The composites industry can be positively influenced by composite materials that are processed faster, are lighter in weight, are higher in stiffness and strength, and that are more recyclable. There has been considerable interest in the use of thermotropic liquid crystalline polymers (TLCPs) to reinforce thermoplastic materials. In a novel process developed by Baird and coworkers, wholly thermoplastic composites are produced via a patented, dual extrusion process. This unique process yields a fiber which consists of numerous continuous fibrils of the liquid crystalline polymer encased in a thermoplastic matrix. These fibers have been used to form random mats and woven pre-forms, which have then been compression molded to form composite parts. Because of the high cost associated with these thermotropic liquid crystalline polymers and the desire to generate recyclable composites, a process was developed in this research to separate the liquid crystalline component from polypropylene (PP) composites. The overall objectives of this work were to develop a process to reclaim the liquid crystalline component of these thermoplastic composites, to determine the effect the process had on the properties of the reclaimed liquid crystalline polymer, and finally to determine whether or not the reclaimed liquid crystalline polymer could be used again to generate a reinforcing component. An ancillary objective was to see if the polypropylene could also be reclaimed, and if it had further use as a polymeric resin. In the present work, a novel process was developed that allows the liquid crystalline component to be reclaimed for further use in the composite material or in other applications that require thermotropic liquid crystalline polymers. The polypropylene component, which has undergone molecular weight reduction, can also be reclaimed by this process. This process consisted of using an organic peroxide and reactive extrusion to selectively degrade only the polypropylene, and not the thermotropic liquid crystalline polymer. The degraded polypropylene was selectively dissolved away from the liquid crystalline polymer by stirring the extruded melt in boiling mineral oil. The remaining solids, of thermotropic liquid crystalline polymer, were collected via centrifugation, cleaned of the mineral oil by boiling in kerosene, and then dried in a convection oven. The purity of the reclaimed thermotropic liquid crystalline polymer was determined by density measurements, while the physical properties of the reclaimed material were determined by rheological tests. The mechanical properties were determined via Instron testing of injection molded plaques made from mixtures of reclaimed material and pure thermotropic liquid crystalline polymer. From this work, it was found that over 70 wt% of the thermotropic liquid crystalline polymer, DuPont HX8000, could be successfully separated from the polypropylene to a degree of 96.0%. From Instron testing, it was found that up to 40 wt% of the reclaimed HX8000 could be blended with the pure HX8000, with no loss in mechanical properties. Furthermore, it was seen that up to 83 % of the HX8000 component (40 wt%) of PP 6523 (60 wt%) composites could be replaced with reclaimed HX8000 without seeing any losses in mechanical properties. It was also found that the degraded polypropylene could be successfully separated, via centrifugation at a temperature of 253 K, and could be potentially used as resin for non-wovens. The projected material cost of the reclaimed HX8000, based on the ability to purchase and to process in bulk, was determined to be 90 % less than the virgin HX8000. / Master of Science

Dealloying is a corrosion process in which one or more elements are selectively removed from an alloy leading to a 3-dimensional porous structure of the more noble element(s). These porous structures have been known to cause stress corrosion cracking in noble metal alloy systems but more recent interest in using the corrosion process to produce porous metals has developed. Applications for these structures range from high surface area electrodes for biomedical sensors to use as skeletal structures for fundamental studies (e.g. low temperature heat exchangers or sensitivity of surface diffusivity to chemical environment). In this work we will review our current understanding of alloy corrosion including our most recent results demonstrating a more accurate method for calculating alloy critical potential based on potential hold experiments. The critical potentials calculated through the potential hold method were â 0.030VMSE, 0.110VMSE, and 0.175VMSE for Cu80Pt20, Cu75Pt25 Cu71Pt29 respectively. We will present the use of porous metals for making surface diffusivity measurements in the Pt systems as a function of chemical environment. A review of the use of small angle neutron scattering to make accurate measurements of pore size is presented and the sensitivity of pore size to electrolyte, electrolyte composition, applied potential and temperature will be explained. The production of porous Pt with pore sizes ranging from 2-200nm is demonstrated. / Ph. D.

