Computer simulation of H and He effects in fusion reactor materials

Fusion power is an appealing source of clean and abundant energy. The radiation resistance of reactor materials is one of the greatest obstacles on the path towards commercial fusion power. These materials are subject to a harsh radiation environment, and cannot fail mechanically or contaminate the fusion plasma. Moreover, for a power plant to be economically viable, the reactor materials must withstand long operation times, with little maintenance. The fusion reactor materials will contain hydrogen and helium, due to deposition from the plasma and nuclear reactions because of energetic neutron irradiation. The first wall divertor materials, carbon and tungsten in existing and planned test reactors, will be subject to intense bombardment of low energy deuterium and helium, which erodes and modifies the surface. All reactor materials, including the structural steel, will suffer irradiation of high energy neutrons, causing displacement cascade damage. Molecular dynamics simulation is a valuable tool for studying irradiation phenomena, such as surface bombardment and the onset of primary damage due to displacement cascades. The governing mechanisms are on the atomic level, and hence not easily studied experimentally. In order to model materials, interatomic potentials are needed to describe the interaction between the atoms. In this thesis, new interatomic potentials were developed for the tungsten-carbon-hydrogen system and for iron-helium and chromium-helium. Thus, the study of previously inaccessible systems was made possible, in particular the effect of H and He on radiation damage. The potentials were based on experimental and ab initio data from the literature, as well as density-functional theory calculations performed in this work. As a model for ferritic steel, iron-chromium with 10% Cr was studied. The difference between Fe and FeCr was shown to be negligible for threshold displacement energies. The properties of small He and He-vacancy clusters in Fe and FeCr were also investigated. The clusters were found to be more mobile and dissociate more rapidly than previously assumed, and the effect of Cr was small. The primary damage formed by displacement cascades was found to be heavily influenced by the presence of He, both in FeCr and W. Many important issues with fusion reactor materials remain poorly understood, and will require a huge effort by the international community. The development of potential models for new materials and the simulations performed in this thesis reveal many interesting features, but also serve as a platform for further studies.

Deformation and crystallization of Zr-based amorphous alloys in homogeneous flow regime

The purpose of this study is to experimentally investigate the interaction of inelastic deformation and microstructural changes of two Zr-based bulk metallic glasses (BMGs): Zr41.25Ti13.75Cu12.5Ni10Be22.5 (commercially designated as Vitreloy 1 or Vit1) and Zr46.75Ti8.25Cu7.5Ni10Be27.5 (Vitreloy 4, Vit4). High-temperature uniaxial compression tests were performed on the two Zr alloys at various strain rates, followed by structural characterization using differential scanning calorimetry (DSC) and transmission electron microscopy (TEM). Two distinct modes of mechanically induced atomic disordering in the two alloys were observed, with Vit1 featuring clear phase separation and crystallization after deformation as observed with TEM, while Vit4 showing only structural relaxation with no crystallization. The influence of the structural changes on the mechanical behaviors of the two materials was further investigated by jump-in-strain-rate tests, and flow softening was observed in Vit4. A free volume theory was applied to explain the deformation behaviors, and the activation volumes were calculated for both alloys.

Rapid growth of nanotubes and nanorods of wurtzite ZnO through microwave-irradiation of a metalorganic complex of zinc and a surfactant in solution

Large quantities of single-crystalline ZnO nanorods and nanotubes have been prepared by the microwave, irradiation of a metalorganic complex of zinc, in the presence of a surfactant. The method is simple, fast, and inexpensive (as it uses a domestic microwave oven), and yields pure nanostructures of the hexagonal wurtzite phase of ZnO in min, and requires no conventional templating. The ZnO nanotubes formed have a hollow core with inner diameter varying from 140-160 nm and a wall of thickness, 40-50 nm. The length of nanorods and nanotubes varies in the narrow range of 500-600 nm. These nanostructures have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and selected area electron diffraction (SAED). The ZnO nanorods and nanotubes are found by SAED to be single-crystalline. The growth process of ZnO nanorods and nanotubes has been investigated by varying the surfactant concentration and microwave irradiation time. Based on the various results obtained, a tentative and plausible mechanism for the formation of ZnO nanostructures is proposed.

