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A eutectic in La-rich La-Cu₀.₅Ni₀.₅-Al alloys was determined by studying the melting behaviors and the microstructure observations. The microstructures of the La-Cu-Ni-Al alloys prepared by Bridgman Solidification and copper mould casting were studied by using scanning electron microscope (SEM). The results show that La₆₆[Cu₀.₅Ni₀.₅]₂₀Al₁₄ alloy is very near to a pseudo-ternary eutectic. When the cooling rate is higher than 450 K/s, fully amorphous can be formed; when the cooling rate is within 15 K/s to 450 K/s, the alloy has a microstructure of dendrite plus amorphous, when the cooling rate is within 12 K/s to 1.5 K/s, the microstructures of the alloy are dendrite plus eutectic, and when the cooling rate is lower than 0.12 K/s, the morphology of the alloy is eutectic microstructure. The off eutectic alloy has better glass forming ability, the best glass forming alloy obtained at La₆₂[Cu₀.₅Ni₀.₅>]₂₄Al₁₄ along the composition line of La₈₆₋x[Cu₀.₅Ni₀.₅]xAl₁₄. It has a potential to form bulk metallic glassy rod samples with diameter larger than 12 mm. / Singapore-MIT Alliance (SMA)

The knowledge of growth and characterizing techniques is essential for the preparation of high quality thin films and multilayers. Here, structural properties have been investigated by X-ray reflectivity, X-ray diffraction, and transmission electron microscopy while the composition was determined by Rutherford backscattering spectrometry. For the magnetic studies, magneto-optical Kerr effect and X-ray magnetic circular dichroism have been used. The structural properties of the metal/insulator multilayer system, Fe/MgO, have been investigated. The coherency of the layers was influenced by the difference of the atomic distance in the Fe and MgO layers, resulting in long range strain fields. As a consequence, the coherency between the layers is not maintained. The atomic steps can not exist in amorphous materials, due to the absence of well defined atomic distances. Furthermore, the magnetic properties of amorphous materials allow a tuning of magnetic properties such as magnetic anisotropy and ordering temperature. The possibility to imprint arbitrary magnetic anisotropy in nanolaminated magnetic amorphous Co68Fe24Zr8 was demonstrated. The ratio of the orbital to spin moments for both Fe and Co was determined, for both thick and thin layers embedded in amorphous Al70Zr30 layers. When growing Co68Fe24Zr8 /Al2O3 the layers exhibit large changes in layer quality with thickness of the layers, ultimately affecting the magnetic properties of the stack. The use of protective layers is of large importance when performing ex-situ measurements. Most of the materials used were capped by Al2O3, effectively hindering both the reaction with oxygen and water. The penetration of hydrogen through different thicknesses of alumina was investigated. The experiments confirmed high degree of passivation as well as the possibility to selectively diffuse hydrogen through these layers. The use of element specific diffusion barriers allows the tailoring of magnetic properties of magnetic thin films and multilayers.

The method of in situ high pressure neutron diffraction was employed to measure reliable diffraction patterns to help illuminate the density-driven structural transformations in GeO2, SiO2, B2O3 and GeSe2 glass. The majority of this neutron diffraction work employed the diffractometer D4c at the ILL with a Paris-Edinburgh press which enabled the pressure range from ambient to 8 GPa to be accessed. In the cases of GeO2 and GeSe2 glass, the neutron diffraction with isotopic substitution (NDIS) protocol was developed to provide benchmark experimental results to test the results obtained from various molecular dynamics simulations using different theoretical schemes. For GeO2 glass, from a combination of neutron diffraction and molecular dynamics results, it was found that the increase in density of the glass initially occurs through a reorganisation of corner-shared GeO4 tetrahedra on an intermediate length scale as the pressure is increased from ambient to 5 GPa. At higher pressures, there is a progression from a tetrahedral to an octahedral glass, via the formation of 5-fold coordinated Ge atoms which have a predominantly square pyramidal geometry. In the work on SiO2 and B2O3 glass the pressure range for the in situ high pressure neutron diffraction results was extended to 14.5 GPa and 17.5 GPa, respectively, by using the PEARL diffractometer at ISIS. For both materials the neutron diffraction results provide complementary information to pressure x-ray diffraction studies helping to elucidate the mechanism of network collapse. In the case of SiO2 glass, densification over the measured pressure range occurs predominantly by a reorganisation of corner shared SiO4 tetrahedra on an intermediate length scale. In the case of B2O3 glass, the B-O coordination number changes from 3 to ∼ 3.9 at the pressure is increased from ∼ 8 to 17.5 GPa. For GeSe2 glass, from a combination of neutron diffraction and molecular dynamics results, it was found that the density increase from ambient pressure up ∼ 8 GPa occurs by a reorganisation of both corner and edge-sharing GeSe4 tetrahedra on an intermediate length scale. Above this pressure, 5- and 6-fold coordinated Ge atoms start to form at a similar density and homopolar bonds play an intimate role in the formation of these higher coordinated polyhedra.