Selective dissolution also known as dealloying is a corrosion process in which one component of a binary alloy system is selectively removed through an electrochemically controlled process which leads to the formation of a porous metal "sponge" with a porosity that is completely interconnected and random in direction. Nanoporous metals are desirable since they have larger surface areas than an equal volume of non-porous material. Because of their enormous surface area per volume, these highly porous metal electrodes are superior materials for high surface area applications such as in biomedical devices, microfilters and catalysts. Understanding the kinetic processes governing the development of porosity during dealloying and having ability to change the electrochemical conditions will allow us to better control over the average ligament size and distribution in porosity. The basic kinetic processes involved in the formation of these structures are related to such issues as environmental effects and electrochemical conditions on diffusion, microscopic coarsening phenomenon at room temperature and elevated temperatures, alloy passivation, and Gibbs-Thomson effects. The average pore size and distribution was found to depend on the electrolyte composition, dealloying rate, applied potential and time. The porosity was found to significantly coarsen at room temperature during the dealloying process and this coarsening was highly dependent on the applied potential. It is showed that the commonly accepted measurement of the critical potential for alloy dissolution calculated based on extrapolation of anodic polarization data results in an overestimation of this quantity. A series of constant applied potential experiments prove to be a more accurate method for critical potential determination. / Ph. D.

L’objectif de cette étude e est de comprendre le processus de déalliage de l’acier inoxydable austénitique 304L avec l’intention de transcrire ce raisonnement aux aciers duplex. Des essais ont été réalisés au sein d’une solution aqueuse désaérée d’hydroxyde de sodium à 50%, portés à une température de 80°C sous pression atmosphérique et à potentiel libre. - L’alliage 304L se dissout en formant une couche nanoporeuse riche en nickel métallique sur sa surface. - L’alliage 2202 se dissout et présente deux comportements différents : o la ferrite s’appauvrit en nickel o l’austénite se recouvre d’une couche nanoporeuse constituée de nickel métallique. o les deux phases ont des vitesses de dissolution distinctes, l’austénite se dissolvant plus rapidement que la ferrite. Les cinétiques de dissolution des deux alliages sont différentes : l’alliage 2202 présente une meilleure résistance à la corrosion que l’alliage 304L. Cependant l’austénite de l’alliage 2202 se comporte de manière identique à l’alliage 304L et présente les mêmes caractéristiques. La ferrite semble conférer à l’alliage duplex une protection contre la corrosion caustique au détriment de l’austénite.La mise en évidence de la couche du nickel métallique presque pur est confrontée avec des modèles existants de déalliage. Des expériences complémentaires ont prouvées la simultanéité des étapes de dissolution de l'alliage, de la redéposition des atomes de Ni et de leur réarrangement sur la surface. / The aim of this study is to understand the process of dealloying of austenitic stainless steel 304L with the intention to put this reasoning to the duplex steels. Tests were conducted in a deaerated aqueous solution of sodium hydroxide at 50%, heated to a temperature of 80°C at atmospheric pressure and free potential. • The alloy 304L is dissolved to form a nanoporous layer rich in nickel metal on its surface. • The alloy 2202 is dissolved and has two different behaviors: o Ferritic phase is depleted in nickel o Austenite is covered by a nanoporous layer consists of metallic nickelo The two phases have different dissolution rates: austenite dissolves faster than ferrite. Kinetic dissolution of two alloys is different: alloy 2202 has better corrosion resistance than alloy 304L. However, the behavior of the austenite of the alloy 2202 is identical to the alloy 304L and has the same characteristics. The ferrite appears to give the duplex alloy corrosion protection against caustic at the expense of austenite. The identification of the layer of almost pure metallic nickel is confronted with existing models of dealloying. Additional experiments proved the simultaneous steps of dissolution of the alloy, redeposition of Ni atoms and their rearrangement on the surface.

