Calcium phosphates and recently also magnesium phosphates, are used for medical applications, due to their biocompatibility and bioactivity. These properites makes spherical particles of calcium and magnesium phosphate suitable for carrier materials for drug delivery applications. By creating porous and/or hollow particles itis possible to load the particles with a drug and control therelease of the active substance. In this work, an ion-induced method for the synthesis of spherical calcium and magnesium phosphates was developed. A simple precipitation reaction was used, where substituting magnesium ions could replace the function of templates, such as surfactants or micelles, to induce the formation of spheres of a certain size and morphology. Experimental results showed that magnesium had an inhibitory effect on the nucleation and crystal growth of calcium phosphates. By using substituting ions as a structural regulator, it was possible to alter the size, morphology and phase composition of the spheres. At low magnesium concentrations, the spheres had a smooth surface andwere between 200 nanometer to 1 micrometer in diameter and composed of hydroxyapatite and/or magnesium-substituted beta-TCP. At higher magnesium concentrations, the spheres were about 10-50 micrometer with a rough, flaky surface. Results also proved that calcium ionshave the same effect on the crystallisation and self-assembly of magnesium phosphates. Apart from the magnesium concentration, reaction temperature proved to have a high influence on the sphereformation, whereas Ca/P ratio and reaction times above three hours did not affect the sphere formation to the same extent.

The method Atomic Layer Deposition, ALD, has been available since the 1970´s and it has opened the possibility to fabricate methods for inorganic thin films on a nanoscale. Later the interest for fabricating organic thin films with Molecular Layer Deposition, MLD, and controlling both the thickness and the composition of the film on a molecular scale. To develop the thin films a bit further a combination of organic and inorganic thin films is fabricated and therefore the best properties of the two types of thin films are combined.  The purpose of this bachelor´s thesis was to fabricate the multilayer thin film AlN-HQ on a silicon substrate. It began with a substantial review of the literature and planning of the approach. Followed by the laboratory work with fabricating the thin film by ALD. The laboratory work ended with analyzing the thin films by ATR-FT/MIR (attenuated total reflectance fourier transform mid-infrared spectroscopy) and XRR (X-ray reflectivity). All data provided where summarized and evaluated. An analysis of the thickness of the thin film was attempted with XRR but was not adequate for these samples. For a development of the method fabrication of the multilayer film AlN-HQ the thickness needs to be known. It could probably be analyzed by Scanning Electron Microscopy, SEM, but that type of analysis was not a part of this study.

Due to concerns for climate change and future supply of phosphorus fertilizer within agriculture, there has been an increased interest in the combustion of phosphorus containing waste residues and opportunity biomass fuels. Previous research has shown that during combustion, phosphorus has large impact on ash transformation reactions and may decrease or increase ash-related problems such as slag formation and bed agglomeration. This is a serious concern if new types of biomass are to be added for heat and power production. Additionally, plant studies and leaching tests of P-rich biomass ash indicate that the plant availability of phosphorus varies greatly with its association in the ash. As such, the ash transformation behavior of phosphorus is of great importance for the success of such ventures. While several studies have been made on the behavior of phosphorus during combustion, no comprehensive study has been made evaluating the effect of fuel composition and combustion conditions. In this work, the behavior of phosphorus was determined for a wide range of fuels and combustion conditions. More specifically, the objective was to determine (i) the effect of fuel ash composition and combustion technologies on the fate of phosphorus during combustion, (ii) investigate potential difference in the behavior of phosphorus during combustion of sewage sludge and plant based biomassand (iii)the effect of phosphorus on slag formation and bed agglomeration for the co-combustion of a wide range of plant based biomasses. The investigation was carried out by comparing experimental data gathered from the combustion of 26different biomass fuelsor fuel blends in a bench scale bubbling fluidized bed (5 kW, 18 experiments), an underfed pellet burner (20kW, 10 experiments) and a swirling powder burner (150 kW, 7 experiments). This included chemical characterization of bed ash, bottom ash and fly ash fractions by X-ray diffraction (XRD), scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS) in addition to qualitative measures of slagging-and bed agglomeration tendencies. It was found that phosphorus, irrespective of combustion technology and fuel composition, was mainly found in bed-, and bottom ash fractions and/or coarse fly ash fractions (>1μm). Based on the crystalline phase composition of the phosphates found in bed-, bottom-and coarse fly ash samples, phosphate speciation was correlated to the molar ratio between P, Ca and Mg for all three combustion technologies. Based on these results, it would be possible to control the behavior of phosphorus during combustion and the plant availability of phosphates in biomassash by designing fuel blends based on their fuel ash composition. In fluidized bed combustion, it was found that for similar combustion conditions and fuel ash compositions (with respect to K, Ca and P), the speciation of phosphorus in coarse ash fractions was significantly different from experiments with plant based biomass compared to sewage sludge. Unlike ash from plant based biomass, the crystalline phase composition of ash from sewage sludge did not change with the relative concentration of K, Ca andP in the fuel. The results suggest that the reaction pathway of phosphorus during combustion of sewage sludge is different to plant based biomass due to difference in the association of phosphorus in the fuel. The effect of phosphorus on slag formation and bed agglomeration in biomass combustion was mainly related to the relative fuel ash concentration of K, Ca, Mg, Si and P. In fluidized bed combustion, P contributes to the formation of agglomerates through the melt induced mechanism, through complex interaction with K, Ca, Mg and Si. Similarly, in fixed bed combustion the composition of slag indicatedthatslag formation involves the formation of P and Si rich ash melt with a varying content of K, Ca and Mg. In both cases, the severity of problems was related to the melting behavior of the (CaO,MgO)-K2O-(SiO2,P2O5) multicomponent system.