Kinetics of two-stage crystallization in Metglas 2826A

Crystallization kinetics of MSI and MSII stages in Metglas 2826A has been investigated by quantitative transmission electron microscopy. The volume fraction of crystallization against time curve has been found to show a plateau in the lower temperature region of annealing. It has been found that the glass transition temperature, T g, has no effect on the sequence reversal of the crystallization reaction. It has been shown that the sequence reversal of transformation stages occurs due to the large difference in the activation energy of crystallization of MSI and MSII. In addition, the change in the morphology of the crystals obtained by annealing the amorphous alloy below and above the glass transition temperature, T g, is reported.

Electron microscopic investigation of high-temperature oxide superconductors

Electron microscopic investigations have been carried out on superconducting YBa2Cu3 O7−δ, NdBa2Cu3 O7−δ and related oxides. All these orthorhombic oxides exhibit twin domains. Based on high resolution electron microscopy, it is shown that there is no significant change in the structure across the twins. Oxides of the La2−x Sr x (Ba x )CuO4 system do not show twins, but exhibit other types of defects. Twins appear to be characteristic of only the orthorhombic 123 structures.

Self-assembled flower-like nanostructures of InN and GaN grown by plasma-assisted molecular beam epitaxy

Nanosized hexagonal InN flower-like structures were fabricated by droplet epitaxy on GaN/Si(111) and GaN flower-like nanostructure fabricated directly on Si(111) substrate using radio frequency plasma-assisted molecular beam epitaxy. Powder X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to study the crystallinity and morphology of the nanostructures. Moreover, X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) were used to investigate the chemical compositions and optical properties of nano-flowers, respectively. Activation energy of free exciton transitions in GaN nano-flowers was derived to be similar to 28.5 meV from the temperature dependent PL studies. The formation process of nano-flowers is investigated and a qualitative mechanism is proposed.

Nonlinear fracture properties of concrete-concrete interfaces

The fracture properties of different concrete-concrete interfaces are determined using the Bazant's size effect model. The size effect on fracture properties are analyzed using the boundary effect model proposed by Wittmann and his co-workers. The interface properties at micro-level are analyzed through depth sensing micro-indentation and scanning electron microscopy. Geometrically similar beam specimens of different sizes having a transverse interface between two different strengths of concrete are tested under three-point bending in a closed loop servo-controlled machine with crack mouth opening displacement control. The fracture properties such as, fracture energy (G(f)), length of process zone (c(f)), brittleness number (beta), critical mode I stress intensity factor (K-ic), critical crack tip opening displacement CTODc (delta(c)), transitional ligament length to free boundary (a(j)), crack growth resistance curve and micro-hardness are determined. It is seen that the above fracture properties decrease as the difference between the compressive strength of concrete on either side of the interface increases. (C) 2010 Elsevier Ltd. All rights reserved.

Structural, optical and electrical characteristics of transparent bismuth vanadate films deposited on indium tin oxide coated glass substrates

Bismuth vanadate (BVO) thin films were fabricated on indium tin oxide (ITO) coated glass substrates using pulsed laser ablation technique and investigated their structural, optical and electrical properties. The use of the indium tin oxide coated glass substrate resulted in reducing the leakage current characteristics of crystalline BVO thin films. The X-ray diffraction (XRD) studies confirmed the monophasic nature of the post annealed (500 A degrees C/1 h) films. The atomic force microscopy indicated the homogeneous distribution of crystallites in the as-deposited films. The as-deposited and the post annealed films were almost 90% transparent (380-900 nm) as confirmed by optical transmission studies. Dielectric constant of around 52 was attained accompanied by the low dielectric loss of 0.002 at 10 kHz for post annealed films. The leakage current of the post annealed BVO films on ITO coated glass substrates measured at room temperature was 8.1 x 10(-8) A at an applied electric field of 33 kV/cm, which was lower than that of the films with platinum and SrRuO3 as the bottom electrodes.

