The growth modes of self-assembled mesocrystals and ordered arrays from dispersions of iron oxide nanocubes with a mean edge length of 9.6 nm during controlled solvent removal have been investigated with a combination of visible light video microscopy, atomic force microscopy and scanning electron microscopy. Mesocrystals with translational and orientational order of sizes up to 10 μm are formed spontaneously during the final, diffusion-controlled, drop-casting stage when the liquid film is very thin and the particle concentration is high. Convection-driven deposition of ordered nanocube arrays at the edge of the drying droplet is a manifestation of the so called coffee-ring effect. Dendritic growth or fingering of rapidly growing arrays of ordered nanocubes could also be observed in a transition regime as the growth front moves from the initial three-phase contact line towards the centre of the original droplet.

Crystallization of ZSM-5 zeolite from a gel using n-butylamine as structure-directing agent was studied. Extreme high-resolution transmission and scanning electron microscopy showed the presence of dendritic features that are present at the crystal surface during most of the reaction time that become smoother towards completion of the crystallization. In addition, a web that likely stems from the gel, comprised of alumina-rich nanoparticles between the dendrites at the surface of the crystals was also identified. When the gel is not in direct contact with the crystal surface, dendrites and the web are not observed, and the crystals grow faster. Thus, the alumina-rich web retards the crystal growth and cause the formation of dendritic features.

Inexpensive raw materials have been used to prepare ZSM-5 zeolites with SiO2/Al2O3 molar ratios in the range 20 - 40. Kaolin or Bolivian diatomaceous earth was used as aluminosilicate raw materials and sodium hydroxide and n-butylamine were used as mineralizing agents and template. Dealumination of the raw materials by acid leaching made it possible to reach appropriate SiO2/Al2O3 ratios and to reduce the amount of iron and other impurities. After mixing the components and aging, hydrothermal treatment was carried out and the products were recovered The results clearly show for the first time that well-crystallized ZSM-5 can be directly prepared from leached metakaolin or leached diatomaceous earth using sodium hydroxide and n-butylamine as mineralizing agents and template under appropriate synthesis conditions. A longer induction time prior to crystallization was observed for reaction mixtures prepared from leached diatomaceous earth, probably due to slower digestion of the fossilized diatom skeletons as compared with that for microporous leached metakaolin. The use of leached diatomaceous earth allowed higher yield of ZSM-5 crystals within comparable synthesis times. However, low amounts of Mordenite formed, which was related to the high calcium content of diatomaceous earth. Another considerable advantage of diatomaceous earth over kaolin is that diatomaceous earth does not require heat treatment at high temperature for metakaolinization.

The synthesis of flat tablet-shaped ZSM-5 crystals from a gel using metakaolin as aluminosilicate source and n-butyl amine as structure directing agent was investigated. The evolution inside the solid phase was characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetry and mass spectrometry. A kinetic study indicated that the nucleation of the majority crystals occurred concurrently with the formation of the gel upon heating the starting liquid suspension. Microstructural evidences undeniably showed that the gel precipitated on ZSM-5 crystals and mineral impurities originating from kaolin. As a result, crystal growth was retarded by gel entrapment, as indicated by the configuration and morphology of the embedded crystals. The results presented herein are harmonized with a solution-mediated nucleation and growth mechanism. Our observations differ from the autocatalytic model that suggests that the nuclei rest inside the gel until released when the gel is consumed. Our results show instead that it is crystals that formed in an early stage before entrapment inside the gel that rest inside the gel until exposed at the gel surface. These results illustrate the limitation of the classical method used in the field to determine nucleation profiles when the crystals become trapped inside the gel.

Porous gel structures are formed during the synthesis of the zeolite ZSM-5 due to the reaction between a source of aluminosilicate, sodium hydroxide, water and a structure directing agent, such as e.g. tetrapropylammonium (TPA) or n-butylamine (NBA). In the present work, the formation of the gel in a heterogeneous system leading to the crystallization of NBA-ZSM-5 zeolite from leached metakaolin was studied extensively. The solid and liquid phases obtained after separation were analyzed by inductively coupled plasma sector field mass spectrometry, dynamic light scattering, extreme high resolution-scanning electron microscopy, energy dispersive spectroscopy, high resolution-transmission electron microscopy, X-ray diffraction and nitrogen gas adsorption. The main gel phase formed after hydrothermal treatment exhibited a sponge-like structure resembling those forming in (Na, TPA)-ZSM-5-based systems. For the first time, the walls of the main gel were shown to be inhomogenous and to possess a biphasic internal structure consisting of a mesoporous skeleton of aluminosilicate nanoparticles embedded in a silicate-rich soluble matrix of soft matter. The data presented in this paper is of primary importance to understand the mechanism by which the gel is consumed and contributes to the growth process of the zeolite crystals.

