Dissertations / Theses on the topic 'Powders characterization'

Microcalorimetric measurements and contact angle measurements were conducted to study the surface chemistry of powdered minerals. The contact angle measurements were conducted on both flat and powdered talc samples, and the results were used to determine the surface free energy components using Van Oss-Chaudhury-Good (OCG) equation. It was found that the surface hydrophobicity of talc increases with decreasing particle size. At the same time, both the Lifshitz-van der Waals (gSLW) and the Lewis acid-base (gSAB) components (and, hence, the total surface free energy (gS)) decrease with decreasing particle size. The increase in the surface hydrophobicity and the decrease in surface free energy (gS) can be attributed to preferential breakage of the mineral along the basal plane, resulting in the exposure of more basal plane surfaces to the aqueous phase. Heats of immersion measurements were conducted using a flow microcalorimeter on a number of powdered talc samples. The results were then used to calculate the contact angles using a rigorous thermodynamic relation. The measured heat of immersion values in water and calculated contact angles showed that the surface hydrophobicity of talc samples increase with decreasing particle size, which agrees with the direct contact angle measurements. A relationship between advancing water contact angle qa, and the heat of immersion (-DHi) and surface free energies was established. It was found that the value of -DHi decrease as qa increases. The microcalorimetric and direct contact angle measurements showed that acid-base interactions play a crucial role in the interaction between talc and liquid. Using the Van Oss-Chaudhury-Goodâ s surface free energy components model, various talc powders were characterized in terms of their acidic and basic properties. It was found that the magnitude of the Lewis electron donor, gS-, and the Lewis electron acceptor, gS+, components of surface free energy is directly related to the particle size. The gS- of talc surface increased with decreasing particle size, while the gS+ slightly decreased. It was also found that the Lewis electron-donor component on talc surface is much higher than the Lewis electron-acceptor component, suggesting that the basal surface of talc is basic. The heats of adsorption of butanol on various talc samples from n-heptane solution were also determined using a flow microcalorimeter. The heats of adsorption values were used to estimate % hydrophilicity and hydrophobicity and the areal ratios of the various talc samples. In addition, contact angle and heat of butanol adsorption measurements were conducted on a run-of-mine talc sample that has been ground to two different particle size fractions, i.e., d50=12.5 mm and d50=3.0 mm, respectively. The results were used to estimate the surface free energy components at the basal and edge surfaces of talc. It was found that the total surface free energy (gS) at the basal plane surface of talc is much lower than the total surface free energy at the edge surface. The results suggest also that the basal surface of talc is monopolar basic, while the edge surface is monopolar acidic. The results explain why the basicity of talc surface increases with decreasing particle size as shown in the contact angle and microcalorimetric measurements. Furthermore, the effects of the surface free energies of solids during separation from each other by flotation and selective flocculation were studied. In the present work, a kaolin clay sample from east Georgia was used for the beneficiation tests. First, the crude kaolin was subjected to flotation and selective flocculation experiments to remove discoloring impurities (i.e., anatase (TiO2) and iron oxides) and produce high-brightness clay with GE brightness higher than 90%. The results showed that a clay product with +90% brightness could be obtained with recoveries (or yields) higher than 80% using selective flocculation technique. It was also found that a proper control of surface hydrophobicity of anatase is crucially important for a successful flotation and selective flocculation process. Heats of immersion, heats of adsorption and contact angle measurements were conducted on pure anatase surface to determine the changes in the surface free energies as a function of the surfactant dosage (e.g. hydroxamate) used for the surface treatment. The results showed that the magnitude of the contact angle and, hence, the surface free energy and its components on anatase surface varies significantly with the amount of surfactant used for the surface treatment.
Ph. D.

Uranoxid (UOx) är ett energitätt material som ofta används i kärnbränsle. UOx-pulver pressas och sintras för att tillverka urandioxidkutsar som förs in i bränslestavar. Stavarna monteras slutligen ihop till ett bränsleknippe. Tillverkningsprocessens stabilitet och förutsägbarhet är viktiga. För att åstadkomma önskvärda egenskaper hos UO2-kutsarna är karaktärisering av UOx-pulvret centralt. Sintringsaktivitet är den viktigaste egenskapen när det kommer till att beskriva hur UOx-pulvret beter sig vid reduktion i högtemperatursintring. Återcyklat UO2 oxideras till U3O8 och kan användas till att styra sintringsaktiviteten tack vare dess porbildande egenskaper. Denna rapport beskriver karaktäriseringen av UOx-pulver och kuts med avseende på fysiokemiska egenskaper relaterade till sintringsaktivitet. Statistiska analyser av historiska data utfördes även och visade på en komplex relation mellan pulveregenskaper och sintringsaktivitet. Effekten av U3O8-pulver i blandningar av UO2-pulver med hög och låg sintringsaktivitet undersöktes. Att variera U3O8-batch hade ingen inverkan på diameterkrympning efter sintring utom i ett fall. Blandningar av UO2-pulver visade på avvikande egenskaper jämfört med det jungfruliga pulvret. UO2-pulvrets kemiska aktivitet undersöktes via oxidering med H2O2. Förbrukningshastigheten av H2O2 var densamma för hög- och lågaktiva UO2-pulver vid samma förhållande mellan specifik yta och lösningsvolym.
Uranium oxide (UOx) is an energy dense material commonly used in nuclear fuel. UOx powder is pressed and sintered to produce uranium dioxide (UO2) pellets which are loaded into fuel rods. The rods are then mounted together in a final nuclear fuel assembly. Stability and predictability of the manufacturing processes during UO2 pellet production is of high importance. To achieve desired properties and quality of the UO2 pellets, the ability to assess the characteristics of the UOx powder is crucial. Sinterability is the most important characteristic which describes the behavior of the UOx powder during reduction in high temperatures. Recycled uranium dioxide is oxidized into U3O8 powder which can be used to modify the sinterability due to its pore forming ability. This study describes the characterization of uranium oxide powders and pellets regarding physicochemical properties relating to sintering behavior. Statistical analyses of historical data were also performed and showed a complexity of the relation between powder properties and  sinterability. The effect of U3O8 powder in different blends of UO2 powders of high and low sinterability were analyzed. Varying U3O8 powder batch did not influence the diameter shrinkage after sintering except for one case. UO2 powder blends showed deviating behavior from their virgin powder constituents. Chemical activity of UO2 was analyzed by oxidation with H2O2. The consumption rate of H2O2 was shown to be equal for active and incative UO2 powders under equal specific surface area/solution volume ratio.

Electrolyte and pyrotechnic pellets are two important components of thermal batteries. Both electrolyte and pyrotechnic pellets are produced by cold compaction of constituent powders. These compacts are integrated in the battery as pellets with sufficient green density, green strength, calorific energy and burning rate (for pyrotechnic only) to provide high performance batteries. In this study, effects of physical properties of the used powders such as particle size distribution, average particle size, particle shape and composition of components and applied compression pressure and their interactions on green density and green strength of electrolyte pellets and in addition, calorific energy and burning rate of pyrotechnic pellets were examined. Statistical experimental designs were constructed to investigate the main and interaction effects of studied variables. 24 two factorial statistically designed experiments&rsquo
results for pyrotechnic pellets exhibited that the compression pressure and iron powder morphology were the most significant factors improving green density and break strength of pyrotechnic pellets. It was shown that the compression pressure had a negative effect on burning rate. Both calorific output and burning rate were increased significantly by increasing KClO4 fraction. In addition, decreasing particle size of KClO4 had also a positive effect on burning rate. The maximum calorific output was obtained at maximum KClO4 fraction. 23 two factorial statistically designed green strength and green density experiments&rsquo
results of electrolyte pellets revealed that, compression pressure was again the dominating factor. Moreover, there was a tendency for higher green density with lower MgO fraction and electrolyte powder average particle size. Besides, the positive effect of decreasing average particle size on green strength was investigated distinctly at low green density values. From the thermal battery perspective, main and interaction effects of variables on the characteristics of electrolyte and pyrotechnic pellets were successfully examined.