A gênese, a química, a macro e micromorfologia dos solos desenvolvidos nos ambientes arenosos da planície costeira do Estado de São Paulo foram investigadas. Nesses ambientes, genericamente denominados de restinga, a podzolização é o processo pedogenético predominante, sendo os Espodossolos e Neossolos Quartzarênicos os solos mais comumente encontrados. Os municípios paulistas de Cananéia, Ilha Comprida e Bertioga foram selecionados para o desenvolvimento desta pesquisa devido à presença de diferentes unidades sedimentares, de vegetação remanescente e de solos, representativos da planície costeira do Estado de São Paulo. Nesses locais foram descritos e amostrados 31 perfis, muitos deles em cronosseqüência. A idade dos sedimentos e da matéria orgânica de horizontes cimentados selecionados (ortstein) também foram investigadas e, juntamente às análises químicas, incluindo procedimentos de dissolução seletiva do Fe e Al (DC, oxalato e pirofosfato para Fe e Al; NaOH, KCl, LaCl3 e CuCl2 para Al) e às micromorfológicas, permitiram concluir que: (a) os Espodossolos mais evoluídos e antigos, dotados de horizontes ortstein, podem ser considerados indicadores dos sedimentos pleistocênicos da Formação Cananéia das planícies costeiras quaternárias estudadas e, possivelmente, são paleossolos; (b) o tempo e o relevo foram os principais fatores de formação, condicionantes da diferenciação dos Espodossolos na paisagem; (c) os solos mais antigos, bem drenados devido às condições de relevo e dinâmica sedimentar (Ilha de Cananéia e Bertioga), apresentam grande variabilidade e diversidade de seus horizontes e atributos morfológicos, diferindo daqueles mais jovens e mal drenados, mais homogêneos, geralmente destituídos de horizonte Bs (Bertioga); (d) a química da maioria dos solos estudados são típicas daqueles já descritos para as áreas sob vegetação de restinga: baixas soma e saturação por bases, extremamente a fortemente ácidos, capacidade de troca de cátions dependente da matéria orgânica e saturada com Al trocável, aumento do carbono orgânico em profundidade; (e) o Al é o principal cátion envolvido na podzolização, sendo que suas formas ativas são: complexos de Alhúmus e compostos inorgânicos pouco cristalinos. Os primeiros predominam nos horizontes superficiais e horizontes espódicos hidromórficos; as formas inorgânicas se relacionam a alguns horizontes espódicos (Bs, Bh, Bhs e Bsm) situados na base de perfis bem drenados; (f) Al inorgânico pouco cristalino também foi extraído pelos reagentes pirofosfato e CuCl2, geralmente utilizados para avaliar Al unido à matéria orgânica; ao contrário, LaCl3 extraiu apenas as formas ativas da interação Al-húmus, sendo que KCl não incluiu todas essas formas reativas; (g) a decomposição de raízes in situ e, sobretudo, os processos de formação e transporte de complexos Al-húmus foram observados em alguns (decomposição de raízes) ou em todos os perfis estudados (complexos Al-húmus), originando os horizontes espódicos às expensas dos eluviais; (h) a imobilização desses complexos se dá por diferentes mecanismos: filtragem físicomecânica dos poros do solo, aumento do pH em profundidade, incorporação adicional de Al durante seu transporte e o efeito da absorção seletiva das raízes. Neste último processo, as raízes absorvem seletivamente água e nutrientes, segregando e precipitando ao seu redor os complexos Al-húmus da solução do solo, mobilizados dos horizontes superiores ou presentes nas águas de drenagem. / The genesis, chemistry and macro and micromorphology of soils developed on the sandy coastal plain of the São Paulo State were investigated. In these environments, often designated restinga, podzolization is the main pedogenetic process, being Spodosols and Quartzipsamments the soils most commonly found. Cananéia, Ilha Comprida and Bertioga cities were selected for the development of this research due to the representativeness of this environmental condition in the São Paulo State. In these environments 31 soil profiles were described and sampled, mainly in chronosequences. Age of sediments and of organic matter of cemented horizons (ortstein) were investigated as well. These data associated to the chemical analysis, including Fe and Al selective dissolution procedures (dithionite-citrate, oxalate and pyrophosphate for Fe and Al; NaOH, KCl, LaCl3 and CuCl2 for Al) and micromorphological analysis allowed the following conclusions: (a) the most developed Spodosols have ortstein horizons and can be considered indicators of sediments of Pleistocene age from the Cananéia Formation of the studied quaternary coastal plain and possibly are paleosols; (b) time and relief were the main soil formation factors responsible for differentiation of Spodosols on the landscape; (c) the oldest and well drained soils due to relief conditions and sedimentary dynamics (Cananéia and Bertioga) showed great variability and diversity of their horizons and morphological properties, differing from the youngest, poorly drained and more homogeneous Spodosols usually without Bs horizon (Bertioga). The youngest and well drained Spodosols (Ilha Comprida) showed an advanced degree of degradation; (d) the chemical properties of the studied soils are similar to other soils already described in the restinga: low in exchangeable bases, low in base saturation, strongly acidic, organic-matter dependent and Al-saturated CEC, increase in organic carbon with depth; (e) Al is main metal related to the podzolization process. The reactive forms of this element are Al-humus complexes and inorganic poorly crystalline compounds. Alhumus complexes predominate in the superficial and spodic, poorly drained horizons; the Alinorganic forms occur in some well drained spodic horizons (Bs, Bh, Bhs and Bsm) situated at the bottom of the well-drained soil profiles; (f) Al inorganic, poorly crystalline forms were extracted by pyrophosphate and CuCl2 reagents, usually used to determinate Al bound to organic matter; unlike, LaCl3 only extracted the reactive forms of Al-humus interaction, whereas KCl did not include these reactive forms; (g) Al-humus formation and mobilization were the main pedogenetic processes, but roots decomposition were observed in some horizons; (h) different mechanisms are related to Al-humus complexes immobilization: physical-mechanical filtering effect on soil pores, precipitation as pH increases with depth, precipitation with the decrease of C-to-metal ratio during organic matter complexation and roots selective absorption effect. In the latter, there is selective absorption of water and nutrients with segregation and precipitation of Al-humus complexes around roots. These Al-humus complexes are either mobilized from the superficial horizons or already dissolved in the draining water.