X-ray microtomography data of iron ore green pellets of approx. 12 mm in diameter were recorded using a commercial instrument. The reconstructed volume after thresholding represented a unique dataset consisting of a three-dimensional distribution of equiaxed objects corresponding to bubble cavities. This dataset was used to successfully validate a stereological method to determine the size distribution of spherical objects dispersed in a volume. This was achieved by investigating only a few cross-sectional images of this volume and measuring the profiles left by these objects in the cross-sectional images. Excellent agreement was observed between the size distribution of the bubble cavities obtained by directly classifying their size in the reconstructed volume and that estimated by applying the aforementioned stereological method to eight cross-sectional images of the reconstructed volume. Subsequently, we discuss the possibility of calibrating X-ray tomography data quantitatively using the size distribution of the bubble cavities as a figure of merit and the results obtained by applying the stereological method to SEM images as reference data. This was justified by considering the validity of the stereological method demonstrated by tomography, the accurate thresholding made possible by back-scattered electron imaging and the solid reproducibility of the results obtained by SEM. Using different threshold values for binarization of the X-ray microtomography data and comparing the results to those obtained by SEM, we found that X-ray microtomography can be used after proper calibration against SEM data to measure the total porosity of the bubble cavities but can only provide a rough estimate of the median diameter because of the limited resolution achieved in this study.

Scanning electron microscopy and image analysis was used for quantitative analysis of bubble cavities in iron ore green pellets. Two types of pellets prepared with and without addition of flotation reagent prior to balling were studied. The bubble cavity porosity amounted to 2.8% in the pellets prepared without addition of flotation reagent prior to balling. When flotation reagent was added prior to balling, the bubble cavity porosity increased by a factor of 2.4 and the median bubble diameter was decreased slightly. It was also shown that mercury intrusion porosimetry is not suitable for determination of the distribution of bubble cavities. Finally, our data suggested that the difference in total porosity determined by mercury intrusion porosimetry and pycnometry between the two types of pellets was due to the bubble cavities.

Sodium-activated calcium bentonite is used as a binder in iron ore pellets and is known to increase strength of both wet and dry iron ore green pellets. In this article, the microstructure of bentonite in magnetite pellets is revealed for the first time using scanning electron microscopy. The microstructure of bentonite in wet and dry iron ore pellets, as well as in distilled water, was imaged by various imaging techniques (e.g., imaging at low voltage with monochromatic and decelerated beam or low loss backscattered electrons) and cryogenic methods (i.e., high pressure freezing and plunge freezing in liquid ethane). In wet iron ore green pellets, clay tactoids (stacks of parallel primary clay platelets) were very well dispersed and formed a voluminous network occupying the space available between mineral particles. When the pellet was dried, bentonite was drawn to the contact points between the particles and formed solid bridges, which impart strength to the solid compact.

nosheets of zeolite H-ZSM-5 were synthesized and characterized by X-ray diffraction, transmission electron microscopy (TEM), N2- physisorption, FT-IR spectroscopy, 27Al and 29Si MAS NMR spectroscopy in addition to catalytic testing in conversion of methanol to hydrocarbons (MTH). It was found that Rietveld analysis, involving anisotropic broadening parameters, gave average crystallite dimensions in good agreement with TEM images. The selectivities in MTH is intact in the mesoporous nanosheet H-ZSM-5 with the largest difference being a higher C3/C2 ratio compared to regular H-ZSM-5.

A method was developed to enhance the arsenic adsorption capacity of porous bodies of sintered hematite. The method comprised the formation of a coating of 1 wt % iron oxide nanoparticles on the raw material. The nanoparticles showed two distinct habits: spherical habit, likely ferrihydrite, and acicular habit, likely goethite and/or akaganéite. The specific surface area of the hematite raw material increased from 0.5 to 3.75 m2/g, and the adsorption capacity increased from negligible to 0.65 mg of [As]/g as calculated from equilibrium and breakthrough adsorption data. Equilibrium adsorption data of arsenate on the adsorbent from a solution at pH 5 followed the Langmuir model, while breakthrough adsorption data for a 500 μg/L arsenate solution at pH 5 followed the Thomas model. The adsorbed arsenic could be desorbed using distilled water at pH 12. These results show the potential for the reutilization of waste products comprising coarse hematite bodies as adsorbents.

The crystallization of ZSM-5 from a gel comprising n-butylamine as structure directing agent was investigated. The samples were characterized by X-ray diffraction, nitrogen gas adsorption, extreme high-resolution transmission and scanning electron microscopy, and energy dispersive spectroscopy. The gel was found to be composed by a silica-rich matrix embedded in a skeleton of alumina-rich nanoparticles. During growth of the crystals, the silica-rich matrix is consumed first, and an increasing fraction of the alumina-rich nanoparticles are utilized later in the growth process. This leads to a non-uniform consumption of the gel walls during crystal growth. Consequently, the Si/Al ratio of the gel is steadily decreasing, which is accompanied by a corresponding decrease in the Si/Al ratio from the center to the outer surface of the crystals, i.e. Al-zoning of the ZSM-5 crystals.

The microstructural evolution of precursors of ZSM-5 zeolite crystallized from a heterogeneous system using fumed silica, sodium aluminate and tetrapropylammonium ions as reagents is investigated. Entities previously described by Ren et al. (Chem. Mater. 2012, 24, 10, 1726–1737) as condensed aggregates, were extensively studied using scanning electron microscopy, and energy dispersive spectroscopy. It was observed that the condensed aggregates first comprise a core of nanocrystals that is enveloped by a shell of amorphous gel phase. During crystallization, the amorphous shell surrounding the core is converted into ZSM-5 crystals that grow to a film surrounding the core. The crystals in the film grow competitively with nutrients provided by the liquid phase from the surroundings, while the nanocrystals in the core show little or no signs of growth.

