren entwirkt, um sowohl die plastische Verformung der metallischer Massivgläser zu erhöhen, als auch um die mechanischen Eigenschaften generell zu verbessern. Eine mögliche Methode, zur Erhöhung der Plastizität und zur Beeinflussung der mechanischen Eigenschaften der metallischen Gläser ist der Einbau zweiter Phasen, wie z.B. durch Fremdpartikel Verstärkung oder Poren in Kompositen. Die Scherband bewegung wird durch die Wechselwirkung mit zweiten Phasen behindert, und gleichzeitig werden durch die in den Grenzflächen entstehenden Spannungsspitzen zwischen der zweiten Phase und der Matrix neue Scherbänder initiert. Dies führt zur Bildung einer Vielzahl von Scherbändern, was eine höhere plastische Dehnung zur Folge hat, da die Deformationsenergie auf ein größeres Volumen verteilt wird. In der vorliegenden Arbeit wurden Ni59Zr20Ti16Si2Sn3 Massivglas und mit Messing- verstärkte Komposite durch Kugelmahlen und Heißpressen mit anschließender Extrusion von Ni59Zr20Ti16Si2Sn3 Pulver oder Ni59Zr20Ti16Si2Sn3 Pulver mit 40 vol.% Messing Partikeln hergestellt. Neben der Herstellung der Ni59Zr20Ti16Si2Sn3 Komposite mit Messing Partikeln, wurden auch Ni59Zr20Ti16Si2Sn3 Komposite mit definierter Porösität durch die selektive Auflösung der zweiten Phase erzeugt. Die verwendete Mischung von Messing und metallischem Glaspulver wurde über zwei verschiedene Ansätzen hergestellt: die Pulver wurden manuell gemischt oder gemahlen, um die optimale Größe und Morphologie der zweiten Phase in den Komositen zu erzeugen. Das Sintern der Pulver erfolgte bei Temperaturen im Bereich der unterkühlten Schmelze, wobei die Legierung eine starke Abnahme der Viskosität zeigte, mit Hilfe optimierter Sinterparameter, die nach der Analyse des Kristallisationsverhaltens der gläsernen Phase ausgewählt wurden, um deren Kristallisation während der Konsolidierung zu vermeiden. Kugelmahlen hat einen signifikanten Einfluss auf die Mikrostruktur der gemahlenen Pulver: Eine verfeinerte Lamellare Struktur, teils bestehend aus Glas und teils aus Messing, wird durch mechanische Verformung gebildet. Kugelmahlen reduziert jedoch den amorphen Anteil der Komposite durch mechanische induzierte Kristallisation und die Reaktion der Glas- und Messing- Phasen durch Erwärmung. Das Kugelmahlen der Komposite (Pulver) und das darauf folgende Sintern führte zur eine Absenkung der freien Enthalpie der amorphen Phase um ca. 50%. Ni59Zr20Ti16Si2Sn3 metallische Massivgläser, welche durch Heißpressen hergestellt werden, weisen eine höhere Streckgrenze von 2.28 GPa als das gegossene Ni59Zr20Ti16Si2Sn3 Massivglas (2.2 GPa) auf. Die mechanischen Eigenschaften der mit Messing Ni59Zr20 Ti16Si2Sn3 verstärkten Komposite sind abhängig von der Kontrolle der Mikrostruktur zwischen den zweiten Phasen und der Matrixphase durch die verschiedenen Verfahren zur Herstellung von Pulvermischungen. Die Festigkeiten der Komposite, welche durch Handmischen und Heißpressen mit nachfolgender Extrusion hergestellt wurden, erhöhten sich von 500 MPa für reines Messing bis auf 740 und 925 MPa für die Komposite mit 40 und 60 Vol. % Glaspartikel- Verstärkung durch Handmischen. Die Festigkeiten erhöhten sich nochmals auf 1240 und 1640 MPa für die Komposite mit 40 und 60 Vol. % an Glaspartikel-Verstärkung mit lamellare Stuktur, die durch Kugelmahlen hergestellt würden. Die Ursache hier für liegt in der Wirkung der Ligamentabmessungen zwischen den Matrixbestandteilen hinsichtlich der Verfestigung der Komposite. Die Porösität im metallischen Glas wurde durch die selektive Auflösung der flüchtigen Messingphasen in den Kompositen mit Salpetersäure-Lösung erhalten. Die Mikrostuktur der porösen metallischen Gläser besteht aus stark elongiert geschichteten Porenstrukturen und/oder unregelmäßig geformten Poren. Die durchschnittliche Größe einer Pore hängt von den behandelnden Parametern ab und kann von 0.4–15 µm variieren. Weitere poröse Proben wurden ausgehend von verschiedenen extrudierten Komposit-Precursoren aus handgemischten und kugelgemahlenen Pulvermixturen erzeugt. Dies führte zu angepassten hybrid-porösen Strukturen bestehend aus einer Kombination von großen und kleinen Poren. Die spezifische Oberfläche des porösen Glaspulvers gemessen mit Hilfe der BET- Methode, beträgt 16m2/g, wohingegen das atomisierte Ni59Zr20Ti16Si2Sn3 MG Ausgangspulver eine spezifische Oberfläche von 0.29 m2/g besitzt. Dies weist darauf hin, dass das Mahlen eine Vergrößerung der Oberfläche durch die Verfeinerung der flüchtigen Messingphase induziert. Die spezifische Oberfläche der porösen-metallischen Gläser beträgt 10 m2/g und entsteht durch die Zerstörung der porösen Struktur während der selektiven Auflösung der nanoskaligen flüchtigen Phase. Obwohl das Kugelmahlen der Komposite (Pulver) und die darauf folgende Konsolidierung zwar den amorphen Anteil um etwa 50% reduziert, bietet die Pulvermetallurgische Herstellung durch die Verwendung von gläsernen Phasen mit verbesserter Stabilität gegenüber mechanisch induzierter Kristallisation, sowie einer reduzierten Affinität mit der flüchtigen Messingphase zur Vermeidung von unerwünschten Reaktionen während des Prozesses eine Möglichkeit, hochaktive poröse metallische Gläser für funktionelle Anwendungen, wie z.B. Katalyse, zu entwickeln. Hier ist eine schnelle Transport von Reaktanten und Produkten, welcher von den großen Poren, sowie eine hohe katalytische Aktivität, die von kleinen Poren und einer großen Oberfläche sichergestellt wird wesentlich. Daher wurden Untersuchungen zur Gasabsorptionsfähigkeit von porösem metallischen Glaspulver durchgeführt, um die Möglichkeit der Ersetzung von konventionellen Trägermaterialen bewerten zu können. Diese ersten Versuche zeigen die grundsäLzliche Eignung nano poröse metallischer Gläser zur Herstellung von porösen Strukturen mit einstellbarer Porenarchitektur auf die Langfristig für spezifische funktionelle Anwendungen von Interesse sein könnten.