Extensive attention has been paid to consolidate nanoparticles into nanocrystalline components that possess better properties than their coarse-grained counterparts. Nanocrystalline monolithic tungsten (W) has been envisaged to possess better properties than coarse-grained tungsten and to improve the performance of many military components. Commercially available nano-W powders were characterized via X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and Brunauer, Emmett, and Teller (BET) measurement. While the bulk of nano-W powders consisted of bcc-W as confirmed by XRD and TEM, much of their surface consisted of WO3 with traces of WO2 and WC. Despite the irregular morphology and agglomerates greater than 1 m in size, the diameter of individual nano-W powders ranged from 30 to 100 nm with a surface area of 10.4 m2/g. To obtain green bodies of higher densities and more homogeneous microstructures after consolidation, W nanopowders were de-agglomerated in water and slip cast in plaster molds. De-agglomeration in water was conducted by repeated ultrasonication, washing, centrifuge and pH adjustment. The change in particle size and morphology was examined via SEM. After the initial surface oxide was removed by repeated washing, the reactivity of W nanoparticles to water was somewhat inhibited. Increasing the number of cycles for ultrasonication and washing increased the pH, the degree of de-agglomeration and the stability of W suspension. The zeta potential was more negative with increasing pH and most negative at pH values close to 5. Viscosity also decreased with increasing pH and reached a minimum at a pH 5. To obtain the highest solid loading with the lowest viscosity, the pH value of W suspension was adjusted to 5 using aqueous tetramethylammonium hydroxide solutions. The relative density of the slip cast increased with longer ultrasonic time, increasing slurry pH up to 5, and consequent increase in solids loading. Smaller particles were separated from larger ones by ultrasonication, washing with water and centrifugation. At a 27.8 vol.% solids loading, the size-separated fine W slurry was slip cast into pellets with relative green densities up to 41.3 % and approximate particle sizes of 100 nm. W powders were also ultrasonicated in aqueous poly (ethyleneimine) (PEI) solutions with various concentrations. SEM examinations of particle sizes showed that 1 wt.% PEI led to the optimum dispersion and ultrasonication for longer time with a low power resulted in better dispersion. 0.5 g of W powders were ultrasonicated in 10 ml aqueous poly (allylamine hydrochloride) (PAH) solutions with molar concentrations ranging from 0.01 to 0.05 M. W suspensions with 0.03 M and 0.04 M PAH after two washing cycles showed improved dispersion. Cold isostatic pressing can further increase the green density following slip casting. Sintered slip casts made from de-agglomerated nanoparticle W showed a lower density, more uniform microstructure, smaller grains and smaller pores than the sintered dry pressed pellets.
M.S.
Department of Mechanical, Materials and Aerospace Engineering
Engineering and Computer Science
Materials Science & Engr MSMSE

Nanocrystalline praseodymium oxide films have been successfully generated on stainless steel substrates. The electrochemical deposition was performed in the cathode compartment of a divided electrochemical cell with a regular three-electrode configuration. The green films obtained by electrodeposition were then annealed at high temperatures for 1-3 hours. X-ray diffraction revealed the fluorite structure of Pr6O11 and the crystallite size was calculated. X-ray photoelectron spectroscopy was employed to study the composition of the oxide films and also the oxidation state of Pr. Scanning electron microscopy was utilized to study the surface texture and microstructure of deposits. Fourier transform infrared spectrometery was used to investigate the composition of the films. The effects of different conditions on the green films were also studied such as different pH values of the electrolyte solution, different deposition modes, different supporting electrolytes and different applied current densities. Sintering experiments were conducted to investigate the properties of the green films. Praseodymium oxide powders were also successfully prepared by combining electrochemical methods with sintering processes. The praseodymium oxide powders were characterized by X-ray diffraction and Fourier transform infrared spectroscopy. The crystallite sizes of the powders were evaluated.

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.

This research project investigates a new technique to efficiently mix crystalline solid additives with polymers by gentle ball milling with steel balls in the presence of carbon dioxide (C02) at 17 to 30°C and 1300 to 2500 psig. As the ball milling system is agitated, the steel balls transfer mechanical energy to the fluoropolymer and additive thereby converting them to powders. C02 is added into the chamber to expand the polymer and make it amenable to impregnation by the additive. At the end of the mixing process, a free flowing powder is produced consisting of the additive coated with fluoropolymer. The additives were extracted from the powders and intrinsic viscosity measurements were done on the remnant fluoropolymer. Viscosity studies showed that the virgin and post-ball milled fluoropolymers had similar intrinsic viscosities, hence similar molecular weights within experimental error limits. This implies that most of the polymer chains were simply disentangled during the mixing process and not broken. Differential Scanning Calorimetry (DSC) and Thermal Gravimetric Analysis (TGA) were done on the virgin polymer, the additives and the fabricated powders to determine the loading levels and to ascertain if there were any changes to the physical properties of the polymer. Scanning electron micrographs showed that some of the powder particles had additive particles stuck on the surface, but when these additives were washed off the surface of the powders with a suitable solvent that did not dissolve the polymer, DSC analysis showed the presence of additive incorporated into the polymer matrix.

There are today strong incentives for an increased understanding of material properties and manufacturing processes to facilitate the development of new technologies in the pharmaceutical industry. The purpose of this thesis was to suggest methods requiring a low sample amount for characterization of technical properties of powders.

Compression analysis was used to evaluate the formulation relevance of some compression equations. Using the mechanics of single granules to estimate powder functionality was part of this work. It was concluded that the formability of granular solids and the plasticity of single granules could be determined with compression analysis by using the Kawakita model for single components and binary mixtures of ductile granules.

Further on, the fragmentation propensity of solid particles could be estimated from compression analysis by using the Shapiro equation, enabling indicators of both the fragmentation and the deformation propensity of particles to be derived in one single compression test.

The interpretations of the compression parameters were only valid if the influence of particle rearrangement was negligible for the overall compression profile. An index indicating the extent of particle rearrangement was developed and a classification system of powders into groups dependent on the incidence of particle rearrangement was suggested as tools to enable rational interpretations of compression parameters.

The application of compression analysis was demonstrated by investigating the relevance of the mechanics of granular solids for their tableting abilities. The plasticity of single gran-ules was suggested to influence both the rate of compactibility and the mode of deformation, and consequently the maximal tablet strength. The degree of granule bed deformation was shown to be a potential in line process indicator to describe the tableting forming ability.

This thesis contributes to a scheme, suitable in formulation work and process control, to describe manufacturability of powders for an enhanced tablet formulation technology.