Cast tungsten carbide (CTC) is a biphasic, pearlitic-like structure composed of WC lamellae in a matrix of W₂C. Besides excellent flowability, spherical CTC powders exhibit superior hardness and wear resistance. Nevertheless, the available literature generally fails to explain the physical mechanisms behind such a phenomenon. In the present work, the microstructure and the mechanical properties of the novel centrifugally-atomized spherical CTC have been extensively investigated. This material exhibited an extremely fine microstructure, with WC lamellae of 27-29 nm in thickness and bulk lattice strains of 1.0-1.4 %, resulting in a microindentation hardness of 31.4 ± 1.6 GPa. The results of this study clearly show that centrifugally-atomized CTC is mechanically superior to both spheroidized CTC and conventional cast-and-crushed CTC. In addition, the effect of a series of heat treatments on the bulk fracture toughness and the fatigue life of entire CTC particles was also investigated. The reduction of residual stresses in the bulk of particles upon annealing dramatically increased the indentation fracture toughness, whereas the bulk microindentation hardness remained essentially unaffected. Regarding the fatigue life of entire particles under uniaxial cyclic compressive loading, local phase transformation phenomena at the surface of the particles upon heat treatment were concluded to play the most critical role. Indeed, the cumulative fatigue damage was minimized in surface-carburized CTC powders, where compressive stresses were induced at the outermost surface.

Hardness is defined as the resistance of a material to localized plastic deformation. Owing to their non-destructive nature, static indentation hardness tests are widely used in industry. Hardness testing is particularly useful for the mechanical characterization of materials that cannot be tested otherwise, e.g. powdered materials. In this study, challenges related to Vickers microindentation hardness testing of hard brittle cast tungsten carbide (CTC) powders were extensively investigated. Test load was optimized to obtain sufficiently large crack-free indentations allowing for precise measurement of the diagonal lengths. The influence of the operator and imaging technique on the measured hardness value was evaluated. Topography of residual imprints was investigated using atomic force microscopy (AFM) and a systematic and operator bias-free method to locate the indentation vertexes was developed. Results suggested that measurement variability introduced by AFM scanning and post-processing was as low as 3.1% and 1.3% with respect to the mean hardness value, respectively. Since the variability due to the measuring system can be isolated, the homogeneity of powders can be reliably evaluated from the hardness measurements thus obtained.

At room temperature diluted TiCl4 and CCl4 were reduced by sodium particles and mixed with a polycarbomethylsilane (PCS) solution to yield a precursor. It was dried and subsequently annealed at 1300 °C, 1400 °C and 1450 °C in a tube furnace using argon with 10 ppm N2. After the 1450 °C annealing a nanocrystalline powder of TiC0.5 N0.5–SiC polyhedron and elongated crystals was obtained. At the low nitrogen concentration during annealing a gradual nitration is proposed. It is promoted by carbon gaseous species, precursor oxidation, a sufficient temperature and a summarised nitrogen surplus compared to the titanium and carbon amount.

Discoloration of zeolite A powder is a common problem when natural raw materials such as kaolin clay are used because of the formation of colored iron compounds. In this study, we report on a novel method to produce zeolite A with excellent optical properties, from clays. The brightness is as high as 94.5 and the yellowness is as low as 3.0. The product is comprised of intergrown zeolite A crystals with cubic habit and a length ranging between 0.5 and 2 μm. Good optical properties are obtained when the raw material contains magnesium, as some natural raw materials do, or alternatively, when a magnesium compound is added to the raw material. Magnesium probably forces iron inside colorless extraneous magnesium aluminosilicate compounds. This simple process appears very promising for the preparation of zeolite A with good optical properties from inexpensive natural raw materials.

In the present work, parameters influencing the selectivity of the synthesis of FAU-zeolites from diatomite were studied. The final products after varying synthesis time were characterized by scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction and gas adsorption. It was found that high concentrations of NaCl could completely inhibit the formation of zeolite P, which otherwise usually forms as soon as maximum FAU crystallinity is reached. In the presence of NaCl, the FAU crystals were stable for extended time after completed crystallization of FAU before formation of sodalite. It was also found that addition of NaCl barely changed the crystallization kinetics of FAU zeolite and only reduced the final FAU particle size and SiO₂/Al₂O₃ ratio slightly. Other salts containing either Na or Cl were also investigated. Our results suggest that there is a synergistic effect between Na⁺ and Cl^-. This is attributed to the formation of (Na₄Cl)³⁺ clusters that stabilize the sodalite cages. This new finding may be used to increase the selectivity of syntheses leading to FAU-zeolites and avoid the formation of undesirable by-products, especially if impure natural sources of aluminosilica are used.