Orientador: Luiz Carlos Barbosa
Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin
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Resumo: Neste trabalho três tipos de vidro telurito são estudados, fabricados e caracterizados, tendo em vista a fabricação de fibras ópticas de cristal fotônico. Basicamente, dois processos de fabricação de fibras de cristal fotônico foram considerados: 1) Empilhamento e puxamento, e 2) Extrusão. Os vidros teluritos fabricados são: 0,77TeO2¿0,23WO3; 0,75TeO2¿0,20Li2O¿0,05TiO2 e 0,68TeO2¿0,155ZnO¿0,05Li2CO3¿0,015Bi2O3¿0,095CsCl (mol%), dos tipos binário, ternário e quinqüenário, respectivamente, os quais foram dopados com Er2O3. As caracterizações efetuadas foram: a) Medida do índice de refração, 2) Fotoluminescência, 3) Absorbância, 4) Tempo de vida dos íons de Érbio, 5) Análise Térmica Diferencial, 6) Análise termogravimétrica e, 7) Viscosidade. Como dito anteriormente, pode-se fabricar fibras microestruturadas de telurito por extrusão, ou pelo método de empilhamento e puxamento. A extrusora disponível no laboratório de materiais vítreos foi feita para extrudar materiais polímeros. Nossa tentativa de utilizá-la para vidros telurito não foi bem sucedida. Porém, pudemos tirar algum proveito desta experiência para futuros projetos. Os tubos de vidro telurito utilizados no método de empilhamento e puxamento foram fabricados tanto por sucção vertical do vidro fundido, quanto por rotação horizontal dos tubos em chama. No primeiro método, o diâmetro interno dos tubos de revestimento diminuiu de baixo para cima, devido ao efeito da gravidade, fazendo com que o preenchimento dos mesmos com tubos capilares fosse inadequado, ou seja, a secção transversal da fibra apresentou espaços vazios não preenchidos pelos capilares. No segundo método, o diâmetro interno dos tubos de revestimento não apresentou variação significativa ao longo de seu comprimento, possibilitando, assim, um melhor preenchimento dos mesmos por tubos capilares. Embora as fibras fabricadas com tubos feitos por rotação horizontal em chama apresentem boa geometria de secção transversal, a contaminação do vidro pela chama acarreta um aumento nas perdas de potência óptica dos modos guiados. Este efeito foi eliminado pela utilização de centrifugação em um forno radiante. Verificamos, também, que as fibras microestruturadas com somente um anel de capilares ao redor do núcleo apresentam grandes perdas por confinamento.
Abstract: In this work, three types of tellurite glasses are synthesized and characterized, aiming the manufacturing of photonic crystal fibers or microstructured fibers. Basically, two types of manufacturing processes are considered: 1) Stacking and draw, and 2) Extrusion. The tellurite glasses are: 0,77TeO 2¿0,23WO3; 0,75TeO2¿0,20Li2O¿0,05TiO2 e 0,68TeO2¿ 0,155ZnO¿0,05Li2C3¿0,015Bi2O3¿0,095CsCl (mol%), composed by two, three and five types of oxides, respectively, and Erbium oxide. The glasses were characterized by: a) index of refraction, 2) photoluminescence, 3) absorbance, 4) Erbium ions lifetime, 5) Differential Thermal Analysis, 6) Thermo gravimetric Analysis, and 7) Viscosity. The extrusion machine of the laboratory was devised for polymers. Nevertheless, we tried with telluride glass but without success. The tellurite glass tubes used for the stack and draw process were manufactured by vertical suction of the melted glass as well as by horizontal rotation of the tubes in flame. For the vertical suction method, the tellurite tube inner diameter shows a taper feature from the bottom to the top of the tube, due to the gravity effect, that makes the jacket tube unsuitable for capillary filling, that is, the fiber transversal section shows empty spaces that could not be filled with capillaries. For the second method, the telluride jacket tube inner diameter do not shows a significant variation with length, so it was possible to better fill it with the capillaries. Although the fibers made with tubes manufactured by horizontal rotation in flame shows good transversal geometry, the contamination of the glass by the flame gases brought about great losses for optical guided modes. The burner was replaced by a radiant oven. We verified, also, that micro structured fibers with only one ring of capillaries around the nucleus shows great confinement loss arising from the leaky nature of the modes
Doutorado
Física da Matéria Condensada
Doutor em Física

Compression of coated pellets is a practical alternative to capsule filling. The current practice is to add cushioning agents to minimize the stress on the coated pellets. Cushioning agents however add bulkiness and reduce the overall drug loading capacity. In this study, we investigated the performance of compressed coated pellets with no cushioning agent to evaluate the feasibility of predicting the coat behaviour using thermo-mechanical and rheological analysis techniques. Different coating formulations were made of ethyl cellulose (EC) as a coating polymer and two different kinds of additives were incorporated into the polymeric coating solution. Triethyl Citrate (TEC) and Polyethylene glycol 400(PEG400) were used as plasticizers at different levels to the coating formulations (10%, 20%, 30%). Thermal, mechanical and rheological measurements of the coating film formulations were achieved to investigate the effect of plasticizers. Thermal gravimetric analysis results (TGA) showed higher residual moisture content in films plasticised with PEG 400 compared to their TEC counterparts. Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA) and Parallel Plate Shear Rheometer (PPSR) were used to study the influence of the level and type of plasticisers incorporated in coating film formulation on the performance of the coating film. In this study, both DSC and DMA were used to investigate the Tg for each film coating formulation in order to evaluate the effect of the additives. In general DMA results for the Tg value of the films were always higher by 10-20% than those measured by the DSC. Furthermore, clamp size and the frequency of the oscillation have an influence on the evaluation of Tg. Complex viscosity for different coating film formulations revealed that the shear hinning gradient changes with temperature and plasticiser type and concentration. The value of complex viscosity from DMA and PPSR exhibits power law behaviour. The rheological moduli were indirectly affected by the level of plasticiser. There was a discrepancy between the complex viscosity results obtained from both DMA and PPSR at similar temperature but they follow the same trend. The non plasticized polymer showed a 10 time higher complex viscosity values when measured by DMA over that measured by PPSR. The difference was smaller in plasticized films but it was not consistent. Therefore a consistent coefficient to correlate the DMA and PPSR couldn’t be accurately determined Coated pellets were compressed and key process parameters were evaluated. The obtained results revealed that the coating thickness has a significant effect on the release profile of the final products. It was found that by increasing the coating film thickness, the percentage released decreased. Also the compression force has lower influence on the drug release profile, while the dwell time has very low effect on the percentage release from the final products. Optimum release profile was obtained at a coating level of 5.5% w/w and a compression force of 4700N In conclusion, the elasticity of the plasticised EC films in this study meant that the internal stress is not dissipated during compression and the dwell time range that was used in this experiment. Increasing the thickness therefore was necessary to enhance the strength of the film and avoid cracking. The mechanical and rheological profiling was helpful therefore to understand the behaviour of the coated pellets and predict the film properties at various steps of the process of coating and compression (i.e., various shear rate regimes). Experimental design approach to studying the key process and formulation parameters helped identify the optimum values for the process.