Two dimensional (2D) materials have received growing interest because of their unique properties compared to their bulk counterparts. Graphene is the archetype 2D solid, but other materials beyond graphene, such as MoS2 and BN have become potential candidates for several applications. Recently, a new family of 2D materials of early transition metal carbides and carbonitrides (Ti2CTx, Ti3C2Tx, Ti3CNTx, Ta4C3Tx, and more), labelled MXenes, has been discovered, where T stands for the surface-terminating groups. Before the present work, MXenes had only been synthesized in the form of exfoliated and delaminated powders, which is not suitable for electronic applications. In this thesis, I demonstrate the synthesis of MXenes as epitaxial thin films, a more suitable form for electronic and photonic applications. Results show that 2D epitaxial Ti3C2Tx films - produced by HF and NH4HF2 etching of magnetron sputter-grown Ti3AlC2 - exhibit metallic conductive behaviour down to 100 K and are 90% transparent to light in the visible-infrared range. The results from this work may open the door for MXenes as potential candidates for transparent conductive electrodes as well as in electronic, photonic and sensing applications. MXenes have been shown to intercalate cations and molecules between their layers that in turn can alter the surface termination groups. There is therefore a need to study the surface chemistries of synthetized MXenes to be able to study the effect of intercalation as well as altering the surface termination groups on the electronic structure and chemical states of the elements present in MXene layers. X-ray Photoelectron Spectroscopy (XPS) in-depth characterization was used to investigate surface chemistries of Ti3C2Tx and Ti2CTx. This thesis includes the discussion of the effect of Ar+ sputtering and the number of layers on the surface chemistry of MXenes. This study serves as a baseline for chemical modification and tailoring of the surface chemistry groups to potential uses and applications. New MXene phases, Nb2CTx and V2CTx, are shown in this thesis to be produced from HF chemical etching of Nb2AlC and V2AlC powders. Characterization of the produced MXenes was carried out using Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), Transmission Electron Microscope (TEM) and XPS. Nb2CTx and V2CTx showed promising performance as electrodes for Li-ion batteries. In this thesis, electrochemical etching was used in an attempt to produce 2D metal carbides (MXene) from their ternary metal carbides, Ti3SiC2, Ti3AlC2 and Ti2AlC MAX phases. MAX phases in the form of highly dense bulk produced by Hot Isostatic Press. Several etching solutions were used such as HF, NaCl and HCl. Unlike the HF chemical etching of MAX phases, which results in MXenes, the electrochemical etching resulted in Carbide Derived Carbon (CDC). Here, I show the characterization of the produced CDC using several techniques such as XRD, TEM, Raman spectroscopy, and XPS. Electrochemical characterization was performed in the form of cyclic voltammetry, which sheds light on the etching mechanism. / <p>The series name <em>Linköping Studies in Science and Technology Licentiate Thesis</em> in this publication is incorrect. Correct name is <em>Linköping Studies in Science and Technology. Thesis</em>.</p>