High-energy ball milling was studied for the ex situ strengthening of aluminum (Al) with nanodiamond (ND). Al-ND metal matrix composite powders with 5 wt% and 10 wt% nanodiamond were synthesized by high-energy ball milling of the blended component powders. Stearic acid was used as a process control agent to minimize agglomeration of the powders upon milling. A uniform distribution of the ND reinforcement was successfully obtained after milling the powders for a period of ten hours with a ball-to-powder ratio of 30:1 in a SPEX 8000M ball mill. Composition and properties of the Al-ND composite was studied using energy dispersive spectrometry (EDS) mapping, scanning electron microscopy (SEM), X-ray diffraction (XRD), optical microscopy, and nanoindentation techniques.

This thesis work is focused on the influence of process parameters during gas atomization on the thermal spraying properties of a Ni-Cr-B-Si hardfacing alloy. The metal powder alloy, known as 1-60-20, is produced by Höganäs AB. There have been problems with insufficient fusing during flame spraying of this particular alloy sometimes, even though the chemical composition is always within spec. This has lead to a theory that the difference in performance is caused by differences in parameters during gas atomization. Several gas-gas and gas-water atomizations with varying parameters were performed at the Höganäs Pilot Centre. The powder samples were then analyzed by sieving, scanning electron microscopy, x-ray diffraction and finally tested by powder welding. The results show that by increasing the cooling rate during gas atomization the formation of unstable Ni-borides is possible for this alloy. If these Ni-borides will enhance the fusing properties of the alloy is unknown. According to the literature studied, it should however improve the fusing properties.

Les nanotubes de carbone (NTC), très petits, creux et monodimensionnels, sont très étudiés du fait de leurs excellentes propriétés thermiques, électriques et mécaniques. Les buts de cette thèse étaient premièrement de préparer des poudres et mousses de solutions solides Fe/Al2O3 et des poudres Fe/Al6Si2O13, servant comme matériaux catalytiques pour la synthèse de nanocomposites NTC-Fe-oxyde, et deuxièmement de faire une étude approfondie de tous ces matériaux par spectroscopie Mössbauer du 57Fe et de corréler les résultats avec ceux issus d'autres techniques, de manière à obtenir des informations sur la formation des NTC, la stabilité thermique et la composition de surface des nanocomposites. L'intérêt d'utiliser la spectroscopie Mössbauer réside dans le fait que l'identification et la quantification des différentes phases contenant du fer peut être réalisée avec précision. De plus, cette technique permet de déterminer l'état d'oxydation du fer, permettant ainsi de connaître le degré de réduction de la solution solide. La combinaison de l'Integral Low-Energy Electron Mössbauer Spectroscopy avec la spectroscopie Mössbauer en transmission a permis d'apporter beaucoup d'informations utiles à la compréhension des relations entre le matériau catalytique de départ, la localisation dans les nanocomposites des espèces réduites du fer (a-Fe, Fe3C et gamma-Fe-C) et les NTC. D'anciennes hypothèses expliquant comment ces espèces sont reliées à la formation des NTC ont pu être affinées : il a été montré que les particules de gamma-Fe-C ne sont pas forcément de toutes petites nanoparticules et que les particules actives pour la formation des NTC ne sont pas toujours détectées comme Fe3C
Carbon nanotubes (CNT), very small, hollow and monodimensional, are one of the most widely investigated nanomaterial because they show excellent thermal, electrical and mechanical properties. The goals of this thesis were firstly to prepare Fe/Al2O3 solid solution powders and foams and Fe/ Al6Si2O13 powders and to use them as catalytic materials for the synthesis of CNT-Fe-oxyde nanocomposites, and secondly to perform a profound investigation of all the materials by 57Fe Mössbauer spectroscopy and to correlate the results with those obtained by other techniques with the aim to obtain information on the formation of the CNT, thermal stability, and surface composition of the nanocomposites. The value of applying the Mössbauer spectroscopy technique is that the identification and quantification of the various Fe-containing phases can be performed precisely. Moreover, this technique has the advantage of determining the oxidation state of iron and thus, the reduction rate of the starting solid solution(s). The combination of the Integral Low-Energy Electron Mössbauer Spectroscopy with transmission Mössbauer spectroscopy has yielded many information concerning the understanding of the relationship between the starting catalytic material, the location of the reduced iron species (a-Fe, Fe3C and gamma-Fe-C) in the nanocomposites and the CNT. Earlier hypotheses, into how these species may be connected to the formation of the CNT, were refined: it was shown that gamma-Fe-C particles are not obviously very small-sized nanometric particles and that the species active for the formation of CNT are not always detected as Fe3C

Thesis (M.S.)--Engineering, Georgia Institute of Technology, 2004.
McDowell, David, Committee Chair; Neu, Richard, Committee Member; Lee, Jim, Committee Member; Cochran, Joe, Committee Member. Includes bibliographical references (leaves 159-162).