Les verres métalliques ont commencé à être produit dans les années 1960 et sous forme massive dans les années 1980. De nombreuses études se sont intéressées à ces matériaux sous leur forme amorphe et ont conclu qu’ils avaient une forte résistance mécanique mais présentaient un comportement très fragile. Dans le cadre du projet EDDAM débuté en 2011, ces matériaux ont été introduits sous forme de petites sphères dans une matrice d’aluminium. Le premier objectif de notre étude est de voir si le verre métallique sous cette forme permet de le rendre peu fragile. Le second objectif est de trouver une alternative aux renforts céramique dans les composites à matrice métallique qui présentent une faible cohésion à l’interface matrice/inclusion. Dans le but de caractériser l’endommagement dans des nouveaux composites amorphe-cristallins métalliques, la tomographie aux rayons X a été utilisée. Cette technique permet de caractériser de manière non destructive l’endommagement des matériaux et de le visualiser en 3D. Cela apporte une contribution à l’étude des matériaux composites par rapport aux techniques classiques utilisées. L’objectif général de cette thèse a été d’étudier l’endommagement en termes d’amorçage, de croissance et de coales- cence des matériaux composites amorphe-cristallins métallique par tomographie aux rayons X lors d’essais de traction monotone in situ. Les matériaux sélectionnés sont constitués d’une matrice aluminium ("molle" de type 1070A ou "dure" de type 5083) et de renforts en verre métallique Zr57Cu20Al10Ni8Ti5 de taille peu dispersée et répartis de manière homogène, avec différentes fractions volumiques (1%, 4% et 10%). Les matériaux composites ont été élaborés par la voie de la métallurgie des poudres au Spark Plasma Sintering (SPS) suivi d’une étape d’extrusion à chaud. Une attention particulière a été portée sur la caractérisation microstructurale des constituants de base. L’analyse qualitative a permis de comparer l’ensemble des composites fabriqués au SPS et ceux extrudés à chaud après SPS. Les différents modes d’amorçage de l’endommagement ont été observés ainsi que la croissance et la coa- lescence amenant la rupture des composites. L’analyse quantitative a été essentiellement consacrée au premier stade de l’endommagement. La croissance et la coalescence étant très rapide, il a été difficile de les suivre lors des essais interrompus. La modélisation d’un composite amorphe-cristallin métallique à matrice molle a été introduite dans le but de reproduire l’endommagement observé lors des analyses expérimentales. Cette première approche nécessite d’être approfondie dans le but de prédire, compte tenu des propriétés mécaniques des différentes phases et de la fraction volumique des renforts, le mode d’endommagement préférentiel apparaissant dans les composites étudiés. Elle montre cependant les prémices d’une modélisation innovante basée sur la microstructure expérimentale
Metallic glasses have been produced in the 1960s and bulk metallic glasses in the 1980s. Many studies, focused on these materials in their amorphous state, concluded that they had high mechanical strength but shown low ductility. As part of EDDAM project that started in 2011, these materials were introduced as small particles in an aluminum matrix. The first objective of this study is to see if the metallic glass is less brittle in this form. The second objective is to find an alternative of ceramic reinforcements in metal matrix composites. These materials have low cohesion at the matrix/inclusion interface. In order to characterize the damage in new amorphous-crystalline composite, X-ray tomography was used. This allows to characterize damage in materials and to obtain a 3D viewing. The main objective of this thesis was to study damage (nucleation, growth and coalescence) in composite materials using X-ray tomography during tensile tests. Selected materials are constituted of an aluminum matrix and small metallic glass reinforcements (Zr57Cu20Al_10Ni8Ti5). Composites with different volume fractions (from 1vol.% to 10vol.%) were prepared by Spark Plasma Sintering (SPS) and hot extrusion. A particular attention was paid to the microstructural characterization of the basic constituents. Qualitative analysis was used to compare SPS composites with SPS plus hot extrusion composites. Damage nucleation, growth and coalescence were observed. Quantitative analysis was mainly devoted to the first damage step. Growth and coalescence were difficult to follow due to fast rupture and interrupted tensile tests. The modeling of an amorphous-crystalline composite has been introduced in order to reproduce experimental damage analyses. The first approach requires further investigation to predict damage with different volume fractions. However, this part shows the beginning of an innovative model based on the experimental microstructure

Ce travail de thèse porte sur les relations entre les paramètres de mise en œuvre à l’état fondu et les propriétés d’un composite hybride à matrice thermoplastique. Les charges étudiées sont les fibres de verre courtes (échelle micrométrique) et les nanotubes de carbone (NTC) (échelle nanométrique) dispersées dans une matrice thermoplastique thermostable, le poly(éther imide) (PEI). Nous avons montré que les fibres de verre participent fortement à la structuration du réseau de NTC et que la conductivité électrique du composite hybride est plus élevée que celle des nanocomposites. Les paramètres de mise en œuvre et notamment le paramètre Energie Mécanique Spécifique (EMS) a une forte influence sur les propriétés des composites hybrides et notamment sur la conductivité électrique. Il a été montré que les variations de conductivité électrique sont la conséquence d’un changement d’état de dispersion des NTC. Le taux de fibres de verre introduit dans le nanocomposite PEI/NTC a une forte influence sur la conductivité du composite hybride. Il est possible de contrôler la conductivité électrique du composite multi-échelles en modifiant le taux de fibres de verre introduit notamment pour des concentrations en NTC proche du seuil de percolation