A gênese, a química, a macro e micromorfologia dos solos desenvolvidos nos ambientes arenosos da planície costeira do Estado de São Paulo foram investigadas. Nesses ambientes, genericamente denominados de restinga, a podzolização é o processo pedogenético predominante, sendo os Espodossolos e Neossolos Quartzarênicos os solos mais comumente encontrados. Os municípios paulistas de Cananéia, Ilha Comprida e Bertioga foram selecionados para o desenvolvimento desta pesquisa devido à presença de diferentes unidades sedimentares, de vegetação remanescente e de solos, representativos da planície costeira do Estado de São Paulo. Nesses locais foram descritos e amostrados 31 perfis, muitos deles em cronosseqüência. A idade dos sedimentos e da matéria orgânica de horizontes cimentados selecionados (ortstein) também foram investigadas e, juntamente às análises químicas, incluindo procedimentos de dissolução seletiva do Fe e Al (DC, oxalato e pirofosfato para Fe e Al; NaOH, KCl, LaCl3 e CuCl2 para Al) e às micromorfológicas, permitiram concluir que: (a) os Espodossolos mais evoluídos e antigos, dotados de horizontes ortstein, podem ser considerados indicadores dos sedimentos pleistocênicos da Formação Cananéia das planícies costeiras quaternárias estudadas e, possivelmente, são paleossolos; (b) o tempo e o relevo foram os principais fatores de formação, condicionantes da diferenciação dos Espodossolos na paisagem; (c) os solos mais antigos, bem drenados devido às condições de relevo e dinâmica sedimentar (Ilha de Cananéia e Bertioga), apresentam grande variabilidade e diversidade de seus horizontes e atributos morfológicos, diferindo daqueles mais jovens e mal drenados, mais homogêneos, geralmente destituídos de horizonte Bs (Bertioga); (d) a química da maioria dos solos estudados são típicas daqueles já descritos para as áreas sob vegetação de restinga: baixas soma e saturação por bases, extremamente a fortemente ácidos, capacidade de troca de cátions dependente da matéria orgânica e saturada com Al trocável, aumento do carbono orgânico em profundidade; (e) o Al é o principal cátion envolvido na podzolização, sendo que suas formas ativas são: complexos de Alhúmus e compostos inorgânicos pouco cristalinos. Os primeiros predominam nos horizontes superficiais e horizontes espódicos hidromórficos; as formas inorgânicas se relacionam a alguns horizontes espódicos (Bs, Bh, Bhs e Bsm) situados na base de perfis bem drenados; (f) Al inorgânico pouco cristalino também foi extraído pelos reagentes pirofosfato e CuCl2, geralmente utilizados para avaliar Al unido à matéria orgânica; ao contrário, LaCl3 extraiu apenas as formas ativas da interação Al-húmus, sendo que KCl não incluiu todas essas formas reativas; (g) a decomposição de raízes in situ e, sobretudo, os processos de formação e transporte de complexos Al-húmus foram observados em alguns (decomposição de raízes) ou em todos os perfis estudados (complexos Al-húmus), originando os horizontes espódicos às expensas dos eluviais; (h) a imobilização desses complexos se dá por diferentes mecanismos: filtragem físicomecânica dos poros do solo, aumento do pH em profundidade, incorporação adicional de Al durante seu transporte e o efeito da absorção seletiva das raízes. Neste último processo, as raízes absorvem seletivamente água e nutrientes, segregando e precipitando ao seu redor os complexos Al-húmus da solução do solo, mobilizados dos horizontes superiores ou presentes nas águas de drenagem. / The genesis, chemistry and macro and micromorphology of soils developed on the sandy coastal plain of the São Paulo State were investigated. In these environments, often designated restinga, podzolization is the main pedogenetic process, being Spodosols and Quartzipsamments the soils most commonly found. Cananéia, Ilha Comprida and Bertioga cities were selected for the development of this research due to the representativeness of this environmental condition in the São Paulo State. In these environments 31 soil profiles were described and sampled, mainly in chronosequences. Age of sediments and of organic matter of cemented horizons (ortstein) were investigated as well. These data associated to the chemical analysis, including Fe and Al selective dissolution procedures (dithionite-citrate, oxalate and pyrophosphate for Fe and Al; NaOH, KCl, LaCl3 and CuCl2 for Al) and micromorphological analysis allowed the following conclusions: (a) the most developed Spodosols have ortstein horizons and can be considered indicators of sediments of Pleistocene age from the Cananéia Formation of the studied quaternary coastal plain and possibly are paleosols; (b) time and relief were the main soil formation factors responsible for differentiation of Spodosols on the landscape; (c) the oldest and well drained soils due to relief conditions and sedimentary dynamics (Cananéia and Bertioga) showed great variability and diversity of their horizons and morphological properties, differing from the youngest, poorly drained and more homogeneous Spodosols usually without Bs horizon (Bertioga). The youngest and well drained Spodosols (Ilha Comprida) showed an advanced degree of degradation; (d) the chemical properties of the studied soils are similar to other soils already described in the restinga: low in exchangeable bases, low in base saturation, strongly acidic, organic-matter dependent and Al-saturated CEC, increase in organic carbon with depth; (e) Al is main metal related to the podzolization process. The reactive forms of this element are Al-humus complexes and inorganic poorly crystalline compounds. Alhumus complexes predominate in the superficial and spodic, poorly drained horizons; the Alinorganic forms occur in some well drained spodic horizons (Bs, Bh, Bhs and Bsm) situated at the bottom of the well-drained soil profiles; (f) Al inorganic, poorly crystalline forms were extracted by pyrophosphate and CuCl2 reagents, usually used to determinate Al bound to organic matter; unlike, LaCl3 only extracted the reactive forms of Al-humus interaction, whereas KCl did not include these reactive forms; (g) Al-humus formation and mobilization were the main pedogenetic processes, but roots decomposition were observed in some horizons; (h) different mechanisms are related to Al-humus complexes immobilization: physical-mechanical filtering effect on soil pores, precipitation as pH increases with depth, precipitation with the decrease of C-to-metal ratio during organic matter complexation and roots selective absorption effect. In the latter, there is selective absorption of water and nutrients with segregation and precipitation of Al-humus complexes around roots. These Al-humus complexes are either mobilized from the superficial horizons or already dissolved in the draining water.