Aquesta Tesi doctoral comprèn la síntesi mitjançant nanoemmotllament (de l’anglès, nanocasting) i autoassemblatge per evaporació induïda (de l’anglès, evaporation–induced self–assembly) i la caracterització exhaustiva de pols i capes de SnO2 mesoporós dopat amb Ni i Cu. L’origen de les propietats magnètiques d’aquests materials es discuteix en detall. En primer lloc, es van sintetitzar per nanoemmotllament a partir de motlles de sílice KIT–6, pols mesoporosa ordenada de SnO2 dopada amb diferents quantitats de Ni. Es va verificar la replicació correcta del motlle de sílice mitjançant microscòpia electrònica de rastreig. No es van detectar fases extres atribuïbles a Ni o NiO en els corresponents difractogrames excepte per a la mostra amb el dopatge més alt (9 at.% Ni), per a la qual es va observar la presència de NiO com a fase secundària. Es va estudiar l’estat d’oxidació i la distribució espaial de Ni en la pols mitjançant espectroscòpia fotoelectrònica de raigs X i espectroscòpia de pèrdua d’energia d’electrons, respectivament. Les mostres dopades amb Ni presenten resposta ferromagnètica tant a temperatura ambient com a baixa temperatura, com a conseqüència de la presència d’espins no compensats a la superfície de nanopartícules de NiO i vacants d’oxigen. En segon lloc, es van sintetitzar capes primes continues i mesoporoses de SnO2 dopades amb Ni a partir de diferents relacions molars [Ni(II)]/[Sn(IV)] mitjançant un procés d’autoassemblatge sol–gel, utilitzant el copolímer tribloc P–123 com a agent director d’estructura. Una caracterització estructural profunda va evidenciar l’obtenció d’una estructura nanoporosa 3–D, de gruix comprès entre els 100 i 150 nm, i mida de porus de 10 nm. Els experiments de difracció de raigs X d’incidència rasant van posar de manifest que el Ni ocupava posicions substitucionals en la xarxa tipus rutil del SnO2, tot i que les anàlisis per dispersió d’energies de raigs X també van revelar la presència de petits clústers de NiO en les capes produïdes a partir de les relacions molars [Ni(II)]/[Sn(IV)] més elevades. Convé remarcar que les propietats magnètiques de les capes mesoporoses varien significativament en funció del percentatge de dopant. Les capes de SnO2 no dopades presenten un comportament diamagnètic, mentre que les dopades amb Ni mostren un clar senyal paramagnètic amb una petita contribució ferromagnètica. En tercer lloc, també es van estudiar les propietats magnètiques de pols mesoporosa ordenada de SnO2 dopada amb Cu, obtinguda mitjançant nanoemmotllament a partir de sílice KIT–6. Per bé que una eventual contaminació amb impureses de Fe or la presència de vacants d’oxigen podrien explicar el comportament ferromagnètic observat a temperatura ambient, el ferromagnetisme a baixa temperatura es va atribuir únicament a la naturalesa nanoestructurada de les nanopartícules antiferromagnètiques de CuO formades (espins no compensats i shape–mediated spin canting). La menor temperatura de bloqueig, situada entre 30 i 50 K, i l’existència de petits desplaçaments verticals en els cicles d’histèresi van confirmar efectes de mida en les nanopartícules de CuO
This Thesis dissertation covers the synthesis by means of nanocasting and evaporation–induced self–assembly (EISA) methods as well as the advanced characterization of Ni, Cu–doped mesoporous SnO2 powders and films. The origin of the magnetic properties in these materials is also discussed in detail. Firstly, ordered mesoporous SnO2 powders doped with different Ni amounts were synthesized by nanocasting from mesoporous KIT–6 silica. Successful replication of the silica template was verified by scanning electron microscopy. No extra phases attributed to Ni or NiO were detected in the corresponding X–ray diffractograms except for the sample with the highest doping amount (e.g., 9 at.% Ni), for which NiO as secondary phase was observed. The oxidation state and spatial distribution of Ni in the powders was investigated by X–ray photoelectron spectroscopy and electron energy loss spectroscopy, respectively. Ni–containing powders exhibit ferromagnetic response at low and room temperatures, due to uncompensated spins at the surface of NiO nanoparticles and the occurrence of oxygen vacancies. Secondly, continuous mesoporous Ni–doped SnO2 thin films were synthesized from variable [Ni(II)]/[Sn(IV)] molar ratios through a sol–gel based self–assembly process, using P–123 triblock copolymer as a structure directing agent. A deep structural characterization revealed a truly 3–D nanoporous structure with thickness in the range of 100–150 nm, and average pore size about 10 nm. Grazing incidence X–ray diffraction experiments indicated that Ni had successfully substituted Sn in the rutile–type lattice, although energy–dispersive X–ray analyses also revealed the occurrence of small NiO clusters in the films produced from high [Ni(II)]/[Sn(IV)] molar ratios. Interestingly, the magnetic properties of these mesoporous films significantly vary as a function of the doping percentage. The undoped SnO2 films exhibit a diamagnetic behaviour, whereas a clear paramagnetic signal with small ferromagnetic contribution dominates the magnetic response of the Ni–doped mesoporous films. Thirdly, the magnetic properties of ordered mesoporous Cu–doped SnO2 powders, prepared by hard–templating from KIT–6 silica, were also studied. While Fe contamination or the presence of oxygen vacancies might be a plausible explanation of the room temperature ferromagnetism, the low–temperature ferromagnetism was mainly and uniquely assigned to the nanoscale nature of the formed antiferromagnetic CuO nanoparticles (uncompensated spins and shape–mediated spin canting). The reduced blocking temperature, which resided between 30 and 5 K, and small vertical shifts in the hysteresis loops confirmed size effects in the CuO nanoparticles.

Cold Spray is a solid-state additive manufacturing process that uses metallic feedstock powders to create layers on a substrate through plastic deformation. This process can be used for the repair of mechanical parts in the aerospace industry as well as for structural applications. Aluminum alloy powders, including Al 6061, 7075, 2024, and 5056, are typically used in this process as feedstock material. Since this process takes place all in the solid state, the properties and microstructure of the initial feedstock powder directly influence the properties of the final consolidated Cold Spray part. Given this, it is important to fully understand the internal powder microstructure, specifically the secondary phases as a function of thermal treatment. This work focuses on the understanding of the internal microstructure of Al 6061, 7075, 2024, and 5056 through the use of light microscopy, scanning electron microscopy, transmission electron microscopy, energy dispersive x-ray spectroscopy, electron backscatter diffraction, and differential scanning calorimetry. Thermodynamic models were used to predict the phase stability in these powders and were calibrated using the experimental results to give a more complete understanding of the phase transformations during thermal processing.

The scope of this thesis is the aqueous synthesis and characterization of titanium dioxide nanostructured powders for the fabrication of thin film photoanodes used in DSC devices. The development and study of this novel process is approached from the standpoint of determining the relationship between the hydrolytic behaviour of isothermally treated titanium tetrachloride aqueous solutions (speciation and kinetics of conversion of Ti(IV) into TiO2(s)) and the properties of the resultant TiO2 products. From an application standpoint, the aqueous synthesized nanocrystalline TiO2 material is studied for the formulation of screen-printing pastes used in the fabrication of mesoporous photoanodes and resultant dye-sensitized solar cell (DSC) performance. The synthesis of TiO2 nanostructured powders by forced hydrolysis of aqueous Ti(IV) chloride solutions is described in terms of precipitation kinetics and nucleation and growth mechanism over the temperature range 70-90 °C and Ti(IV) concentration 0.2-1.5 M. Several techniques are used to characterize the resultant solid products, among which are XRD, FEG-SEM/FEG-TEM, BET surface area, TGA, FT-IR, and EDS analyses. Via appropriate selection of conditions, the aqueous synthesis process is shown that can lead to the preferential production of nanostructured rutile powder with unique self-assembled nanofibre (100 nm – 3 µm) spheroidal particles or colloids made of well dispersed 4-8 nm crystallites with anatase as the major crystalline phase (85 wt.%). These results are explained and discussed based on the effect of various process parameters (T, agitation), but most importantly based on the pronounced effect of the initial concentration of the TiCl4 aqueous solution on the speciation of the solution and related kinetics of the hydrolysis reaction. When compared to benchmark products such as the P25 TiO2 from Degussa (50 m2/g, 30 nm average crystallite size, very little to no surface -OH/-OH2, and 3.15 eV band gap), the two types of aqueous-synthesized materials are found to possess a high specific surface area, with 80-120 m2/g for the rutile powders and 250-350 m2/g for the anatase powders, enhanced surface hydroxylation, and larger band gap (3.37 eV) in the case of the anatase nanopowder. These materials are shown that can be used for the fabrication of thin film photoanodes prepared by the screen-printing method either separately (i.e. anatase) or as hybrid (anatase-rutile) with the latter being superior in terms of photovoltaic performance. Finally, the direct preparation of paste without drying of the nanocolloids is demonstrated.
Cette étude porte sur la synthèse en milieu aqueux de particules nano-structurées de dioxide de titane utilisées pour la fabrication de photoanodes, une composante des cellules photovoltaïques à pigments colorés (DSCs). Le développement et l'étude de ce nouveau procédé de synthèse est abordé de façon à déterminer la relation existante entre le comportement hydrolytique de solutions aqueuses de tetrachlorure de titane traitées de manière isothermique (spéciation et cinétique de conversion de Ti(IV) en TiO2(s)) et les propriétés des produits de TiO2 résultant. D'un point de vue pratique, le produit de TiO2 nanocristallin synthétisé en milieu aqueux est examiné pour la formulation de pâtes à imprimer utilisées dans le procédé de fabrication de photoanodes mésoporeuses; l'impact de ce matériau sur l'efficacité des cellules photovoltaïques à colorant est également considéré. La synthèse de poudres de TiO2 nano-structurées, effectuée par hydrolyse de solutions aqueuses de TiCl4, est décrite d'un point de vue de la cinétique de précipitation et des mécanismes de nucléation et de croissance des particules de TiO2, sur des intervalles de température et de concentration variant respectivement de 70 à 90 °C et de 0.2 à 1.5 M. Plusieurs techniques sont utilisées afin de caractériser les produits solides, parmi lesquels la DRX, le MEB et le MET, les spectroscopies FT-IR et EDS, et des mesures d'aire de surface BET et de thermogravimétrie. Il est montré qu'en choisissant les conditions expérimentales de manière appropriée, le procédé de synthèse en milieu aqueux mène à la production de poudres nano-structurées de rutile composées de particules sphéroïdales dont la forme résulte de la croissance radiale de nanofibres (de 100 nm à 3 µm) ou bien de colloïdes contenant des nano-cristaux de 4 à 8 nm dont la principale phase cristalline est l'anatase (85 % m/m). Ces résultats sont expliqués et commentés sur la base des effets induits par les paramètres expérimentaux (T, agitation) et plus particulièrement l'effet prononcé de la concentration de la solution aqueuse de TiCl4 sur la nature des espèces en solution et la cinétique associée à la réaction d'hydrolyse. Si l'on compare les matériaux synthétisés en milieu aqueux avec des produits standards commerciaux tels que la poudre de TiO2 P25 de Degussa (50 m2/g, 30 nm de taille moyenne de particules, présence faible voire nulle de groupes de surface -OH/-OH2 et un band gap de 3.15 eV), ceux-ci sont caractérisés avec une aire de surface plus importante, 80-120 m2/g pour les poudres de rutile et 250-350 m2/g pour les poudres d'anatase, un taux d'hydroxylation de surface plus élevé et un band gap plus large dans le cas de l'anatase (3.37 eV). Il est montré que ces matériaux, plus précisément la poudre d'anatase seule ou bien une poudre hybride d'anatase et de rutile, peuvent être utilisés afin de fabriquer des photoanodes préparées par méthode d'impression, la deuxième poudre ayant montré une qualité supérieure en termes de performance photovoltaïque. Enfin, la préparation de pâtes à imprimer directement à partir de nanocolloides de TiO2, sans avoir à recourir à l'extraction et au séchage des poudres, est décrite.