This PhD work deals with the relationship between the processing parameters at the melt state and the polymer matrix hybrid composite material’s properties. The fillers studied are short glass fibres (micrometric scale) and carbon nanotubes (CNT) (nanometric scale) dispersed in a high temperature polymer matrix, the poly(etherimide) (PEI). We showed that glass fibres strongly participate in the CNT network structuration and that electrical conductivity of multiscale composite materials is higher than the one of nanocomposite materials. The combination of the two fillers allows obtaining a synergy effect for the mechanical properties especially for the elongation at break which is due to a preferential localization of CNT at the PEI/glass fibres interfaces. The study of the influence of processing parameters on the properties of nanocomposite materials and hybrid composite materials showed that Specific Mechanical Energy (SME) has a strong influence on the hybrid composite material properties and especially on the electrical conductivity. These variations are the consequences of CNT network modifications. Glass fibres concentration has also a strong influence on the electrical conductivity of the hybrid composite materials. It is possible to adjust the electrical conductivity with modifying the concentration of glass fibres especially for the CNT amount closed to the electrical percolation threshold

Com o intuito de elevar os valores de resistência à fratura dos dentes que sofreram tratamento endodôntico, várias técnicas restauradoras têm sido desenvolvidas. Atualmente os sistemas de pinos de fibras de carbono e de vidro são os dispositivos mais utilizados, devido às suas vantagens de possuírem módulo de elasticidade próximo ao da dentina, o que causa menor estresse e conseqüentemente menor quantidade de fraturas radiculares, além de não necessitarem da fase laboratorial. A escolha do cimento utilizado para a cimentação desses pinos, tem grande importância e o advento dos cimentos resinosos e dos sistemas adesivos que com eles podem ser empregados, representam uma grande evolução em razão das possibilidades de se obter retenções micromecânicas no interior dos condutos. Assim, o objetivo deste estudo foi avaliar a resistência à extrusão de pinos de fibras de vidro cimentados com cimento resinoso Rely X ARC com a aplicação de três diferentes sistemas adesivos: Scotchbond, Single bond e Adper Prompt LPop. Após a cimentação os espécimes foram seccionados em duas regiões, apical e cervical, que constituía cada uma um corpo de prova. Para possibilitar a realização do teste de extrusão, utilizou-se um dispositivo de aço inoxidável que estabilizava o corpo de prova. Este dispositivo tinha um orifício central que permitia o deslocamento do pino ou do cimento, durante o teste de extrusão. Para o teste de extrusão o corpo de prova foi adaptado no dispositivo com a face cervical voltada para baixo e uma ponta ativa com extremidade plana (1mm de diâmetro) foi adaptada à máquina de ensaios universal que exercia uma força de extrusão o mais próximo possível do centro do pino. O teste foi realizado com um deslocamento de 0,5mm por minuto, onde a carga máxima de falha foi registrada em kgf. No que diz respeito ao cimento resinoso Rely X ARC, em combinação com os adesivos utilizados, os melhores resultados na região cervical da raiz foram obtidos com o cimento Rely X com o sistema adesivo Scotchbond, seguido pelos sistemas Adper Prompt e Single bond. Na região apical o Scotchbond foi melhor que o Adper Prompt e o Single bond, mas não houve diferença estatisticamente significante entre o Adper Prompt e Single bond.
In order to increase strength to fracture of endodontically treated teeth, a number of restorative techniques were developed. Nowadays, carbon and glass fiber post systems are the most used due to their advantages of modulus of lasticity similar to dentin, which lead to lower stress and consequently lower number of root fractures, besides no laboratorial work is needed. The choice of the best cement for luting these posts is an important step and the development of resin cements and adhesive systems that can be use with posts are a great evolution due to the possibility of micromechanical retention in roots. Therefore, the aim of this study was to evaluate extrusion strength of glass fiber posts cemented with resin luting cement Rely X ARC using three different adhesive systems: Scothbond, Single bond and Adper Prompt L Pop. After luting, samples were seccionated in two regions, apical and cervical, each one representing one sample. A stainless steel device was used to perform extrusion test, stabilizing samples. This device had a central orifice that allowed movement of post or cement, during extrusion test. For extrusion test, sample was adapted in the device with cervical face directed to down and a plane surface active point (1 mm diameter) was adapted to the universal test machine which exerted an extrusion force in the center of post. Test was performed with 0.05 mm per minute and the maximum load at failure was registered in kgf. Regarding resin luting cement Rely X ARC combining with adhesive systems, the best results at cervical were obtained with Rely X and Scotchbond adhesive, followed by Adper Prompt and Single bond systems. At apical region Scotchbond was better than Adper Prompt and Single bond, but there was no statistically significant difference between Adper Prompt and Single bond.