Microscale bi-material lattices with near zero thermal expansion are designed to create a thermally stable optical surface for applications in a space telescope. To facilitate the design, the thermal expansion of a unit cell with spacers is derived analytically and validated via finite element studies. Predicting the lattice behaviour also requires knowledge of the constituent properties. To this end, molecular dynamics simulations are performed to determine the thermal expansion and recrystallization behaviour of aluminum and titanium thin films, and nanoindentation experiments are conducted to extract their elastic-plastic properties. Unit cell configurations giving near zero thermal expansion are obtained through iterative analysis. The resulting designs are analyzed and validated via finite element simulations and shown to exhibit long term stability.

Microscale bi-material lattices with near zero thermal expansion are designed to create a thermally stable optical surface for applications in a space telescope. To facilitate the design, the thermal expansion of a unit cell with spacers is derived analytically and validated via finite element studies. Predicting the lattice behaviour also requires knowledge of the constituent properties. To this end, molecular dynamics simulations are performed to determine the thermal expansion and recrystallization behaviour of aluminum and titanium thin films, and nanoindentation experiments are conducted to extract their elastic-plastic properties. Unit cell configurations giving near zero thermal expansion are obtained through iterative analysis. The resulting designs are analyzed and validated via finite element simulations and shown to exhibit long term stability.

This thesis employs experimental and theoretical methods to characterise carbon nitride solids and proposes a generalstructural model for amorphous carbon nitride (a-C:N). It finds that a-C:N deposited by several methods is essentially identical, with similar bonding environments for carbon and nitrogen atoms. Using evidence from several techniques, the saturation of nitrogen in an sp2 carbon matrix is discussed. The experimental studies on a range of carbon nitride solids show no evidence for a crystalline form of carbon nitride. In addition to the experimental characterisation of a-C:N, ab initio molecular dynamics were used to investigate bonding and structure in carbon nitride. These simulations show that the most common form of nitrogen bonding was three-fold sites with a lone pair of electrons. Two-fold nitrogen sites were also found in agreement with experimental findings. An increase of nitrogen in a-C:N decreases the sp3-carbon fraction, but this is not localised on the nitrogen and the effect is most severe at high densities. A simulation of a low density/high nitrogen content network shows that the nitrogen saturation seen experimentally may be due to the formation of N2 dimers and C-N molecules which are easily driven out of the structure. The ab initio simulations also explore the nature of charged nitrogen and carbon sites in a-C:N. An analysis based on Wannier Function centres provided further information about the bonding and allowed for a detailed classification of these sites. The removal of electrons from the networks caused structural changes that could explain the two-state conductivity in ta-C:N memory devices. Finally, a theoretical study of the electron energy-loss near-edge structure (ELNES) calculated using multiple scattering theory is presented. The calculated ELNES of diamond, graphite and boron, silicon and carbon nitride structures compare well to experiment and supports the experimental finding that no crystalline carbon nitride had (or has) been produced. These ELNES calculations will however, provide a means of identifying crystalline beta-C3N4 should it be synthesised.