Cette thèse porte sur le problème fondamental du mottage des poudres suite aux mécanismes de transition de phase. Le projet vise à étudier l'impact des facteurs intrinsèques (structure moléculaire des matériaux, propriétés physiques et/ou physicochimiques, etc.) ou des facteurs environnementaux (conditions de stockage ou paramètres de procédé) sur la stabilité de la structure des poudres. Plus précisément, notre étude a mis en évidence le rôle prépondérant du phénomène de cristallisation et des transitions entre les différents polymorphes du lactose. L'accent a été mis sur le rôle des phénomènes de cristallisation et de la transition de phase dans l'apparition du mottage des poudres de lactose. Deux cas ont particulièrement retenu notre attention: (1) des poudres de lactose monohydrate contenant une fraction de particules amorphes et (2) des échantillons de poudre anhydre composés des anomères α et β du lactose. Dans les deux cas, le mottage a été induite par l'exposition des échantillons à l'air humide, soit dans un dispositif de sorption dynamique de vapeur (SPS), soit par des tests accélérés utilisant deux appareils conçus et réalisés dans notre laboratoire (CLAIR & OLAF). Nos résultats ont montré que, dans les deux cas, la principale cause de prise en masse était la formation de lactose monohydrate, qui est la forme la plus stable parmi tous les polymorphes de lactose. Cependant, les mécanismes élémentaires, les étapes limites et la cinétique du processus de transformation étaient différents dans chaque cas. Les paramètres les plus déterminants étaient l’humidité relative et la température alors que la pression n’a pas eu d’effet significatif. La résistance mécanique des échantillons mottés était étroitement liée au taux et à la cinétique de cristallisation. Enfin, des simulations numériques basées sur la méthode des éléments discrets (DEM) de la résistance mécanique des échantillons mottés ont été réalisées. Le modèle permet de décrire le comportement des échantillons mottés soumis à des contraintes mécaniques de compression ou de traction
This PhD study focuses on the fundamental problem of powder caking due to phase transition mechanisms. The project aims to study the impact of intrinsic factors (molecular structure of materials, physical and/or physicochemical properties, etc.) or environmental factors (storage conditions or process parameters) on the stability of the structure of powders. More precisely, our study has highlighted the preponderant role of the crystallization phenomenon and the transitions taking place between the different polymorphs of lactose. Emphasis was placed on the role of crystallization phenomena and phase transition on the advent of lactose powder caking. Two cases attracted particular attention: (1) lactose monohydrate powders containing a fraction of amorphous particles and (2) anhydrous powder samples composed of ð and anomers of lactose. In both cases, the caking was induced by exposure of the samples to moist air, either in a Dynamic Vapor Sorption device (SPS) or in accelerated caking tests using two home-made equipment (CLAIR & OLAF). Our results showed that in both cases, the main cause of caking was the formation of lactose monohydrate, which is the most stable form among all lactose polymorphs. However, the elementary mechanisms, the limiting steps and the kinetics of the transformation process were different in each case. The more influencing parameters were the relative humidity and the temperature whereas the pressure has no significant effect. The yield stress of caked samples was closely linked with crystallization extent and kinetics. Finally, numerical simulations based on Discrete Element Method (DEM) of mechanical resistance of caked samples were performed using the "beam model". The model allows describing the behavior of the caked samples subjected to compressive or tractive mechanical stresses