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O presente estudo teve como objetivo avaliar a influência do tratamento da dentina radicular com clorexidina a 2% e ácido cítrico a 10% na resistência de união de pinos de fibra de vidro cimentados com cimento resinoso RelyX Ultimate (3M ESPE) associado a um adesivo autocondicionante Single Bond Universal (3M ESPE). Quarenta e cinco dentes humanos unirradiculares foram selecionados e seccionados na junção cemento-esmalte, padronizando-os com 14 mm de comprimento. Após tratamento endodôntico, as raízes foram divididas aleatoriamente em 3 grupos (n=15) de acordo com o tratamento prévio do conduto radicular: G1, nenhum tratamento; G2, aplicação de gel de clorexidina a 2% (Rioquímica®) por 60 segundos; G3, aplicação de ácido cítrico a 10% (Idem per Idem Farmácia de Manipulação Ltda) por 60 segundos. Posteriormente, foi aplicado o adesivo nos condutos e nos pinos de fibra de vidro (White Post, FGM) e estes foram cimentados com cimento resinoso (RelyX Ultimate - 3M ESPE), sendo fotopolimerizados por 40 segundos. As raízes foram seccionadas axialmente em discos de 2 mm e os espécimes foram submetidos ao teste de push-out. As médias dos valores obtidos (MPa) foram analisadas por meio dos testes one-way ANOVA e Tukey (α=0,05) e os tipos de falhas analisadas em estereomicroscópio com aumento de 8,0X. Os resultados mostraram que não houve diferença estatisticamente significativa entres os grupos avaliados, assim como quando comparados os terços radiculares em cada grupo (p>0,05), entretanto resultados significantes foram encontrados entre os grupos G1 e G2 na região cervical (p=0,045). Falhas mista e adesiva entre cimento e dentina foram mais prevalentes. Pôde-se concluir que o uso da clorexidina a 2% no conduto radicular pode interferir na resistência de união de pinos de fibra de vidro e que o ácido cítrico não influenciou nos resultados.
The aim of this study was to investigate the influence of root dentine treatment with 2% chlorhexidine and 10% citric acid on bond strength of fiberglass post cemented with self-etching cement. Forty five human single-rooted teeth were selected and sectioned in the cement-enamel junction, standardizing them with 14 mm length. After endodontic treatment the roots were randomly divided in 3 groups (n=15) according to the previous treatment of the root canal: G1, no treatment; G2, application of 2% chlorhexidine (Rioquímica®) for 60s; G3, application of 10% citric acid (Idem per Idem - Farmácia de Manipulação Ltda) for 60s. Subsequently, the self-etching adhesive Single Bond Universal (3M ESPE) was applied in the canals and on the fiberglass post (White Post, FGM) and these ones were cemented with resin cement (RelyX Ultimate - 3M ESPE), and light polymerized for 40s. The roots were sectioned transversely in slides of 2 mm thickness and the push-out test was performed. Data were analyzed by one-way ANOVA and Tukey test (α=0.05) and the types of failures were analyzed under stereomicroscopy (8.0X). The results show that there was no statistically significant difference between the groups, as well as when comparising bond strength in root thirds in each group (p>0.05), however, significant results were found between groups G1 and G2 in the cervical third (p=0.045). Mixed and adhesive failures between cement and dentine were predominant. It can be concluded that the use of 2% chlorhexidine in the root canal can interfere in the fiberglass posts bond strength.

The Queensland University of Technology (QUT) allows the presentation of a thesis for the Degree of Doctor of Philosophy in the format of published or submitted papers, where such papers have been published, accepted or submitted during the period of candidature. This thesis is composed of Seven published/submitted papers and one poster presentation, of which five have been published and the other two are under review. This project is financially supported by the QUTPRA Grant. The twenty-first century started with the resurrection of lignocellulosic biomass as a potential substitute for petrochemicals. Petrochemicals, which enjoyed the sustainable economic growth during the past century, have begun to reach or have reached their peak. The world energy situation is complicated by political uncertainty and by the environmental impact associated with petrochemical import and usage. In particular, greenhouse gasses and toxic emissions produced by petrochemicals have been implicated as a significant cause of climate changes. Lignocellulosic biomass (e.g. sugarcane biomass and bagasse), which potentially enjoys a more abundant, widely distributed, and cost-effective resource base, can play an indispensible role in the paradigm transition from fossil-based to carbohydrate-based economy. Poly(3-hydroxybutyrate), PHB has attracted much commercial interest as a plastic and biodegradable material because some its physical properties are similar to those of polypropylene (PP), even though the two polymers have quite different chemical structures. PHB exhibits a high degree of crystallinity, has a high melting point of approximately 180°C, and most importantly, unlike PP, PHB is rapidly biodegradable. Two major factors which currently inhibit the widespread use of PHB are its high cost and poor mechanical properties. The production costs of PHB are significantly higher than for plastics produced from petrochemical resources (e.g. PP costs $US1 kg-1, whereas PHB costs $US8 kg-1), and its stiff and brittle nature makes processing difficult and impedes its ability to handle high impact. Lignin, together with cellulose and hemicellulose, are the three main components of every lignocellulosic biomass. It is a natural polymer occurring in the plant cell wall. Lignin, after cellulose, is the most abundant polymer in nature. It is extracted mainly as a by-product in the pulp and paper industry. Although, traditionally lignin is burnt in industry for energy, it has a lot of value-add properties. Lignin, which to date has not been exploited, is an amorphous polymer with hydrophobic behaviour. These make it a good candidate for blending with PHB and technically, blending can be a viable solution for price and reduction and enhance production properties. Theoretically, lignin and PHB affect the physiochemical properties of each other when they become miscible in a composite. A comprehensive study on structural, thermal, rheological and environmental properties of lignin/PHB blends together with neat lignin and PHB is the targeted scope of this thesis. An introduction to this research, including a description of the research problem, a literature review and an account of the research progress linking the research papers is presented in Chapter 1. In this research, lignin was obtained from bagasse through extraction with sodium hydroxide. A novel two-step pH precipitation procedure was used to recover soda lignin with the purity of 96.3 wt% from the black liquor (i.e. the spent sodium hydroxide solution). The precipitation process is presented in Chapter 2. A sequential solvent extraction process was used to fractionate the soda lignin into three fractions. These fractions, together with the soda lignin, were characterised to determine elemental composition, purity, carbohydrate content, molecular weight, and functional group content. The thermal properties of the lignins were also determined. The results are presented and discussed in Chapter 2. On the basis of the type and quantity of functional groups, attempts were made to identify potential applications for each of the individual lignins. As an addendum to the general section on the development of composite materials of lignin, which includes Chapters 1 and 2, studies on the kinetics of bagasse thermal degradation are presented in Appendix 1. The work showed that distinct stages of mass losses depend on residual sucrose. As the development of value-added products from lignin will improve the economics of cellulosic ethanol, a review on lignin applications, which included lignin/PHB composites, is presented in Appendix 2. Chapters 3, 4 and 5 are dedicated to investigations of the properties of soda lignin/PHB composites. Chapter 3 reports on the thermal stability and miscibility of the blends. Although the addition of soda lignin shifts the onset of PHB decomposition to lower temperatures, the lignin/PHB blends are thermally more stable over a wider temperature range. The results from the thermal study also indicated that blends containing up to 40 wt% soda lignin were miscible. The Tg data for these blends fitted nicely to the Gordon-Taylor and Kwei models. Fourier transform infrared spectroscopy (FT-IR) evaluation showed that the miscibility of the