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.

Scaling in green liquor handling systems is a persistent problem in many kraft mills. Scaling is commonly believed to be the result of pirssonite (Na2Ca(CO3)2∙2H2O) deposition. In this work, scale characterization was performed by analyzing 12 scale samples obtained from 10 kraft mills. Only 4 samples were identified as pirssonite while the remaining consisted of CaCO3. The predominant presence of CaCO3 in the scale samples was found to be the result of selective dissolution of Na2CO3 from pirssonite scale, leaving CaCO3 behind. Experimental studies were also conducted to study pirssonite solubility under green liquor conditions. Results obtained from these studies were used to create and validate a database for pirssonite in the OLI Systems® software to predict its formation. This database was used to generate a family of pirssonite solubility curves that can be used by the kraft mills as operational guidelines to prevent pirssonite precipitation.

Scaling in green liquor handling systems is a persistent problem in many kraft mills. Scaling is commonly believed to be the result of pirssonite (Na2Ca(CO3)2∙2H2O) deposition. In this work, scale characterization was performed by analyzing 12 scale samples obtained from 10 kraft mills. Only 4 samples were identified as pirssonite while the remaining consisted of CaCO3. The predominant presence of CaCO3 in the scale samples was found to be the result of selective dissolution of Na2CO3 from pirssonite scale, leaving CaCO3 behind. Experimental studies were also conducted to study pirssonite solubility under green liquor conditions. Results obtained from these studies were used to create and validate a database for pirssonite in the OLI Systems® software to predict its formation. This database was used to generate a family of pirssonite solubility curves that can be used by the kraft mills as operational guidelines to prevent pirssonite precipitation.

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.