La manutention et la mise en œuvre des matériaux granulaires libèrent de fines particules de poussière qui, dans un contexte professionnel, peuvent gravement affecter la santé et la sécurité des travailleurs, ainsi que le fonctionnement global de l'installation. L’émission de poussières et la capacité d'un matériau à libérer des particules de poussière, dépendent de plusieurs paramètres relatifs au matériau mais aussi au procédé. Ces émissions sont généralement mesurées par des tests d'empoussièrement à l'échelle du laboratoire. Ces tests reposent principalement sur des études expérimentales et manquent de capacité prédictive fiable en raison d'une compréhension limitée des mécanismes mis en jeu et des interactions complexes entre particules, paroi et fluide, survenant simultanément pendant la génération de poussières. Dans le cadre du projet EU ITN T-MAPPP, cette thèse utilise des approches expérimentales et statistiques pour comprendre les mécanismes de génération de poussières en étudiant: a) les effets des caractéristiques des particules et poudres en vrac sur l’émission de poussières; b) la nature et l'ampleur des interactions entre particules, entre particules et parois, et entre particules et fluides; c) l'évolution de l'empoussièrement et des mécanismes de génération pour des applications de poudre de longue durée. Les résultats indiquent que les mécanismes de génération de poussière diffèrent en fonction de la taille des particules et de la distribution de taille de la poudre. Pour les échantillons d'essai et les conditions expérimentales donnés, les différences dans les modèles initiaux de libération de poussière peuvent être caractérisées par trois groupes différents de poudres : - des poudres contenant des particules cohésives fines, - des poudres bimodales (constituées de fines et de grosses particules), - et enfin des poudres constituées de grosses particules. Tandis que la cohésion globale, surtout celle due aux forces de van der Waals (mesurée à l'aide de testeurs de cisaillement) détermine le niveau de poussières pour les poudres fines, de telle sorte qu'une cohésion globale plus élevée conduit à moins de poussière, la fraction de particules fines et la cohésion déterminent toutes deux l'empoussièrement provenant des poudres bi-modales. Les grosses particules peuvent émettre de la poussière uniquement par usure des particules primaires en particules fines aérosolisables plus petites. L'analyse d'un mouvement de particules tracées à l'intérieur d'un tube cylindrique agité par un testeur d'empoussiérage à vortex montre une nature cyclique du mouvement des particules. Le mouvement des particules (position et vitesse) est symétrique et isotrope dans le plan horizontal, les vitesses radiales les plus basses et les plus élevées étant proches du centre du tube et de la paroi, respectivement. Les particules ont tendance à s'élever lentement au milieu du tube tout en descendant rapidement près de la paroi. Les valeurs les plus élevées de la vitesse se trouvent aux hauteurs les plus élevées et près de la paroi interne du tube à essai, où les densités de population sont les plus faibles. Les valeurs plus élevées de la vitesse pourraient provenir d’une diminution du nombre de chocs due à des densités de population plus faibles. L'augmentation de la taille des particules et des vitesses de rotation des tourbillons tend à augmenter la vitesse des particules tandis que l'augmentation de la masse de poudre conduit à une diminution de la vitesse des particules pour des vitesses de rotation allant jusqu'à 1500 tr / min. Pour les échantillons donnés (carbure de silicium, alumine et coke d'acétylène) et les conditions expérimentales, l'empoussièrement initial est déterminé par la fraction de fines particules respirables présentes dans la poudre, mais les modèles et les niveaux de génération de poussière à long terme sont influencés par le comportement d’attrition matérielle
Handling and processing of granular material release fine solid dust particles, which in an occupational setting, can severely affect worker health & safety and the overall plant operation. Dustiness or the ability of a material to release dust particles depends on several material and process parameters and is usually measured by lab-scale dustiness testers. Dustiness tests remain mostly experimental studies and lack reliable predictive ability due to limited understanding of the dust generation mechanisms and the complex interactions between the particles, wall and fluid, occurring simultaneously during dust generation. In the framework of EU ITN project T-MAPPP, this thesis uses an experimental approach to understand the dust generation mechanisms by studying: a) the effects of key bulk and particle properties on powder dustiness; b) the nature and magnitude of inter-particle, particle-wall and particle-fluid interactions; c) the evolution of dustiness and generation mechanisms for long duration powder applications. The results indicate that the dust generation mechanisms differ based on particle size and size distribution of the powder. For the given test samples and experimental conditions, the differences in powder dustiness and dust emission patterns can be characterized by three different groups of powders; powders containing fine cohesive particles, bi-modal (consisting of fine and large particles) powders and lastly, powders consisting of only large particles. While bulk cohesion, especially that stemming from van der Waals forces (measured using shear testers) determines the level of dustiness for the fine powders (in such a way that higher bulk cohesion leads to lower dustiness), both the fraction of fine particles and cohesion determine the dustiness of bi-modal powders. The large particles can emit dust only through attrition of the primary particles into smaller aerosolizable fine particles. Analysis of a traced particle motion inside a cylindrical tube agitated by a vortex shaker dustiness tester shows the cyclic nature of the particle motion. The motion (position and velocity) is symmetric and isotropic in the horizontal plane with lowest radial velocities close to the tube centre and highest at the boundary wall of the test tube. The particles tend to rise up slowly in the middle of the tube while descending rapidly close to the wall. The highest values of the velocity are found at the highest heights and close to the wall of the test tube, where the population densities are lowest. Increasing particle size and vortex rotation speeds tends to increase particle velocity whereas increase in powder mass leads to a decrease in particle velocity for rotation speeds up to 1500 rpm. For the given samples (silicon carbide, alumina and acetylene coke) and the experimental conditions, the initial dustiness is determined by the fraction of fine respirable particles present in the powder but the long-term dust generation patterns and levels are influenced by the material attrition behaviour. Dust is generated by the fragmentation and/or abrasion of primary particles, which may lead to the production and emission of fine daughter particles as dust. The samples with large irregularly shaped particles are likely to show high dustiness by shedding angular corners through inter-particle and particle-wall collisions, thus becoming more spherical in shape. On the contrary, the smaller particles are more resistant to abrasion and generate relatively less dust. While the vortex shaker dustiness tests show similar trends as an attrition tester, our study using alumina and acetylene coke indicate that the results are not interchangeable. Results from this thesis help understand the influence of powder and process parameters which may be manipulated to reduce dust generation. Furthermore, experimental results can be used to develop and validate numerical models to predict dustiness

Study of the metastable phases obtained by non-equilibrium processing techniques has come a long way during the past five decades. New metastable phases have often given new perspectives to the research on synthesis of novel materials systems. Metastable materials produced by two non-equilibrium processing methods were studied for this dissertation- 304-type austenitic stainless steel (SS304 or Fe-18Cr-8Ni)+aluminum coatings produced by plasma enhanced magnetron sputter-deposition (PEMS) and nanocrystalline Ti, Zr and Hf powders processed by mechanical milling (MM). The objective of the study was to understand the crystallographic and microstructural aspects of these materials. Four SS304+Al coatings with a nominal Al percentages of 0, 4, 7 and 10 wt.% in the coatings were deposited on an SS304 substrate by PEMS using SS304 and Al targets. The as-deposited coatings were characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and three-dimensional atom probe microscopy (3DAP). Surface morphology and chemical analysis were studied by SEM. Phase identification was carried out by XRD and TEM. The microstructural features of all the coatings, as observed in the TEM, consisted of columnar grains with the columnar grain width (a measure of grain size) increasing with an increase in the Al content. The coatings had grains with average grain sizes of about 100, 290, 320 and 980 nm, respectively for 0, 4, 7 and 10 wt.% Al. The observed grain structures and increase in grain size were related to substrate temperature during deposition. XRD results indicated that the Al-free coating consisted of the non-equilibrium ferrite and sigma phases. In the 4Al, 7Al and 10Al coatings, equilibrium ferrite and B2 phases were observed but no sigma phase was found. In 10Al coating, we were able to demonstrate experimentally using 3DAP studies that NiAl phase formation is preferred over the FeAl phase at nano scale. During mechanical milling of the hexagonal close packed (HCP) metals Hf, Ti and Zr powders, unknown nanocrystalline phases with face centered cubic (FCC) structure were found. The FCC phases could be either allotropes of the respective metals or impurity stabilized phases. However, upon MM under high purity conditions, it was revealed that the FCC phases were impurity stabilized. The decrease in crystallite size down to nanometer levels, an increase in atomic volume, lattice strain, and possible contamination were the factors responsible for the transformation.
Ph.D.
Department of Mechanical, Materials and Aerospace Engineering;
Engineering and Computer Science
Materials Science & Engr PhD

Development of products which can be produced from a country’s natural resources is very important as far as the industrialization of a nation and saving foreign exchange is concerned. Presently, industries in Uganda and the other states in the Lake Victoria region import all refractory-related-consumables, as the demand cannot be met locally. Based on the abundance of ceramic raw materials for high temperature applications in the region and the demand for refractories by industries it is pertinent to develop and manufacture firebricks by exploiting the locally available raw materials.