blends was because of specific hydrogen bonding (and similar interactions) between reactive phenolic hydroxyl groups of lignin and the carbonyl group of PHB. The thermophysical and rheological properties of soda lignin/PHB blends are presented in Chapter 4. In this chapter, the kinetics of thermal degradation of the blends is studied using thermogravimetric analysis (TGA). This preliminary investigation is limited to the processing temperature of blend manufacturing. Of significance in the study, is the drop in the apparent energy of activation, Ea from 112 kJmol-1 for pure PHB to half that value for blends. This means that the addition of lignin to PHB reduces the thermal stability of PHB, and that the comparative reduced weight loss observed in the TGA data is associated with the slower rate of lignin degradation in the composite. The Tg of PHB, as well as its melting temperature, melting enthalpy, crystallinity and melting point decrease with increase in lignin content. Results from the rheological investigation showed that at low lignin content (.30 wt%), lignin acts as a plasticiser for PHB, while at high lignin content it acts as a filler. Chapter 5 is dedicated to the environmental study of soda lignin/PHB blends. The biodegradability of lignin/PHB blends is compared to that of PHB using the standard soil burial test. To obtain acceptable biodegradation data, samples were buried for 12 months under controlled conditions. Gravimetric analysis, TGA, optical microscopy, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), FT-IR, and X-ray photoelectron spectroscopy (XPS) were used in the study. The results clearly demonstrated that lignin retards the biodegradation of PHB, and that the miscible blends were more resistant to degradation compared to the immiscible blends. To obtain an understanding between the structure of lignin and the properties of the blends, a methanol-soluble lignin, which contains 3× less phenolic hydroxyl group that its parent soda lignin used in preparing blends for the work reported in Chapters 3 and 4, was blended with PHB and the properties of the blends investigated. The results are reported in Chapter 6. At up to 40 wt% methanolsoluble lignin, the experimental data fitted the Gordon-Taylor and Kwei models, similar to the results obtained soda lignin-based blends. However, the values obtained for the interactive parameters for the methanol-soluble lignin blends were slightly lower than the blends obtained with soda lignin indicating weaker association between methanol-soluble lignin and PHB. FT-IR data confirmed that hydrogen bonding is the main interactive force between the reactive functional groups of lignin and the carbonyl group of PHB. In summary, the structural differences existing between the two lignins did not manifest itself in the properties of their blends.

碩士
國立成功大學
材料科學及工程學系
107
Mg-Cu-Gd metallic glass powders were synthesized by Rapid-Solidifying Atomization (RSA). The RSAed powder was fully amorphous shown by X-Ray Diffractometry (XRD), and the glass transition temperature (Tg), crystallization temperature (Tx) and incubation time were determined by Differential Scanning Calorimeter (DSC). The value of Trg and γ were criterion with the glass forming ability (GFA) of Mg-based metallic glass. The Mg-Cu-Gd/Cu ex-situ metallic glass powders is synthesized by electroless plating via different coating time. The bulk Mg-Cu-Gd/Cu ex-situ metallic glass composite is consolidated by hot pressing and backward extrusion. The micro structure is studied by Scanning Electron Microscope(SEM).

碩士
國立成功大學
材料科學及工程學系
105
SUMMARY Mg-Cu-Gd metallic glass powders were synthesized by Rapid-Solidifying Atomization (RSA). The RSAed powder was fully amorphous shown by X-Ray Diffractometry (XRD), and the glass transition temperature (Tg), crystallization temperature (Tx) and incubation time were determined by Differential Scanning Calorimeter (DSC). The value of Trg and γwere criterion with the glass forming ability (GFA) of Mg-based metallic glass. The Mg-Cu-Gd in situ bulk metallic glass composite (BMGC) consolidated by backward extrusion. The microstructure of the stress-induced nano-crystalline/amorphous composites was studied by Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM), and the crystalline phases of the Mg-rich nanocrystals were shown metastable Mg2Cu phase by XRD. Key word: Rapid-Solidifying Atomization, Mg-based BMGC, Nanocrystal, Stress-induced Crystallization

The aim of the present thesis is to explore sustainable low cost environmentally friendly composite materials. It is a step by step experimental research. Firstly, taking under consideration the so far commercial available non-organic materials used as reinforcement and the petroleum based resins used as matrices, composite materials were fabricated and mechanically characterized. Different components in micro- and nano- scale were combined. Afterwards, the non-organic materials used as reinforcements were substituted by different types of non conventional natural-based fillers. The fillers (corn starch and olive pit granules) were in powder form, derived from agricultural local resources and additionally flax fabric used to produce laminated composites. All the semi-green epoxy composites were characterized by means of three-point bending testing. Moreover, the manufactured composites were induced in several sources of damage and their residual properties were extensively investigated. More precisely, the effect of the strain-rate and low velocity impact as well as of thermal fatigue, on the mechanical properties of the olive pit and the flax fabric reinforced resin was studied. Since, conventional and semi-green composite materials were fabricated and experimentally investigated, the final objective of the present thesis was to produce novel green composites materials by substituting the petroleum-based epoxy resin with a biodegradable derived from natural resources biopolyester. In order to accomplish this target, polylactic acid (PLA) was combined with olive pits in powder form at different concentrations. Olive pits, is almost unknown non-traditional filler to composites, obtained during the oil extraction process. It is a raw material characterized by its low cost and its abundance, since it consists a waste product of the olive oil industry. In order to successfully accomplish this part of research, experiments were taken place in France at the CMGD (Centre des Matériaux de Grande Diffusion) Institute of the École Nationale Supérieure des Mines d’ Alés, under the guidance of Prof. A. Bergeret within the framework of research cooperation with the main supervisor of this thesis, Prof. G. Papanicolaou. The most important feature of the present green composites is their satisfactory mechanical and thermal performance in combination with their complete biodegradability. The PLA/olive pit composites could be applied to various components with moderate strength such as automotive interiors, interior building applications, durable goods, serviceware and food packaging material The aim of this part of the study was to investigate the effect of three types of olive pit powder at different weights fractions on the physical and mechanical properties of polylactide (PLA) matrix composites. For the preparation of the powder, two different grinding procedures were applied, producing three types of olive pit powder. Various measurements were accomplished to determine characteristics such as the density and the size distribution and the shape of the powder. Different PLA/ olive pits powder composites were manufactured by extrusion and injection molding. A comparative study between the different composites was made in order to investigate the matrix-filler interactions, occurring between the PLA and olive pit granules and their overall physical, mechanical and thermomechanical properties were investigated by means of TGA, FT-IR, DSC, SEM, flexural and uni-axial tensile testing. Finally, theoretical predictive models were applied in most of the composite materials manufactured in the present work. These models making use of minimal number of experimental results can satisfactorily predict the residual properties of damaged materials, irrespectively of the type of the material investigated and the damage source. Namely, the Modulus Predictive Model (ΜPM), the Residual Properties Model (RPM) and the Residual Strength after Impact Model (RSIM), have been successfully applied. A big number of interesting conclusions have been derived from the present work. However, a general conclusion is that a totally green composite with useful properties and applications is a promising target for the humanity and the planet survivability.