<p>This work is part of a research program where the aim is to develop an</p><p>electroanalytical technique to determine the amount of dissolved oxide and hydroxide in industrial Mg electrolytes. The systems studied were mixtures of MgCl₂ and NaCl, ranging from pure MgCl₂ to melts containing 10 mole % MgCl₂ / 90 mole % NaCl. To these melts, additions of MgO and MgOHCl were done at temperatures ranging from 475 to 850°C. Voltammetric measurements were performed before and after addition of MgO or MgOHCl and melt samples were taken for analysis. The quenched melt samples wereanalysed by carbothermal reduction analysis and the acid consumption method to obtain the O^2- and OH^-contents in the samples. Linear sweep voltammetry was performed with a sweep rate of 200 mV/sec in two potential regions to detect the concentration of dissolved MgOHCl and MgO. The experiments were performed inside a glove box having water and oxygen contents of, respectively, <1 ppm and <2 ppm. The results indicate that the rate of decomposition of MgOHCl increases with increasing temperature, as expected. In melts with high content of NaCl the underpotential deposition of sodium has a large influence on the uncertainty in the reading of the current density of MgOHCl reduction. Linear relations between MgO and MgOHCl concentrations and the peak current densities for the electrochemical reactions of the dissolved MgO and MgOHCl species in the melt, respectively, were observed. The diffusion coefficients of MgO and MgOHCl in the different melts were calculated. The diffusion coefficients decrease with increasing content of MgCl₂. For MgOHCl the diffusion coefficient decreases from 5.6*10^-5 cm²/sec in 20 mole % MgCl₂ / 80 mole % NaCl to 2.1*10^-5 cm²/sec in pure MgCl₂, both measurements done at 800°C. For MgO the diffusion coefficient decreases from 6*10^-5 cm²/sec in 41.5 mole % MgCl2 / 58.5 mole % NaCl to 0.8*10^-5 cm²/sec in pure MgCl₂, both measurements done at 730°C. The results show that it is possible to use cyclic voltammetry for quantitative analysis of MgOHCl in MgCl₂based melts.</p>

<p>Smaller cellular telephones and more energy-efficient windows are just two examples of technological advances which call for new materials. Materials chemists seek to develop new materials, both out of pure curiosity to see which combination of elements and structures can be obtained and in efforts to produce materials, with specific properties. The starting materials (in solid, liquid or gaseous form) can then be combined and prepared in various ways. A chemical method that is gaining more attention for thin-film growth is Atomic Layer Deposition (ALD). This is a sophisticated type of vapor deposition in which the precursor gases are introduced separately into the reaction chamber.</p><p>Silicon carbide (SiC) and cubic boron nitride (c-BN) are extremely hard diamond-like materials, both with a high potential for application within the modern microelectronics and tool industry. Hexagonal boron nitride (h-BN), with its graphite-like layered structure, is a promising ceramics material.</p><p>Deposition of thin SiC and BN films from gaseous precursors has been studied by theoretical and experimental methods. The chemical composition and atomic arrangement of a growing surface is important for vapor growth. The surface may be terminated (e.g., by hydrogen atoms) and adopt various geometrical structures. Reconstruction of unterminated SiC(0001) surfaces, as well as H abstraction from the corresponding H-terminated surfaces, were studied using quantum mechanical calculations. Elementary reactions for vapor growth of SiC and BN, and <i>in situ</i> incorporation of dopant and contaminant species into these surfaces were also investigated theoretically. Moreover, thin films of BN were deposited by means of laser-assisted ALD. The general goal has been to predict and/or explain experimental results by investigating growth mechanisms.</p>