This thesis thus, concerns the characterisation of ceramic raw mineral powders from the Lake Victoria region, more particularly, Uganda, with the aim of developing firebrick refractories from the minerals. Two main deposits of kaolin and a ball clay deposit were investigated to assess their potential in the manufacture of refractory bricks. Raw- and processed sample powders were investigated by means of X-ray diffraction (XRD), thermal analysis (DTA-TG) and Scanning Electron Microscopy (SEM). In addition, the chemical composition, particle size distribution, density, and surface area of the powders were determined.

A comprehensive study on beneficiation of Mutaka kaolin was carried out using mechanical segregation of particles. The aim of the study was to explore other potential applications like in paper filling and coating. The beneficiation process improves the chemical composition of kaolin to almost pure, the major impurity being iron oxide.

A general production process scheme for manufacturing fireclay bricks starting with raw powder minerals (Mutaka kaolin and Mukono ball clay) was used to make six groups of sample fireclay brick. Experimental results from the characterization of formulated sample bricks indeed revealed the viability of manufacturing fireclay bricks from the raw minerals. Based on these results, industrial samples were formulated and manufactured at Höganäs Bjuf AB, Sweden. Kaolin from the Mutaka deposit was used as the main source of alumina while ball clay from Mukono was the main plasticizer and binder material. The formulated green body was consolidated by wet pressing and fired at 1350°C in a tunnel kiln. Characterization of the sintered articles was done by X-ray diffraction, scanning electron microscopy, and chemical composition (ICP-AES). In addition, technological properties related to thermal conductivity, thermal shock, alkali resistance, water absorption, porosity, shrinkage, permanent linear change (PLC), linear thermal expansion, refractoriness under load (RUL), and cold crushing strength were determined. The properties of the articles manufactured from the selected naturally occurring raw minerals reveal that the produced articles compare favourably with those of parallel types. Thus, the raw materials can be exploited for industrial production.

Accurate statistical characterization of nanomaterials is crucial for their use in emerging technologies. This work investigates how different structural characteristics of metal nanoparticles influence the line profiles of the corresponding powder diffraction pattern. The effects of crystallite size, shape, lattice dynamics, and surface strain are all systematically studied in terms of their impact on the line profiles. The studied patterns are simulated from atomistic models of nanoparticles via the Debye function. This approach allows for the existing theories of diffraction to be tested, and extended, in an effort to improve the characterization of small crystallites. It also begins to allow for the incorporation of atomistic simulations into the field of diffraction. Molecular dynamics simulations are shown to be effective in generating realistic structural models and dynamics of an atomic system, and are then used to study the observed features in the powder diffraction pattern. Furthermore, the characterization of a sample of shape controlled Pt nanoparticles is carried out through the use of a developed Debye function analysis routine in an effort to determine the predominant particle shape. The results of this modeling are shown to be in good agreement with complementary characterization methods, like transmission electron microscopy and cyclic voltammetry.

Les poussières (<3 mm) générées chaque année par les industries minières et métallurgiques ont un impact économique et écologique conséquent. Le recyclage de ces matériaux par l’agglomération à froid et sans liant est la meilleure option, mais ces procédés manquent de prédictibilité. La présente étude vise à améliorer cette prédictibilité grâce à une meilleure compréhension des phénomènes.Une caractérisation étendue des propriétés chimiques, physiques et morphologiques a été réalisée sur les matériaux fins généré durant la production d’alliages de ferromanganèse. Une prédiction qualitative a pu être développée selon des considérations théoriques et empiriques. Des tests de compaction uniaxiale ont été réalisés sur des échantillons de bentonite, kaolinite, minerai enrichi et hausmannite pour tester les hypothèses formulées. Ils ont confirmé l’importance de la présence de matériaux en feuillet et/ou qui se déforment de façon plastique. L’ajout d’humidité et l’accroissement de la pression ont une limite maximale d’efficacité, dépendante du matériau. Des tests de modélisation DEM préliminaires ont été réalisés pour estimer l’impact des variation du module d’Young et de la force et la taille des liens sur la force des agglomérés et leur comportement à la cassure
The mining and metallurgical industries produce significant amount of fine materials (<3mm) each year, which bears a high economic and ecological impact. Recycling these materials through cold, binder-free agglomeration is the best course of action, but still lacks predictability. The present study aims increases this predictability through a deeper comprehension of the phenomena. An extensive characterization of the chemical, physical and morphological characteristics of the fine materials generated along the ferromanganese alloy production process was performed. A qualitative prediction of the agglomeration potential of the material was developed based on theoretical and empirical comparisons. Agglomeration experiments using uniaxial compaction were performed on bentonite, kaolinite, enriched ore and hausmannite samples to test the hypothesis formulated. They confirmed the importance of the presence of materials with a layered structure (such as clays) and/or that deform plastically. The moisture addition and the pressure increase have an upper limit of efficiency, depending on the material. Preliminary DEM modelling were performed to assess the impact of the variation of young’s modulus, bond strength and bond size on the simulation of the agglomerate strength and breakage style

Dissertação de Mestrado Integrado em Engenharia Mecânica apresentada à Faculdade de Ciências e Tecnologia da Universidade de Coimbra
Tungsten Carbide mixed with Nickel (WC-Ni) is of great importance in applications that requires high levels of hardness and wear resistance due to the combination of properties granted by the presence of two different phases: Tungsten Carbide phase imparts the hardness and the strength while metallic matrix acts to increase ductility and toughness. The dynamic behaviour of WC-Ni powders, with Nickel content of 11% was studied under planar loading conditions. A gas gun was used to conduct planar impact experiments at velocities of 320, 500 and 620 m/s to determine the shock and wave propagation characteristics of the material stablishing the Hugoniot relations in different planes. When the material is shocked between 1.1 to 4.8 GPa, a steady shock wave is generated which propagates at a velocity ranging from 866 to 1620 m/s and transfers energy into particles that moves at velocities between 151 and 300 m/s after its passage. Based on the achieved results, recommendations will be made for performing future works aimed at improving the experimental technique, with the purpose of enhancing the understanding of the behaviour of materials when subjected to shock.
O carboneto de tungsténio com adição de uma matriz secundária de Níquel (WC-Ni) é de grande importância em aplicações em que são exigidas grandes valores de resistência e abrasão. Estas propriedades são garantidas pelas diferentes fases da estrutura, em que o WC garante rigidez enquanto que o Ni adiciona plasticidade e ductilidade ao material. O comportamento ao choque dos pós de WC-Ni (mistura com 11% de Níquel) é estudado com recurso a condições de impacto planar. Esta experiência recorre a um canhão de gás comprimido para realizar impactos a altas velocidades de projétil na ordem de 320, 500 e 620 m/s. Esta metodologia permite obter informação suficiente para caracterizar a propagação das ondas de choque no material estabelecendo a chamada relação de Hugoniot. Quando o impacto dos corpos gera pressões entre 1,1 e 4,8 GPa, é gerada uma frente de onda de choque que se propaga a velocidades compreendidas entre 866 e 1620 m/s. A passagem da onda no material transfere energia às partículas induzindo-lhes velocidades entre 151 e 300 m/s. Com base na análise dos resultados, são propostos trabalhos futuros para o melhoramento da metodologia experimental com o intuito de aprofundar o conhecimento do comportamento dos materiais face ao choque.