Σκοπός της παρούσας διδακτορικής διατριβής είναι η κατασκευή και μελέτη συνθέτων υλικών χαμηλού κόστους ενισχυμένων με φυσικά υλικά, φιλικά προς το περιβάλλον. Η επίτευξη αυτού του στόχου πραγματοποιήθηκε σταδιακά. Αρχικά, πραγματοποιήθηκε μια εκτεταμένη μελέτη διαφορετικών συνθέτων υλικών τα οποία ήταν εξ’ ολοκλήρου κατασκευασμένα από ανόργανα και συνθετικά υλικά. Γι’ αυτό το σκοπό κατασκευάστηκαν και μελετήθηκαν οι μηχανικές ιδιότητες συνθέτων υλικών που έχουν ως μήτρα μια εμπορικά διαθέσιμη πετροχημική εποξειδική ρητίνη. Η εποξειδική ρητίνη ενισχύθηκε με ανόργανα υλικά σε μικρο- (συμπαγή και κενά σφαιρίδια γυαλίου) και νανο- (νανοσωλήνες άνθρακα πολλαπλού τοιχώματος) διαστάσεις. Στη συνέχεια, βασιζόμενη στο ήδη υπάρχον επιστημονικό υπόβαθρο, καθώς η μεταπτυχιακή μου εργασία ειδίκευσης ήταν στο ίδιο ερευνητικό πεδίο με το αντικείμενο της διδακτορικής μου διατριβής, γίνεται προσπάθεια περαιτέρω εξέλιξης της έρευνας που σχετίζεται με την μελέτη και κατασκευή συνθέτων φιλικών προς το περιβάλλον. Ως εκ τούτου, το επόμενο στάδιο της πειραματικής μελέτης στα πλαίσια εκπόνησης της διατριβής αυτής, ήταν η κατασκευή και χαρακτηρισμός, ως προς την μηχανική τους συμπεριφορά, συνθέτων υλικών πολυμερικής εποξειδικής μήτρας ενισχυμένης με διαφορετικού τύπου φυσικές ενισχύσεις και περιεκτικότητες. Οι φυσικές ενισχύσεις που επιλέχθηκαν να μελετηθούν ήταν τόσο σε μορφή κόκκων και μικρο-ινών, όσο και σε μορφή υφάσματος. Τα εγκλείσματα που χρησιμοποιήθηκαν ήταν σκόνη από κόκκους ελαιοπυρήνα και σκόνη αμύλου καλαμποκιού. Στα σύνθετα υλικά ενισχυμένα με κόκκους ελαιοπυρήνα, έγινε μελέτη της επίδρασης των διαφορετικών ρυθμών παραμόρφωσης στις μηχανικές τους ιδιότητες, ενώ στα σύνθετα υλικά ενισχυμένα με την σκόνη αμύλου μελετήθηκαν εκτενώς οι στατικές μηχανικές τους ιδιότητες. Επιπλέον, κατασκευάστηκαν πολύστρωτα σύνθετα υλικά χρησιμοποιώντας για τις διάφορες στρώσεις ύφασμα από ίνες λιναριού. Τα πολύστρωτα σύνθετα υλικά χαρακτηρίστηκαν ως προς τις μηχανικές τους ιδιότητες, υποβλήθηκαν σε θερμική κόπωση και υπέστησαν κρούση χαμηλής ενέργεια. Οι εναπομένουσες μηχανικές ιδιότητες των υλικών αυτών μελετήθηκαν τόσο πειραματικά όσο και θεωρητικά. Ο απώτερος στόχος αυτής της διδακτορικής διατριβής ήταν να γίνει η δυνατή η κατασκευή συνθέτων υλικών τα οποία να είναι πλήρως βιοδιασπώμενα και φιλικά προς το περιβάλλον. Για το σκοπό αυτό, το τρίτο και τελευταίο στάδιο της έρευνας που διεξήχθη στα πλαίσια της παρούσας διατριβής, ήταν η κατασκευή εξολοκλήρου φυσικών συνθέτων υλικών έχοντας ως μήτρα ένα βιοδιασπώμενο πολυεστέρα φυτικής προέλευσης, το πολύ (γαλακτικό οξύ), ενισχυμένο με σκόνη από κόκκους ελαιοπυρήνα. Ο ξηρός ελαιοπυρήνας που χρησιμοποιήθηκε, αποτελεί μέρος των αποβλήτων που προκύπτουν από την διαδικασία παραγωγής ελαιολάδου. Ο ελαιοπυρήνας σε αυτή την μορφή έχοντας μηδαμινό κόστος απαντάται σε εξαιρετικά μεγάλες ποσότητες και σε σημαντικό ποσοστό εναποτίθεται στους περιβάλλοντα χώρους των μονάδων παραγωγής του ελαιολάδου. Η ερευνητική εργασία που σχετίζεται με αυτό το αντικείμενο του διδακτορικού έλαβε χώρα στην Γαλλία στο École Nationale Supérieure des Mines d’ Alés, στο ερευνητικό ινστιτούτο CMGD (Centre des Matériaux de Grande Diffusion) υπό την επίβλεψη της καθηγήτριας A. Bergeret, στα πλαίσια ερευνητικής συνεργασίας του επιβλέποντα καθηγητή Γ. Παπανικολάου και της ερευνητικής του ομάδας. Τα πειράματα που διεξήχθησαν στο ερευνητικό ινστιτούτο CMGD, περιελάμβαναν αρχικά την προετοιμασία των κόκκων του ελαιοπυρήνα στην κατάλληλη μορφή για να είναι