Bolivian diatomite was successfully used as a silica source for the synthesis of zeolite Y. Prior to synthesis, the diatomite was leached with sulfuric acid to remove impurities and aluminum sulfate was used as an aluminum source. The raw materials were reacted hydrothermally at 100 °C in water with sodium hydroxide and different Na2O/SiO2 ratios were investigated. The final products were characterized by scanning electron microscopy, X-ray diffraction, gas adsorption and inductively coupled plasma-atomic emission spectroscopy. Diatomites originating from different locations and therefore containing different types and amounts of minerals and clays as impurities were investigated. After optimization of synthesis time, zeolite Y with low SiO2/Al2O3 ratio (3.0–3.9) was obtained at a high yield for high alkalinity conditions (Na2O/SiO2 = 0.85–2.0). Lower Na2O/SiO2 ratios resulted in incomplete dissolution of diatomite and lower yield. Nevertheless, decreasing alkalinity resulted in a steady increase of the SiO2/Al2O3 ratio in zeolite Y. Consequently, it was possible to synthesize almost pure zeolite Y with a SiO2/Al2O3 ratio of 5.3 for a Na2O/SiO2 ratio of 0.6, albeit at a low yield. In this respect, diatomite enables the synthesis of high silica zeolite Y and behaves similarly to colloidal silica in traditional syntheses, with both sources of silica having in common a high degree of polymerization. Interestingly, the presence of minerals and clays in the starting diatomite had marginal effects on the outcome of the synthesis. However, their dissolution resulted in presence of calcium and magnesium in the zeolite Y crystals. Finally, overrun of all investigated compositions resulted in the formation of zeolite P nucleating and growing onto dissolving zeolite Y crystals, which was shown to be triggered when aluminum was completely depleted at high alkalinity

Uniform 13X films with thicknesses of 3 and 11 µm were grown on supports in the form of steel monoliths with a cell density of 1600 cpsi and microchannels width of 0.5 mm. Sharp breakthrough fronts and a dynamic uptake of 3.4 mmol CO₂ g^-1 zeolite were observed in the forwarding step of breakthrough experiments for a feed of 10 % CO₂ in N₂ with a high flow rate at 293 K and 1 bar. Numerical modeling showed that the adsorption process was very fast and that the transport of CO₂ in the thin zeolite layer was the rate-limiting step, the mass transfer resistance for the 11 µm film is 2.2 times lower than zeolite 13X pellets and 100 times lower than zeolite 4A beads. Axial dispersion, pressure drop, and gas film resistance were shown to be negligible. The steel monolith support provides good mechanical strength and excellent thermal conductivity for the 13X films. The combination of properties makes this adsorbent a good performer when compared with other types of structured zeolite adsorbents in reported literatures. This microchannel adsorbent is a promising alternative to traditional adsorbents in processes of fast CO₂ separation with short cycle times.

Fully biobased composite membranes for water purification were fabricated with cellulose nanocrystals (CNCs) as functional entities in chitosan matrix via freeze-drying process followed by compacting. The chitosan (10 wt%) bound the CNCs in a stable and nanoporous membrane structure with thickness of 250-270 μm, which was further stabilized by cross-linking with gluteraldehyde vapors. Scanning electron microscopy (SEM) studies revealed well-individualized CNCs embedded in a matrix of chitosan. Brunauer, Emmett and Teller (BET) measurements showed that the membranes were nanoporous with pores in the range of 13-10 nm. In spite of the low water flux (64 L m-2 h-1), the membranes successfully removed 98%, 84% and 70% respectively of positively charged dyes like Victoria Blue 2B, Methyl Violet 2B and Rhodamine 6G, after a contact time of 24 h. The removal of dyes was expected to be driven by the electrostatic attraction between negatively charged CNCs and the positively charged dyes.

The abatement of defects in zeolite membranes is essential for achieving high selectivity. In the present work, a simple and effective method for blocking defects in ultra-thin (ca. 0.5 μm) MFI zeolite membranes has been developed. The method is based on deposition of an ultra-thin (∼15 nm) layer of amorphous silica on the top surface of the membrane. Permporometry data indicated that the amount of defects, especially defects larger than 4 nm, in the membranes was significantly reduced after the modification. In mixture separation experiments, the CO2/H2 separation factor increased dramatically after blocking the defects in a defective membrane that was selected for the experiments. For instance, at 263 K and 9 bar feed pressure, the CO2/H2 separation factor increased from 8.5 to 36 after modification of the membrane, whereas the CO2 flux only decreased by ca. 40%.

Permporometry was used for the first time to characterize flow-through micropore defects down to 0.7 nm in size in MFI zeolite membranes. Helium was used as the non-adsorbing gas and n-hexane or benzene was used as the adsorbate. The helium flow through zeolite pores was estimated using percolation theory and the remaining flow was assigned to flow-through defects. The area distribution of flow-through defects was estimated from the data using a simple model and similar results were obtained using both adsorbates. The total area of defects determined using n-hexane as the adsorbate was as low as about 0.7% of the membrane area and defects with a width below 1 nm constituted 97% of the total defect area for the best membrane. The permporometry results were supported by n-hexane/1,3,5-trimethylbenzene separation experiments. The permporometry data were also consistent with HR-SEM observations indicating the presence of narrow open grain boundaries, and absence of large cracks and pinholes

In the present work, two ultra-thin MFI membranes, prepared using hydroxide and fluoride ions as mineralizing agents, respectively, were carefully examined by permporometry. The amount of micropore defects, as determined by permporometry, differed significantly between the two different membranes. For the first time, it was demonstrated that the micropore defects determined by permporometry were most likely open grain boundaries. The results were verified by direct observation of the open grain boundaries by a state-of-the-art XHR-scanning electron microscopy instrument. In addition, the permporometry data were also consistent with permeation data using 1,3,5-trimethylbenzene (TMB) as a probe molecule, separation data using an equimolar mixture of n-hexane and TMB, and nitrogen adsorption data.