碩士
國立成功大學
化學工程學系碩博士班
101
Cerium dioxide (CeO2) powders were synthesized with adding hydrogen peroxide (H2O2) by the precipitation technique. The investigation of precipitation reaction and properties of products were emphasized in this work. Experimentally, the precipitation reactions were performed under various adding time of H2O2, H2O2 concentrations, reaction temperatures, and valences of cerium precursors. The effects of preparation conditions on the particle size, shape, crystalline structure, surface area and catalytic activity of final CeO2 products were investigated. Moreover, the formation mechanismof CeO2 particle was also discussed via the particle evolution. The experimental results revealed that, the addition of H2O2 in the precipitation showed great influences on the properties of CeO2 products. As the H2O2 was added prior to the precipitation, the product was particulate powder with a size smaller than 5 nm. However, if H2O2 was added after the precipitation reaction started, the CeO2 product became rodlike shape with a size smaller than 20 nm. At reaction temperature of 90oC, as the H2O2 concentration was increased, the shape of resulting CeO2 product changed from fully particulate into partially rodlike. In other words, the rodlike/particulate ratio of product was increased with increasing the H2O2 concentration. With the presence of H2O2, the surface area of the product was larger than that without adding H2O2. Besides, rodlike CeO2 powders came out in the final product only at temperature above 50oC; otherwise the product shaped particulate. The catalytic oxidation of carbon monoxide (CO) was carried out over the calcined CeO2 powders. As compared with the CeO2 powders prepared without H2O2, the catalytic activity of those with H2O2 was much higher, and it was increased with the increase of H2O2 concentration, which was in a good agreement with the TPR results. To make a comparison between products obtained from Ce(III) and Ce(IV) precursors, it revealed that the former had higher rodlike/ particulate ratio. Nevertheless, the later comprised of many tiny particles exhibited larger surface area. From the particle evolution of CeO2 powers, it was inferred that, the hydrogen peroxide played a role of oxidizing agent in the precipitation reaction, with which the oxidation rate was accelerated. More importantly, it could provide a large numbers of peroxy (OOH-) and hydroxyl(OH-) species complexing with cerium to form Ce intermediates. This retarded the grain growth of CeO2, resulting in the small size and large surface area of the final product.

碩士
國立臺灣大學
化學工程學研究所
94
Nanocrystalline magnetite powders were synthesized by an electrocoagulation technique and the microstructure of the oxide powder was found to evolve in roughly three stages: formation and growth of severely defective colloidal crystallites, agglomeration, and coarsening. A mechanism involving competition between nucleation and growth of free colloids and coarsening of the skeletal framework was proposed to explain the temporary level-off in crystallite size during the synthesis. A modified method was developed to synthesize ultrafine magnetite (less than 10 nm) revealing superparamagnetism with saturation magnetization of 64.5 emu/g. The crystallites were characterized by XRD, TEM, DLS, and SQUID. The ferrofluid was also synthesized in the presence of PVA. The PVA will inhibit the growth of magnetite and the magnetite crystallite size reduced to 5 nm. The particles also show a superparamagnetic behavior with saturation magnetization of 64.5 emu/g. to 4.57 emu/g due to the PVA-coated layer and the oxidation.

Master of Science
Food Science Institute
Jayendra K. Amamcharla
Milk protein concentrate (MPC) powders are high-protein dairy ingredients obtained from membrane filtration processes and subsequent spray drying. MPC powders have extensive applications due to their nutritional, functional, and sensory properties. However, their flow properties, rehydration behavior, and morphological characteristics are affected by various factors such as processing, storage, particle size, and composition of the powder. Literature has shown that knowledge about the powder flowability characteristics is critical in their handling, processing, and subsequent storage. For this study, FT4 powder rheometer (FT4, Freeman Technologies, UK) was used to characterize the flowability of MPC powders during storage. This study investigated the flowability and morphological characteristics of commercial MPC powders with three different protein contents (70, 80, and 90%, w/w) after storage at 25ºC and 40ºC for 12 weeks. Powder flow properties (basic flowability energy (BFE), flow rate index (FRI), permeability, etc.) and shear properties (cohesion, flow function, etc.) were evaluated. After 12 weeks of storage at 40ºC, the BFE and FRI values significantly increased (P < 0.05) as the protein content increased from 70 to 90% (w/w). Dynamic flow tests indicated that MPC powders with high protein contents displayed higher permeability. Shear tests confirmed that samples stored at 40ºC were relatively less flowable than samples stored at 25ºC. Also, the lower protein content samples showed better shear flow behavior. The results indicated that MPC powders stored at 40ºC had more cohesiveness and poor flow characteristics than MPC powders stored at 25ºC. The circle equivalent diameter, circularity, and elongation of MPC powders increased as protein content and storage temperature increased, while the convexity decreased as protein content and storage temperature increased. Overall, the MPC powders evidently showed different flow properties and morphological characteristics due to their difference in composition and storage temperature. Literature has shown various methods for determining the solubility of dairy powders, but it requires expensive instruments and skilled technicians. The front-face fluorescence spectroscopy (FFFS) coupled with chemometrics could be used as an efficient alternative, which is commonly used as fingerprints of the various food products. To evaluate FFFS as a useful tool for the non-destructive measurement of solubility in the MPC powders, commercially procured MPC powders were stored at two temperatures (25 and 40ºC) for 1, 2, 4, 8, and 12 weeks to produce powders with different rehydration properties, which subsequently influenced their fluorescence spectra. The spectra of tryptophan and Maillard products were recorded and analyzed with principal components analysis. The solubility index and the relative dissolution index (RDI) obtained from focused beam reflectance measurement was used to predict solubility and dissolution changes using fluorescence spectra of tryptophan and Maillard products. The solubility index and RDI showed that the MPC powders had decreased solubility as the storage time and temperature increased. The results suggest that FFFS has the potential to provide rapid, nondestructive, and accurate measurements of rehydration behavior in MPC powders. Overall, the results indicated that solubility and dissolution behavior of MPC powders were related to protein content and storage conditions that could be measured using FFFS.

碩士
國立成功大學
化學工程學系
88
Abstract In order to increase the specific surface area, the hydrothermal and sol-gel methods were employed to prepare the nanosized Perovskite-type LaBO3 (B= Fe, Co, Mn) catalysts. The effects of alkalinity (R), reaction time, temperature and pressure on the formation of LaBO3 powders were investigated. PAA and nitrates were chosen as the reactants and the pH value was controlled at 2 when the sol-gel method was applied. High molecular weight of PAA was preferred for the sake of high coiling. These powders were characterized by the techniques such as XRD, SEM, TEM, BET and TGA methods. The following results were obtained: In the preparation of the La-Fe series oxide, the powder is amorphous when no hydrothermal treatment was applied. However, when the hydrothermal treatment was utilized, the powders, with crystalline La(OH)3, having a specific surface area in the range of 54~100 m2/g was obtained first. Note that the treatment was undertaken at 150℃ and the reaction became equilibrium after 2 hours. When the powders were calcined at 800℃, very pure LaFeO3 Perovskite crystallines were obtained. The higher the alkalinity, the purer LaFeO3 is. The crystalline size of LaFeO3 was about 20~40nm and the specific surface areas were 14~23 m2/g. The favorable conditions for preparing LaFeO3 Perovskite-type oxides were high alkalinity, high temperature and high pressure. For preparing LaCoO3 Perovskite-type oxides by the hydrothermal method, the optimal conditions were at low pressures and 6