δυνατή η χρησιμοποίησή τους ως ενισχυτικό υλικό. Έγινε κονιορτοποίηση των κόκκων από την οποία προέκυψαν δύο τύπου σκονών που διέφεραν ως προς την διασπορά του μεγέθους των κόκκων, ενώ μια τρίτη σκόνη ελαιοπυρήνα είχε ήδη προετοιμαστεί με διαφορετική μέθοδο κονιορτοποίησης στο τμήμα Επιστήμης των Υλικών του Πανεπιστήμιου Πατρών. Έγινε εκτενής χαρακτηρισμός των φυσικών και μορφολογικών ιδιοτήτων όλων των σκονών ελαιοπυρήνα που χρησιμοποιήθηκαν για την κατασκευή των συνθέτων υλικών με μήτρα το PLA. Προσδιορίστηκαν διαφορετικού τύπου πυκνότητες και η διασπορά του μεγέθους των κόκκων. Έγινε θερμική ανάλυση με δοκιμή θερμοζυγού (TGA), μορφολογικός χαρακτηρισμός με χρήση ηλετρονικού μικροσκοπίου σάρωσης (SEM) καθώς και χαρακτηρισμός με φασματοσκοπία υπερύθρου με μετασχηματισμό Fourier (FT IR) και ακτίνων-Χ. Αφού ολοκληρώθηκε ο χαρακτηρισμός των ιδιοτήτων της ενισχυτικής φάσης, στη συνέχεια κατασκευάστηκαν σύνθετα υλικά μήτρας PLA ενισχυμένα με τους κόκκους ελαιοπυρήνα σε διαφορετικές περιεκτικότητες. Η προετοιμασία των σύνθετων αυτών υλικών πραγματοποιήθηκε σε δύο στάδια. Αρχικά έγινε μια πρώτη μορφοποίηση με εξώθηση (extrusion). Τα σύνθετα υλικά που προέκυψαν από την εξώθηση που ήταν στη μορφή δισκίων (pellets) χαρακτηρίστηκαν και αυτά με διάφορες τεχνικές (WAXD, DSC, TGA). Τα σύνθετα υλικά υπό μορφή δισκίων για να αποκτήσουν την τελική τους μορφή ως δοκίμια κατάλληλα για μηχανικές δοκιμές κατά τα πρότυπα ISO 527, μορφοποιήθηκαν με έγχυση (Injection molding). Τα σύνθετα υλικά στην τελική τους μορφή χαρακτηρίστηκαν με διάφορες τεχνικές (WAXD, DSC, TGA), έγινε χαρακτηρισμός των μηχανικών τους ιδιοτήτων και μορφολογική παρατήρηση των επιφανειών τους ύστερα από την μηχανική τους αστοχία (SEM). Τέλος, σε πολλά από τα σύνθετα υλικά που κατασκευάστηκαν και μελετήθηκαν πειραματικά, εφαρμόστηκαν διαφορετικά ημιεμπειρικά μοντέλα ανάλυσης και πρόβλεψης της μηχανικής τους συμπεριφοράς. Στο κυρίως κείμενο της διδακτορικής διατριβής, περιγράφεται σε ξεχωριστό κεφάλαιο το σύνολο των θεωρητικών μοντέλων που εφαρμόστηκαν στα πειραματικά αποτελέσματα. Στα επιμέρους κεφάλαια που παρουσιάζονται και αναλύονται τα πειραματικά αποτελέσματα, παρατίθενται η σύγκρισή τους με τις αντίστοιχες προβλέψεις που πρόεκυψαν από την εφαρμογή των θεωρητικών μοντέλων. Από τη σύγκριση αυτή παρατηρούμε ότι τα θεωρητικά μοντέλα που εφαρμόστηκαν που είναι το μοντέλο πρόβλεψης του μέτρου ελαστικότητας κοκκωδών υλικών, ΜPM (Modulus Predictive Model), το μοντέλο πρόβλεψης της υποβάθμισης ιδιοτήτων ύστερα από διαφορετικές είδους καταπονήσεις (θερμική κόπωση, κρούση χαμηλής ενέργειας και του ρυθμού παραμόρφωσης σε κάμψη τριών σημείων), RPM (Residual Properties Model) και το μοντέλο πρόβλεψης της υποβάθμισης της αντοχής των υλικών ύστερα από κρούση, Residual Strength after Impact Model (RSIM), έδωσαν ικανοποιητικές προβλέψεις για την μεταβολή των ιδιοτήτων κάνοντας χρήση ελάχιστων μόνο πειραματικών σημείων. Στην παρούσα διατριβή συνδυάστηκαν δύο διαφορετικού τύπου πολυμερικές ρητίνες με πληθώρα ενισχυτικών υλικών για την κατασκευή και μελέτη της μηχανικής τους συμπεριφοράς, τόσο πειραματικά όσο και θεωρητικά με την εφαρμογή ημιεμπειρικών μοντέλων πρόβλεψης και ανάλυσης. Για την κατασκευή των δοκιμίων, ανάλογα με τον τύπο του υλικού της μήτρας και της ενίσχυσης, εφαρμόστηκαν διαφορετικές τεχνικές και σύνθετες πειραματικές διαδικασίες. Ενώ, για την μελέτη των μηχανικών, θερμομηχανικών και μορφολογικών τους ιδιοτήτων εφαρμόστηκε σημαντικός αριθμός διαφορετικών τεχνικών χαρακτηρισμού.