In the present work, two ultra-thin MFI membranes, prepared using hydroxide and fluoride ions as mineralizing agents, respectively, were carefully examined by permporometry. The amount of micropore defects, as determined by permporometry, differed significantly between the two different membranes. For the first time, it was demonstrated that the micropore defects determined by permporometry were most likely open grain boundaries. The results were verified by direct observation of the open grain boundaries by a state-of-the-art XHR-scanning electron microscopy instrument. In addition, the permporometry data were also consistent with permeation data using 1,3,5-trimethylbenzene (TMB) as a probe molecule, separation data using an equimolar mixture of n-hexane and TMB, and nitrogen adsorption data

Photoelectrochemical (PEC) water splittingreactions are promising for sustainable hydrogen productionfrom renewable sources. We report here, the preparation of α-Fe₂O₃/Fe₃O₄ composite films via a single-step chemical vapordeposition of [Fe(O^tBu)₃]₂ and their use as efficient photoanode materials in PEC setups. Film thickness and phase segregation was controlled by varying the deposition time and corroborated through cross-section Raman spectroscopy and scanning electron microscopy. The highest water oxidationactivity (0.48 mA/cm² at 1.23 V vs RHE) using intermittent AM 1.5 G (100 mW/cm²) standard illumination was found forhybrid films with a thickness of 11 μm. This phenomenon is attributed to an improved electron transport resulting from ahigher magnetite content toward the substrate interface and an increased light absorption due to the hematite layer mainly located at the top surface of the film. The observed high efficiency of α-Fe₂O₃/Fe₃O₄ nanocomposite photoanodes is attributed to the close proximity and establishment of 3D interfaces between the weakly ferro- (Fe₂O₃) and ferrimagnetic (Fe₃O₄) oxides, which in view of their differential chemical constitution andvalence states of Fe ions (Fe²⁺/Fe³⁺) can enhance the charge separation and thus the overall electrical conductivity of the layer.

The present work highlights the microstructural features and mechanical properties of Y2O3 prepared with and without Yb3+ doping that processed through combustion synthesis involving various organic fuels such as urea, citric acid and glycine. Properties such as powder-now, particle packing, green density, % of shrinkage, sintered density, grain size, Vicker's microhardness (H-v) and fracture toughness (K-IC) were analyzed and compared with respect to the fuel sources. The as combusted precursors were calcined at 1100 degrees C for 4 h under oxygen atmosphere to obtain fully crystalline Y2O3 powders. Cylindrical pellets were fabricated as test specimens and sintered at 1600 degrees C for 3 h. The SEM images of the sintered yttria samples show an average grain size of < 3 mu m irrespective of the fuels. However, the mechanical properties show significant dependence on the fuels used. A maximum hardness of 6.8 +/- 0.1 and 7.0 +/- 0.1 GPa was obtained for Y2O3 and Yb3+ doped Y2O3 derived from glycine fuel. Whereas the maximum fracture toughness of 2.6 +/- 0.3 MPa m(1/2) was obtained for the samples derived from urea. The Yb3+ doping found to increase the bulk hardness of yttria from 0.2 to 0.6 GPa. The study contributes to appropriately select the fuels for obtaining high dense, mechanically stable yttria ceramics through combustion process.

An in-situ sulphated-combustion reaction was conducted on the precursor mixture consisting of yttrium nitrate, organic fuels (urea, citric acid and glycine) and 10 mol% ammonium sulphate [(NH4)(2)SO4] at 500 degrees C. Effect of sulphate addition on yttria particles morphology has been analyzed with respect to the types of fuels. In un-sulphated combustion, the calcined yttria powders showed rectangular particle morphology and low specific surface area. Whereas in sulphated-combustion spherical shaped yttria particles were achieved for glycine fuel. In the case of citric acid fuel, yttria powders with high specific surface area [26 m(2)/g] were obtained. For all the fuels, the sulphated-combustion reaction produced nanocrystalline yttria powders and they also had primary crystallite size below 4 nm in the as prepared conditions. Upon calcination at 1100 degrees C, these powders attained mean particle size of 50 nm which was confirmed by TEM.

Microwave assisted combustion synthesis is used for fast and controlled processing of advanced ceramics. Single phase and sinter active nanocrystalline cubic yttria powders were successfully synthesized by microwave assisted combustion using the organic fuels urea, citric acid and glycine as reducing agents. The precursor powders were investigated by thermogravimetry (TG) and differential scanning colorimetry (DSC) analyses. The as-prepared precursors and the resulting oxide powders calcined at 1100 °C in oxygen atmosphere were characterized for their structure, particle size and morphology. The thermal analyses (TG/DSC), X-ray diffraction (XRD) and Fourier transform infra red (FT-IR) results demonstrate the effectiveness of the microwave assisted combustion synthesis. The scanning electron microscopy (SEM) observations show the different morphologies of as-prepared powders and transmission electron microscopy (TEM) shows the particle sizes in the range of 30-100 nm for calcined powders for different fuels. The results confirm that the homogeneous, nano scale yttria powders derived by microwave assisted combustion have high crystalline quality and the morphology of the as-prepared precursor powders depends on the nature of organic fuel used.

