A study of the subsolidus region of the BaO-La2O3-V 2O5 phase diagram has been carried out. Four ternary phases can be prepared, one of which has not been previously identified. The four ternary phases are a palmierite solid solution Ba3-3xLa2x V2O8, Ba2LaV3O11, BaLa10V4O26 (new phase) and Ba3La 40V12O93. Addition of BaLa10V 4O26 and the previously omitted phase La1.42V 0.58)3.58 to the ternary system has resulted n a re-determination of the complete phase diagram. A comprehensive study of the Ba3-3xLa 2xV2O8 solid solution has been carried out, employing a number of techniques including x-ray diffraction, infra-red spectroscopy, thermogravemetric analysis, impedance spectroscopy, electron paramagenetic resonance spectroscopy, inductively coupled plasma mass spectroscopy and x-ray absorption near edge structure spectroscopy. Conductivity measurements show the end-member Ba3V2O8 to be an oxide ion conductor, with the conduction mechanism being facilitated by the ease of transformation of the BaO3 layers to BaO2 and vice versa. The La-doped members show an increase in conductivity, with electrons becoming the dominant conducting species. The crystal structure of Ba2LaV 3O11 was confirmed to be isostructural with Ba2BiV 3O11. A full refinement of the structural parameters has been performed. The unit cell is primitive monoclinic, a = 12.44510(3)A, b = 7.78854(12)A, c = 11.26245(21)A and beta = 103.134(4)°, space group P21/c. Preliminary structural studies have begun on the new phase BaLa10V4O26. The x-ray powder pattern has been fully indexed and a possible monoclinic unit cell of a = 20.2939A, b = 5.886A, c = 12.6234A and beta = 118.05° is proposed. The serendipitous synthesis of a barium-deficient celsian phase, Ba0.8A11.6 Si2.4O8, is reported; the structure was solved using Patterson methods. The phase has a monoclinic unit cell with, a = 8.6090(8)A, b = 13.0858(12)A, c = 7.2047(7)A and beta = 115.418(2)°, space group C2/m.

Microwave holography is a well established method of using the Fourier relationship between an antenna’s current distribution and its complex beam-pattern to produce surface maps of large parabolic antennas. As the final part of a surface upgrade, a holographic map of the HartRAO 26 m telescope was produced. This showed that the surface has an RMS error of 0.45 mm. The measurement used a small reference dish to correlate against and retrieve amplitude and phase values. Due to system phase instabilities, this dish had to be attached to the measured antenna in order to enable sharing a high frequency local oscillator (LO). The movement was modelled and corrected for. However, a slight distortion remained. It is recommended that, either the LO distribution system is stabilised by using multiple PLLs or amplifiers and low loss cables are used to enable moving the reference antenna to a stationary position.

Les charrées de chrome, résidus d’extraction du minerai de chrome (ou COPR), sont des matériaux de pH très basique (>10) composés de phases minérales cimentaires peu stables incorporant le chrome d’état d’oxydation +VI. La solution porale du matériau est chargée en Cr(VI) à des concentrations souvent supérieures à 100 mg/L. Les teneurs du matériau s’élèvent à 4-7 g Cr(VI)/kg. Le chrome VI est toxique. Par le passé, les charrées de chrome ont été utilisées en remblai d’infrastructures. C’est le cas d'une infrastructure dans le nord de la France. Notre étude a visé à développer une méthode de dépollution. Nous avons élaboré un couplage de la technique électrocinétique et d’une réduction chimique du Cr(VI). Nous apportons un réducteur qui migre à travers le matériau grâce à un champ électrique. Nous montrons que la réduction du chrome VI en chrome III précipité et moins toxique est possible avec une efficacité de 97 % et que les phases minérales ciment résistent à ce traitement. Nos travaux montrent que 60 à 70 % de la matière dans les charrées de chrome étudiées sont constitués de phases minérales amorphes. Elles sont sensibles aux variations de pH dans le milieu lors du traitement et réagissent en partie par dissolution, re-précipitation et transport. L’hydroxyde de Cr(III) formé lors du traitement est colloïdal et en partie mobiles. Des ajustements de la méthode sont possibles, en particulier le contrôle des variations de pH et la suppression de la mobilité indésirable du Cr(III). Les perspectives industrielles de cette méthode également adaptable à d’autres polluants rédox-sensibles, sont prometteuses. / Chromite Ore Processing Residues (COPR) are materials with strongly alcaline pH (>10) containing fairly soluble cement phases bearing hexavalent chromium as a substituted anion. The pore water contains high concentrations of mobile Cr(VI) often above 100 mg/L. The bulk concentration of Cr(VI) is 4 - 7 g /kg COPR. Hexavalent chromium is a toxic compound. Historically, COPR was used for embankments and backfills in construction works. This was the case for an infrastructure in the north of France. In this study we aimed to develop a remediation method suitable for treatment of this backfills in-situ. We coupled the electrokinetics technique with in situ chemical reduction of Cr(VI). In this method, the added reductive compound migrates through the material under the effect of an electric field. We show that Cr(VI) reduction to the less toxic Cr(III) is possible with as high as 97% efficiency. Results show that the crystallized mineral phases are not impacted by the treatment. However, 60 to 70% of the mineral phases are amorphous as quantification studies show. The pH change during treatment fragilizes them, resulting in some dissolution, reprecipitation, electromigration and electrophoretic transport phenomena. Cr(III)-hydroxide, produced during the treatment, also appear to be in a mobile colloidal form. Optimisations of the technique are possible, in particular the control of pH changes and the suppression of colloidal Cr(III) mobility. Industrial perspectives are promising. This method can be adapted to other materials and redox sensitive pollutants.