Heterogeneous nucleation of solidification of cadmium particles embedded in an aluminium matrix

A hypomonotectic alloy of Al-4.5wt%Cd has been manufactured by melt spinning and the resulting microstructure examined by transmission electron microscopy. As-melt spun hypomonotectic Al-4.5wt%Cd consists of a homogeneous distribution of faceted 5 to 120 nm diameter cadmium particles embedded in a matrix of aluminium, formed during the monotectic solidification reaction. The cadmium particles exhibit an orientation relationship with the aluminium matrix of {111}Al//{0001}Cd and lang110rangAlAl//lang11¯20> Cd, with four cadmium particle variants depending upon which of the four {111}Al planes is parallel to {0001}Cd. The cadmium particles exibit a distorted cuboctahedral shape, bounded by six curved {100}Al//{20¯23}Cd facets, six curved {111}Al/{40¯43}Cd facets and two flat {111}Al//{0001}Cd facets. The as-melt spun cadmium particle shape is metastable and the cadmium particles equilibrate during heat treatment below the cadmium melting point, becoming elongated to increase the surface area and decrease the separation of the {111}Al//{0001}Cd facets. The equilibrium cadmium particle shape and, therefore, the anisotropy of solid aluminium-solid cadmium and solid aluminium -liquid cadmium surface energies have been monitored by in situ heating in the transmission electron microscope over the temperature range between room temperature and 420 °C. The anisotropy of solid aluminium-solid cadmium surface energy is constant between room temperature and the cadmium melting point, with the {100}Al//{20¯23}Cd surface energy on average 40% greater than the {111}Al//{0001}Cd surface energy, and 10% greater than the {111}Al//{40¯43Cd surface energy. When the cadmium particles melt at temperatures above 321 °C, the {100}Al//{20¯23}Cd facets disappear and the {111}Al//{40¯43}Cd and {111}A1//{0001}Cd surface energies become equal. The {111}Al facets do not disappear when the cadmium particles melt, and the anisotropy of solid aluminium-liquid cadmium surface energy decreases gradually with increasing temperature above the cadmium melting point. The kinetics of cadmium solidification have been examined by heating and cooling experiments in a differential scanning calorimeter over a range of heating and cooling rates. Cadmium particle solidification is nucleated catalytically by the surrounding aluminium matrix on the {111}Al faceted surfaces, with an undercooling of 56 K and a contact angle of 42 °. The nucleation kinetics of cadmium particle solidification are in good agreement with the hemispherical cap model of heterogeneous nucleation.

Evaluation of Erosion Resistance of Metallic Materials and the Role of Material Properties in Correlations

A study of the correlations between material properties and normalized erosion resistance (inverse of erosion rates) of various materials tested in the rotating disk and the flow venturi at various intensities indicates that different individual properties influence different stages of erosion. At high and low intensities of erosion, energy properties predominate the phenomenon, whereas at intermediate intensities strength and acoustic properties become more significant. However, both strength and energy properties are significant in the correlations for the entire spectrum of erosion when extensive cavitation and liquid impingement data from several laboratories involving different intensities and hydrodynamic conditions are considered. The use of true material properties improved the statistical parameters by 3 to 37%, depending on the intensity of erosion. It is possible to evaluate qualitatively the erosion resistances of materials based on the true stress-true strain curves.

Hollow hemisphere and microcapsules of nonionic copolymer

Hemispherical colloidal nanowells or microwells with hollow interiors are becoming increasingly important for the encapsulation of functional materials. There has been rapid progress to develop new methods to obtain such structures. In this work, we present emulsification approach to generate hemisphere and microcapsules of biocompatible organic polymer. The precise control over the size is exhibited by applying variable vortex effect. The hemispheres and microcapsules of a copolymer (BPVA-PVA) were characterized by scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM). These structures were used for loading of hydrophilic molecules and submicron colloidal particles to demonstrate their potential application. The introduction of hydrophobic groups on poly(vinyl alcohol) was crucial to obtain these structures.