In the industry of today, materials which can adsorb and hold large amounts of water are playing an important role. Here, the free and bound water carrying capacity of an amorphous magnesium carbonate is investigated. It is also determined how these parameters depend on the relative humidity of the surrounding environment. To do this, the technique of dielectric spectroscopy is employed. Along with the water binding properties, the concentration of charge carriers and the diffusion coefficient was determined. A smaller part of around 10-30 % of the water adsorbed was shown to behave as free water in the material. The concentration of charge carriers was calculated to be in an order of magnitude of 1018-1022 m-3 for the higher relative humidity environments. The diffusion coefficient was shown to be about 5*10-9 m2/s for the adsorption spectrum. This value is in good agreement with the value for OH- ions in water.

This thesis deals with various functional materials from first-principles methods and is divided into two major parts according to the underlying atomic structure of the system under study. The first part of the thesis deals with the temperature-induced structural phase transitions in metallic  β'-AuZn and perovskite oxide LiOsO3. The former one, i.e. binary AuZn, belongs to a class of shape-memory alloys that regain their initial shape due to a reversible martensitic phase transformation. Here, by means of density functional and density functional perturbation theories, we show that the martensitic transition is due to coupling between the Fermi surface nesting and anomalies in the phonon dispersion relations. The other metallic system, perovskite LiOsO3, exhibits a ferroelectric-like transition and is currently the first and sole realization of the Anderson and Blount idea. By means of ab initio molecular dynamics simulations, we investigate the mechanism behind this structural phase transformation. Another part of the thesis is dedicated to modelling and characterization of topologically disordered materials on atomic level. The structural and electronic properties of amorphous W-S-N are addressed regarding its outstanding tribological properties, i.e. almost vanishing friction coefficient. Molecular dynamics “melt-and-quench” technique has been employed in order to construct a model structure of amorphous W-S-N. Further analysis of the atomic structure revealed a formation of quasi-free N2 molecules trapped in S cages, which, together with the complex atomic structure of W-S-N, is the key to ultra-low-friction in this functional material. In the last chapter of the thesis a magnetic class of amorphous materials is addressed. Magnetic order in amorphous Gd-Fe ferrimagnet has been shown to undergo magnezation switching driven by a femtosecond laser pulse. Here, we combine first-principles density functional theory and atomistic spin dynamics simulations to explore this phenomena. A possible mechanism behind magnetization reversal in Gd-Fe based on a combination of the Dzyaloshinskii-Moriya interaction and exchange frustration is proposed.

This thesis employs experimental and theoretical methods to characterise carbon nitride solids and proposes a generalstructural model for amorphous carbon nitride (a-C:N). It finds that a-C:N deposited by several methods is essentially identical, with similar bonding environments for carbon and nitrogen atoms. Using evidence from several techniques, the saturation of nitrogen in an sp2 carbon matrix is discussed. The experimental studies on a range of carbon nitride solids show no evidence for a crystalline form of carbon nitride. In addition to the experimental characterisation of a-C:N, ab initio molecular dynamics were used to investigate bonding and structure in carbon nitride. These simulations show that the most common form of nitrogen bonding was three-fold sites with a lone pair of electrons. Two-fold nitrogen sites were also found in agreement with experimental findings. An increase of nitrogen in a-C:N decreases the sp3-carbon fraction, but this is not localised on the nitrogen and the effect is most severe at high densities. A simulation of a low density/high nitrogen content network shows that the nitrogen saturation seen experimentally may be due to the formation of N2 dimers and C-N molecules which are easily driven out of the structure. The ab initio simulations also explore the nature of charged nitrogen and carbon sites in a-C:N. An analysis based on Wannier Function centres provided further information about the bonding and allowed for a detailed classification of these sites. The removal of electrons from the networks caused structural changes that could explain the two-state conductivity in ta-C:N memory devices. Finally, a theoretical study of the electron energy-loss near-edge structure (ELNES) calculated using multiple scattering theory is presented. The calculated ELNES of diamond, graphite and boron, silicon and carbon nitride structures compare well to experiment and supports the experimental finding that no crystalline carbon nitride had (or has) been produced. These ELNES calculations will however, provide a means of identifying crystalline beta-C3N4 should it be synthesised.