Nanosized yttrium oxide and ytterbium doped yttrium oxide powders were prepared by ceramic combustion techniques such as flash combustion, citrate gel decomposition and glycine combustion using urea, citric acid and glycine respectively as fuels. As synthesized precursors and calcined powders were characterized for their structural, particle size and morphology, and the optimization of calcination process by differential scanning calorimetry and thermal gravimetry. The thermal analyses together with XRD results demonstrate the effectiveness of the combustion process for the synthesis of pure phase nanocrystalline powders. Nanocrystalline pure yttria powders were obtained by the calcination of as-prepared precursors at 1100 °C for 4 h.

Spark plasma sintered zirconia (3Y-TZP) specimens have been produced of 140 nm 372 nm and 753 nm grain sizes by sintering at 1250 C, 1450 C and 1600 C, respectively. The sintered zirconia specimens were grinded using a diamond grinding disc with an average diamond particle size of about 60 µm, under a pressure of 0.9 MPa. The influence of grinding and annealing on the grain size has been analysed. It was shown that thermal etching after of ruff grinding of specimens at 1100 C for one hour induced an irregular surface layer of about a few hundred nanometres in thickness of recrystallized nano-grains, independently of the initial grain size. However, if the ground specimens were exposed to higher temperature, e.g. annealing at 1575 °C for one hour, the nano-grain layer was not observed and the final grain size was similar to that achieved by the same heat treatments on carefully polished specimens. Therefore, by appropriate grinding and thermal etching treatments, nanograined surface layer can be obtained which increases the resistance to low temperature degradation.

More efficient laser materials are needed for space applications in order to save weight and make cost-savings. The fabrication of polycrystalline ceramic materials is a solution to obtain new compositions with better efficiency. In order to produce a Yb doped Y2O3 laser material, we developed a process to obtain yttrium oxide nanosized particles doped with ytterbium and a sintering method that leads to transparent polycrystalline ceramics. First, nano-powder of yttria was fabricated from a precursor with transient morphology, i.d. yttrium hydroxynitrate platelets that decompose into spherical yttria nano-particles during calcination. The influence of different dewatering methods on such precursors was investigated. Water removal by freeze-drying was shown to be optimal for the production of non- agglomerated nano-particles compared with other methods that involve solvent removal by evaporation. This was attributed to the ability of freeze-drying to avoid the formation of solid bridges, since water is directly removed by sublimation. In a second step, doping with ytterbium was performed. Two precipitation routes were compared: precipitation of hydroxynitrate platelets and precipitation of amorphous carbonate. This latter was shown to allow a better distribution of ytterbium in the yttrium oxide matrix after calcination of the corresponding precursor. This was explained in terms of the good cation mixing in the amorphous particles, while formation of the hydroxynitrate platelets resulted in segregation of ytterbium, probably because a second phase with different ytterbium/yttrium composition precipitates in the first stages of the synthesis. Finally, a method combining pre-sintering in vacuum followed by hot isostatic pressing was shown to be successful to produce transparent yttria ceramics from agglomerated powders with high purity. Pre-sintering in vacuum agglomerates of closely-packed particles enables differential sintering, which is responsible for the complete elimination of porosity in the agglomerates and for the formation of intergranular porosity only. Then, hot isostatic pressing treatment of the pre-sintered samples using the glass-canning technique reactivates sintering and coarsening, which causes almost complete pore elimination. Furthermore, a liquid phase formed during sintering because of pollution from the furnace. This liquid phase is thought of as to have helped densification to some extent. The best transparent ceramic showed a transmittance of 43% at 400 nm.

In this thesis, the author reports on a ceramic process leading to transparent ytterbium doped yttrium oxide ceramics. The full production route was investigated, namely: powder preparation, compaction and sintering. First, yttria nano-powder was fabricated from a precursor with transient morphology, i.e. yttrium hydroxynitrate platelets that decomposed into spherical yttria nano-particles during calcination. The influence of different dewatering methods on such precursors was investigated. Water removal by freeze-drying was shown to be optimal for the production of non- agglomerated nano-particles compared to other methods that involve solvent removal by evaporation. This was attributed to the ability of freeze-drying to avoid the formation of solid bridges, since water is directly removed by sublimation. In a second step, doping with ytterbium was performed. Two precipitation routes were compared: precipitation of hydroxynitrate platelets and precipitation of amorphous carbonate. The latter route was shown to allow a better distribution of ytterbium in the yttrium oxide matrix after calcination of the corresponding precursor. This was attributed to good cation mixing within the amorphous particles, while formation of the hydroxynitrate platelets resulted in segregation of ytterbium because of the precipitation of an ytterbium-rich secondary phase. Because of the laborious character of the above techniques, an alternative method for synthesizing yttrium oxide powder was developed. This method not only allows for producing weakly-agglomerated nano-particles with equiaxed morphology, but is also a very time-efficient process. Its characteristic feature lies in the ability to skip two processing steps encountered in common precipitation techniques (i.e. filtration and drying). The method is based on combustion synthesis, sulfation, and calcination at high temperature. Through careful tailoring of the process parameters, evolution of the cellular nanostructure towards individual yttrium oxide nano- particles was obtained during firing. A method combining pre-sintering in vacuum followed by hot isostatic pressing (HIP) using glass encapsulation was shown to be successful to produce transparent yttria ceramics from agglomerated powders. Pre- sintering in vacuum of compact agglomerates enables differential sintering, resulting in only intergranular porosity. Subsequent HIP treatment of the pre-sintered samples caused almost complete pore elimination and achievement of transparency. However, macro-defects were present in the final material. From these results it became obvious that the packing homogeneity must be improved. For comparison, green-bodies were produced by slip-casting or pressing followed by cold isostatic pressing (CIP). Rheology studies were performed in order to tailor the milling conditions and the quantity of dispersant to obtain slurries with minimum viscosity and which were suitable for slip-casting. Although slip-cast pellets exhibited similar densities as pressed samples after pre-sintering, they showed more homogeneous optical properties after HIP. This was attributed to density gradients in the pressed compacts. By using the novel powder synthesis and HIP methods developed in this work, yttrium oxide transparent ceramics doped with 30 at% ytterbium were fabricated. The best sample showed a transmittance of 25% at 400 nm for a thickness of 3mm.