This work is part of a research program where the aim is to develop an electroanalytical technique to determine the amount of dissolved oxide and hydroxide in industrial Mg electrolytes. The systems studied were mixtures of MgCl2 and NaCl, ranging from pure MgCl2 to melts containing 10 mole % MgCl2 / 90 mole % NaCl. To these melts, additions of MgO and MgOHCl were done at temperatures ranging from 475 to 850°C. Voltammetric measurements were performed before and after addition of MgO or MgOHCl and melt samples were taken for analysis. The quenched melt samples wereanalysed by carbothermal reduction analysis and the acid consumption method to obtain the O2- and OH- contents in the samples. Linear sweep voltammetry was performed with a sweep rate of 200 mV/sec in two potential regions to detect the concentration of dissolved MgOHCl and MgO. The experiments were performed inside a glove box having water and oxygen contents of, respectively, &lt;1 ppm and &lt;2 ppm. The results indicate that the rate of decomposition of MgOHCl increases with increasing temperature, as expected. In melts with high content of NaCl the underpotential deposition of sodium has a large influence on the uncertainty in the reading of the current density of MgOHCl reduction. Linear relations between MgO and MgOHCl concentrations and the peak current densities for the electrochemical reactions of the dissolved MgO and MgOHCl species in the melt, respectively, were observed. The diffusion coefficients of MgO and MgOHCl in the different melts were calculated. The diffusion coefficients decrease with increasing content of MgCl2. For MgOHCl the diffusion coefficient decreases from 5.6*10-5 cm2/sec in 20 mole % MgCl2 / 80 mole % NaCl to 2.1*10-5 cm2/sec in pure MgCl2, both measurements done at 800°C. For MgO the diffusion coefficient decreases from 6*10-5 cm2/sec in 41.5 mole % MgCl2 / 58.5 mole % NaCl to 0.8*10-5 cm2/sec in pure MgCl2, both measurements done at 730°C. The results show that it is possible to use cyclic voltammetry for quantitative analysis of MgOHCl in MgCl2 based melts.

Smaller cellular telephones and more energy-efficient windows are just two examples of technological advances which call for new materials. Materials chemists seek to develop new materials, both out of pure curiosity to see which combination of elements and structures can be obtained and in efforts to produce materials, with specific properties. The starting materials (in solid, liquid or gaseous form) can then be combined and prepared in various ways. A chemical method that is gaining more attention for thin-film growth is Atomic Layer Deposition (ALD). This is a sophisticated type of vapor deposition in which the precursor gases are introduced separately into the reaction chamber. Silicon carbide (SiC) and cubic boron nitride (c-BN) are extremely hard diamond-like materials, both with a high potential for application within the modern microelectronics and tool industry. Hexagonal boron nitride (h-BN), with its graphite-like layered structure, is a promising ceramics material. Deposition of thin SiC and BN films from gaseous precursors has been studied by theoretical and experimental methods. The chemical composition and atomic arrangement of a growing surface is important for vapor growth. The surface may be terminated (e.g., by hydrogen atoms) and adopt various geometrical structures. Reconstruction of unterminated SiC(0001) surfaces, as well as H abstraction from the corresponding H-terminated surfaces, were studied using quantum mechanical calculations. Elementary reactions for vapor growth of SiC and BN, and in situ incorporation of dopant and contaminant species into these surfaces were also investigated theoretically. Moreover, thin films of BN were deposited by means of laser-assisted ALD. The general goal has been to predict and/or explain experimental results by investigating growth mechanisms.

No description available.

In this thesis, a synthesis concept has been developed, which uses nitrogen-rich liquid phases for sintering of Ca-α-sialon ceramics. First, keeping the Si/Al ratios constant, the effects of N/O ratio on the properties and microstructure were investigated through a liquid phase sintering process. Second, nitrogen-rich Ca-α-sialon ceramics, with nominal compositions: CaxSi12-2xAl2xN16, x &lt; 2.0, was synthesized and characterized. Third, mechanical and thermal properties of nitrogen-rich Ca-α-sialons were investigated in terms of high temperature deformation resistance,reaction mechanism, phase stability and oxidation resistance, and further correlated to their phase assemblage and microstructure observation. It has been found that increasing the N/O and Ca/Al ratio simultaneously in the materials could result in development of a microstructure with well shaped, high-aspect-ratio Ca-α-sialon grains, and an improvement in both toughness and hardness. For the nitrogen-rich Ca-α-sialon, mono-phasic α-sialon ceramics were obtained for 0.51 ≤ x ≤ 1.32. The obtained Ca-α-sialon ceramics with elongated-grain microstructures show a combination of high hardness and high fracture toughness. Compared with the oxygen-rich Ca-α-sialons, the nitrogen-rich Ca-α-sialons exhibited approximately 150 oC higher deformation onset temperatures and decent properties even after the deformation. The α-sialon phase was first observed at 1400 oC, however the phase pure Ca-α-sialon ceramics couldn’t be obtained until 1800 oC. The nitrogen-rich Ca-α-sialons were thermal stable, no phase transformation observed in the temperatures range1400-1600 oC. In general, mixed α/β-sialon showed better oxidation resistance than pure α-sialon in the low temperature range (1250-1325 oC), while α-sialons with compositions located at α/β-sialon border-line showed significant weight gains over the entire temperature range (1250-1400 oC).