The PhD research presented here is part of the new nuclear manufacturing (NNUMAN) research group, looking into novel materials and manufacturing processes. NNUMAN is an EPSRC funded (EP/J021172/1) program with direct support from Rolls Royce plc. The fabrication of MAX phase coatings by different means and assessing their tribological properties was the original theme of this thesis. However, due to issues with fabrication processes the overriding direction was moved towards assessing the response of bulk MAX phases to irradiating and corrosive environments. It is believed that this research will contribute to the understanding of suitable compositions and applications within nuclear. The MAX phases comprise an early transition metal (M), an A-group element (A) and either carbon or nitrogen (X). They have an inherently nano-layered structure with alternating ceramic (MX) and metallic (A) layers. The unique mix of both ceramic and metallic properties have made MAX phases a proposed material for nuclear applications. Proton irradiation is performed on Ti3SiC2, Ti3AlC2, Ti2AlC and Cr2AlC bulk MAX phases to 0.1 dpa at 350oC. Crystallographic instabilities are observed through x-ray diffraction (XRD) analysis after irradiation. A mechanism for irradiation induced point defect swelling is proposed, by matching XRD and modelling data. Anti-site point defects are proposed to be a major contributor to anisotropic lattice parameter changes in Ti3SiC2. Additional carbon interstitial defects are also proposed in Ti3AlC2, as well as anti-site defects, making them less radiation tolerant. Further proton irradiations on Ti3SiC2 and Ti3AlC2 were performed at elevated temperatures to propose a temperature at which lattice changes are not observed. It is concluded that high proton fluences require temperatures in excess of ~700oC and ~1,000oC for Ti3SiC2 and Ti3AlC2, respectively. Corrosion of bulk MAX phases in simulated primary water also suggests a deleterious response to normal light water reactor (LWR) operations. Advanced scanning transmission electron microscopy (STEM) techniques, such as energy dispersive x-ray spectroscopy (EDS) and electron energy loss spectroscopy (EELS), is employed to understand corrosion mechanisms. Selective oxidation of A-layers is observed, with no evidence of passivation for Ti3SiC2, Ti3AlC2 and Ti2AlC. The response of Cr2AlC was most promising as little oxidation occurred, which is confirmed also with XRD analysis. A comprehensive corrosion mechanism is proposed, whereby compositions of MAX phase in LWR coolants is limited.