There are generally two problems associated with cryogenic scanning electron microscopy (cryo-SEM) observations of large wet powder compacts. First, because water cannot be vitrified in such samples, formation of artefacts is unavoidable. Second, large frozen samples are difficult to fracture but also to machine into regular pieces which fit in standard holders, especially if made of hard materials like ceramics. In this article, we first describe a simple method for planning hard cryo-samples and a low-cost technique for cryo-fracture and transfer of large specimens. Subsequently, after applying the entire procedure to green pellets of iron ore produced by balling, we compare the influence of plunge- and unidirectional freezing on large entrapped bubbles throughout the samples as well as the degree of water filling at the outer surface of the pellets. By carefully investigating the presence of artefacts in large areas of the samples and by controlling the orientation of the sample during freezing and preparation, we demonstrate that unidirectional freezing enables the observation of large entrapped bubbles with minimum formation of artefacts, whereas plunge freezing is preferable for the characterization of the degree of water filling at the outer surface of wet powder compacts. The minimum formation of artefacts was due to the high packing density of the iron ore particles in the matrix

Imaging by extreme high resolution-scanning electron microscopy (XHR-SEM) with a monochromated and decelerated beam was applied on 5% (wt/wt) Na and Ca-montmorillonite gels frozen by high pressure freezing (HPF). In order to visualize the three-dimensional structure and the contacts between clay platelets, a new approach was developed. It consists in recording a sequence of micrographs on a region of interest during controlled sublimation. This simple method allows to rewind and to relate the instantaneous configuration between several particles to their original position in the hydrated state. Consequently, aggregates of parallel platelets (i.e. curved tactoids) were present in the Ca-sample and the instantaneous position of these aggregates in the course of sedimentation was revealed. The Na-sample consisted of a continuous network of flexible platelets sharing mostly face-to-face (FF) contacts caused by jamming at the relatively high concentration of the suspension (5% (wt/wt)), which was above the gel transition. Yet individual platelets belonging to the smallest size fraction were observed to be fully dispersed within the entangled structure, which confirmed the repulsive character of the gel. Substructures consisting of several platelets connected by FF-associations were also evidenced. The origin and potential impact of such substructures on the occurrence of the sol–gel transition and birefringence are discussed.

Transparent yttrium oxide ceramics doped with 30 at.% ytterbium were successfully produced by a combination of pre-sintering and hot isostatic pressing. The influence on the final transparency of different densification states and porosity configurations obtained by varying pre-sintering conditions were investigated by optical and electron microscopy. Our results show that densification prior to the final stage of sintering is necessary to limit final porosity. Samples showing open porosity were found to lead to pore entrapment because of the diffusion of argon inside the glass capsule during hot isostatic pressing. Transmittance measurements showed that the valence charge of the ytterbium ions was 3+ at the end of the process, indicating no effect of reduction when pre-sintering in vacuum was employed.

Slip casting and uniaxial pressing were compared as first consolidation stages prior to cold isostatic pressing (CIP) to produce translucent yttria ceramics. In the first step, yttria slurries suitable for slip casting were prepared. The viscosity was optimized with respect to the starting agglomeration state, amount of dispersant, milling time, and number of milling balls. Secondly, pellets were prepared either by slip casting or uniaxial pressing and then cold-isostatically pressed. Finally, the pellets were made translucent by a combination of pre-sintering and hot isostatic pressing (HIP). Although slip-cast and pressed samples exhibited similar green-body densities after CIP and pre-sintering, the samples prepared by slip casting were more homogeneous in terms of translucency and microstructure throughout their bodies. This was attributed to the ability of slip casting to minimize density gradients during packing, and to the beneficial effect of ball-milling to remove larger agglomerates before casting. Therefore, slip casting as a first consolidation stage prior to CIP appears to be more suitable than uniaxial pressing in order to prepare homogeneous optical ceramics.