Computer simulation of multi-elemental fusion reactor materials

Thermonuclear fusion is a sustainable energy solution, in which energy is produced using similar processes as in the sun. In this technology hydrogen isotopes are fused to gain energy and consequently to produce electricity. In a fusion reactor hydrogen isotopes are confined by magnetic fields as ionized gas, the plasma. Since the core plasma is millions of degrees hot, there are special needs for the plasma-facing materials. Moreover, in the plasma the fusion of hydrogen isotopes leads to the production of high energetic neutrons which sets demanding abilities for the structural materials of the reactor. This thesis investigates the irradiation response of materials to be used in future fusion reactors. Interactions of the plasma with the reactor wall leads to the removal of surface atoms, migration of them, and formation of co-deposited layers such as tungsten carbide. Sputtering of tungsten carbide and deuterium trapping in tungsten carbide was investigated in this thesis. As the second topic the primary interaction of the neutrons in the structural material steel was examined. As model materials for steel iron chromium and iron nickel were used. This study was performed theoretically by the means of computer simulations on the atomic level. In contrast to previous studies in the field, in which simulations were limited to pure elements, in this work more complex materials were used, i.e. they were multi-elemental including two or more atom species. The results of this thesis are in the microscale. One of the results is a catalogue of atom species, which were removed from tungsten carbide by the plasma. Another result is e.g. the atomic distributions of defects in iron chromium caused by the energetic neutrons. These microscopic results are used in data bases for multiscale modelling of fusion reactor materials, which has the aim to explain the macroscopic degradation in the materials. This thesis is therefore a relevant contribution to investigate the connection of microscopic and macroscopic radiation effects, which is one objective in fusion reactor materials research.

The influence of dislocations on the nonlinearity of ZnO:Cu varistors

Zinc Oxide doped only with Cu shows highly nonlinear I–V characteristics. Microstructural observations of these ceramics reveal the presence of extensive dislocation network. The transmission electron microscopy (TEM) indicates that the dislocations are impurity decorated which arise as a result of limited solubility of CuO in ZnO. It is envisaged that the depletion region is generated in the region containing the dislocations because of the presence of acceptor type traps.

Role of alumina in flexure of glass/epoxy composites

The influence of particulate additions of alumina on the flexural properties of glass-fabric/epoxy composites was studied. The additions improved translaminar flexural strength, while decreasing interlaminar strength. The translaminar bending modulus showed an increasing trend whereas its interlaminar value showed a decrease, up to additions of 3 vol%. The mechanisms of deformation and the fracture features have been discussed with the aid of scanning electron microscopy.

Characterization and evaluation of melibiose as novel excipient in tablet compaction

Lactose is probably the most used tablet excipient in the field of pharmacy. Although lactose is thoroughly characterized and available in many different forms there is a need to find a replacer for lactose as a filler/binder in tablet formulations because it has some downsides. Melibiose is a relatively unknown disaccharide that has not been thoroughly characterized and not previously used as an excipient in tablets. Structurally melibiose is close to lactose as it is also formed from the same two monosaccharides, glucose and galactose. Aim of this research is to characterize and to study physicochemical properties of melibiose. Also the potential of melibiose to be used as pharmaceutical tablet excipient, even as a substitute for lactose is evaluated. Current knowledge about fundamentals of tableting and methods for determinating of deformation behavior and tabletability are reviewed. In this research Raman spectroscopy, X-ray powder diffraction (XRPD), near-infrared spectroscopy (NIR) and Fourier-transform infrared spectroscopy (FT-IR) were used to study differences between two melibiose batches purchased from two suppliers. In NIR and FT-IR measurements no difference between materials could be observed. XPRD and Raman however found differences between the two melibiose batches. Also the effects of moisture content and heating to material properties were studied and moisture content of materials seems to cause some differences. Thermal analytical methods, differential scanning calorimetry (DSC) and thermogravimetry (TG) were used to study thermal behaviour of melibiose and difference between materials was found. Other melibiose batch contains residual water which evaporates at higher temperatures causing the differences in thermal behaviour. Scanning electron microscopy images were used to evaluate particle size, particle shape and morphology. Bulk, tapped and true densities and flow properties of melibiose was measured. Particle size of the melibiose batches are quite different resulting causing differences in the flowability. Instrumented tableting machine and compression simulator were used to evaluate tableting properties of melbiose compared to α-lactose monohydrate. Heckel analysis and strain-rate sensitivity index were used to determine deformation mechanism of melibiose monohydrate in relation to α–lactose monohydrate during compaction. Melibiose seems to have similar deformation behaviour than α-lactose monohydrate. Melibiose is most likely fragmenting material. Melibiose has better compactibility than α – lactose monohydrate as it produces tablets with higher tensile strength with similar compression pressures. More compression studies are however needed to confirm these results because limitations of this study.