In this work, five yttria powders with slightly different states of agglomeration, inherited from various procedures of dewatering the same precursor, were densified by a combination of vacuum sintering followed by hot isostatic pressing (HIP). In order to relate the densification behavior of each powder to its state of agglomeration, all powders were characterized by tap density measurements, X-ray diffraction, nitrogen adsorption, and laser scattering, while the microstructures of the corresponding densified samples were studied by optical and scanning electron microscopy. The five yttria powders produced sintered samples that differed remarkably from each other in terms of transparency. These discrepancies were related to the degree of fineness in the powders at two different levels. At the level of primary particles, fine and weakly agglomerated powder was very sinterable, causing abnormal grain growth to occur only in the very late stage of sintering. However, the resulting entrapped pores and reduction due to vacuum sintering were responsible for poor optical properties. At the agglomerate level, a bimodal size distribution was identified for all powders. For powders showing severe agglomeration of the primary particles, increasing the relative content of the smaller size population of agglomerates was found to trigger abnormal grain-growth earlier during presintering. This was attributed to the density around large agglomerates exceeding a critical threshold in the green bodies. Finally, transparency was achieved in samples for which presintering was stopped before grain growth became abnormal. This confirmed that the key to successfully obtaining transparency was to keep porosity intergranular, which could be removed subsequently by HIP treatment.

This method consists of a combination of vacuum sintering at 1600 °C followed by hot isostatic pressing (HIP) at 1500 °C of a highly agglomerated commercial powder. The use of evacuated glass capsules to perform HIP treatment allowed samples that showed open porosity after vacuum sintering to be sintered to transparency. The sintering response of the investigated powder was studied by careful microstructural observations using scanning electron microscopy and optical microscopy both in reflection and transmission. The successful key of this method was to keep porosity intergranular during pre-sintering, so that it can be removed subsequently by HIP treatment. It was found that agglomerates of closely packed particles are helpful to reach that purpose, since they densify fully and leave only intergranular porosity. However, performing HIP treatment at 1625 °C was found to result in opaque samples. This was attributed to the diffusion of argon inside the capsule. Contamination at different steps of processing was also investigated by inductively coupled plasma mass spectrometry (ICP-MS).

Two different precipitation routes leading to (YbxY1-x)2O3 nano-particles (with x = 0; 0.027; and 0.31) were compared, namely, precipitation of hydroxynitrate platelets and amorphous carbonate spherical particles. For both methods, the particle morphology was observed by scanning electron microscopy. X-ray diffraction studies of the unit cell, energy dispersive X-ray analysis and inductive coupled plasma spectroscopy were used to check the ytterbium distribution. The precipitation of amorphous carbonate was found to produce particles with uniform morphology and homogeneous distribution of ytterbium, while hydroxide precipitation favours the formation of hard and dense ytterbium-rich agglomerates. These differences are discussed in terms of precipitation, growth and agglomeration behaviour. The sinterability of both resulting powders is also discussed.

Yttrium oxide nano-powder has been successfully synthesized by a novel approach. In the first step, a foamy structure was produced by combustion synthesis using yttrium nitrate and glycine. This was followed by the addition of sulfate ions and calcination at 1100 °C for 4 h. The sulfated and unsulfated powders were characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM) and the Brunauer-Emmett-Teller method (BET). The sinterability of the resulting powders was also studied by dilatometry. The studies indicated that this method not only allows for producing weakly-agglomerated nano-particles, but is also a very time-efficient process in comparison to precipitation techniques. Moreover, the possibility of performing all processing steps in a fully automated batch reactor was also considered.

The influence of drying and dewatering of a yttrium hydroxynitrate precursor with transient morphology was investigated. The ability of this precursor to form soft agglomerated nanoparticles after calcination is dependent on the dewatering method. Freeze drying leads to finer particles than other dewatering methods that involve removal of the solvent from its liquid state. As water is directly removed by sublimation during freeze drying, this method inhibits the formation of solid bridges between hydroxynitrate platelets. These bridges, which form with the other dewatering methods, destabilize the spheroidization process of the platelets during subsequent firing at high temperatures.

Mechanism of MFI film growth from seed crystals and evolution of defects during the film growth were investigated. The hydrothermal growth of colloidal silicalite-1 crystals of 50 nm on silicon substrate was used to reveal the MFI film formation mechanism at different time intervals using high resolution-transmission electron microscopy (HR-TEM) and extreme high resolution-scanning electron microscopy (XHR-SEM). It was found that the MFI seeds started to grow in the early stages of hydrothermal treatment from 50 nm to 75 nm in size and connect to the crystals in the vicinity, showing the onset of film formation. The film growth mechanism was led by the sub-colloidal particles in the synthesis solution arriving at the crystal surfaces contributing to the film growth. A continuous film with a thickness of 100 nm was formed after 12 h of hydrothermal treatment containing pinhole defects. Pinhole defects disappeared after 24 h of hydrothermal treatment with a film thickness of 200 nm and grain boundaries thickness of 2 nm were formed. Furthermore, mesoporous defects were found in the grains of the film, which appeared due to the film growth by sub-colloidal particles of synthesis solution. The growth rate of the MFI film was calculated to 0.007 (μm/h) and compared with the crystal growth inside the synthesis solution.

ZSM-5 zeolite crystals with carefully controlled thicknesses in the range 20–110 nm, i.e. in the colloidal domain, were synthesized in fluoride and hydroxide media. The crystals were treated in steam at high temperature to evaluate the stability and evaluated by SEM, XRD, NMR and NH3-TPD. The results showed that the framework of crystals synthesized in fluoride media was more stable than the framework of crystals synthesized in hydroxide media. This should be an effect of lower concentration of structural defects and silanol groups in the former zeolites as reported by other groups. However, independently of the synthesis conditions, all crystals dealuminated rapidly when treated with steam at the conditions investigated in the present work.