La ferrite allotriomorphe est une des morphologies de la ferrite dont la répartition spatiale influe fortement sur les propriétés mécaniques dans les aciers dual-phase. En fonction des traitements qu'ils subissent, la ferrite peut s'y répartir suivant les bandes de ségrégation en manganèse, issues de l'étape de solidification. Pour établir le rôle que joue le processus de croissance de la ferrite allotriomorphe sur la mise en place de la structure en bandes, nous avons développé un modèle de champ de phases possédant deux spécificités originales, imposées par le problème. D'une part, ce modèle est capable de reproduire les différents régimes cinétiques observés dans les alliages ternaires Fe-C-X, pilotés par la présence concomittante du carbone diffusant rapidement,et d'un élément substitutionnel X diffusant lentement. Nous avons ainsi mis en évidence la transition d'un régime initial rapide de paraéquilibre vers une croissance lente en orthoéquilibre, en bon accord avec des résultats expérimentaux de la littérature. D'autre part, notre modèle incorpore de manière économe la présence des joints de grains austénitiques, dont le rôle dans l'élimination des structures en bande est souligné par nos calculs. Nous observons ainsi qu'il existe un seuil d'intensité deségrégation en manganèse en dessous duquel le mouillage de la ferrite le long des joints de grain de plus grande énergie peut contrecarrer la croissance dans les bandes ségrégées négativement / The growth of allotriomorphic ferrite plays a major role in the formation of martensite bands in Dual-Phase steels. We have thus developed a phase field model to study the ferritic growth in different ternary Fe-C-X alloys, incorporating two necessary features. First, we have paid a particular attention to recover the different growth regimes due to the huge difference between the diffusion rates of Cand X substitutional species. Our calculations have exhibited a transition from fast paraequilibrium to slow orthoequilibrium in good agreement with experimental measurements in the literature. Second, austenite grain boundaries have been included in the model because they can conterbalance the manganese segregation bands, as shown in our calculations. Indeed, our results show that the bands can be broken bythe wetting of ferrite along the austenite grain boundaries, provided that the segregation is below a threshold value, and provided that the grain boundary energies are sufficiently high

The next generation of nuclear safety analysis computer codes will include detailed modeling of the interfacial area concentration. The interfacial area concentration is the essence of the two-fluid model. It is the most accurate of the two-phase models since it considers each phase independently and links the two phases together with six conservation equations. The interfacial area concentration, along with a driving potential, determines the energy, momentum and mass transfer between the two phases. The importance of this research lies in obtaining a greater understanding of the developing nature of two-phase flows and the application of the two-fluid model. With proper characterization of two-phase flow, the next generation of nuclear safety analysis computer codes will be able to incorporate this information to predict parameters during an accident scenario with greater precision. This research will provide a first order look into the developing nature of two-phase flow. As part of this research, the development of two-phase flow in a vertical column was analyzed using double sensor impedance probes. The resident vapor and liquid times were recorded along with the velocity of the vapor phase. By creating distributions of the bubble residence times, liquid residence times, velocities, and sizes, one can characterize the developing nature of the two-phase flow. Data was taken at four different axial locations for six different flow rates. The resulting data show clear trends in how the standard deviation and mean values for the measured parameters change as a function of flow rate and axial position. The void fraction contribution from the spherical/distorted bubble group as well as the cap/slug bubble group was also recorded to determine the net transfer rate of vapor between the two bubble groups. Interfacial area concentration was not included in the measurement since the probes that were used can only determine interfacial area concentration for spherical bubbles. Further research will be conducted with the inclusion of interfacial area concentration at a later time. / Graduation date: 2002

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This thesis describes 80−94GHz and 70−77GHz interpolating phase shifters and the corresponding transmitter and receiver ICs, fabricated in 65-nm CMOS and SiGe BiCMOS technologies, respectively. Lumped inductors and transformers are employed to realize small-form factor 90 degree hybrids as needed in high density phased arrays. The CMOS transmitter exhibits absolute phase and amplitude errors of 4 degrees and 4dB, respectively, at 90GHz, when the phase is varied from 0 degrees to 360 degrees in steps of 22.5 degrees. The absolute phase error in the SiGe BiCMOS receiver is less than 5 degrees, with a maximum gain imbalance below 3dB at 74GHz. The peak gain and power consumption are 3.8dB and 142mW from 1.2V supply for the CMOS transmitter, and 17dB and 128mW from 1.5V and 2.5V supplies for the SiGe BiCMOS receiver.

This thesis describes 80−94GHz and 70−77GHz interpolating phase shifters and the corresponding transmitter and receiver ICs, fabricated in 65-nm CMOS and SiGe BiCMOS technologies, respectively. Lumped inductors and transformers are employed to realize small-form factor 90 degree hybrids as needed in high density phased arrays. The CMOS transmitter exhibits absolute phase and amplitude errors of 4 degrees and 4dB, respectively, at 90GHz, when the phase is varied from 0 degrees to 360 degrees in steps of 22.5 degrees. The absolute phase error in the SiGe BiCMOS receiver is less than 5 degrees, with a maximum gain imbalance below 3dB at 74GHz. The peak gain and power consumption are 3.8dB and 142mW from 1.2V supply for the CMOS transmitter, and 17dB and 128mW from 1.5V and 2.5V supplies for the SiGe BiCMOS receiver.

A voltage controlled oscillator (VCO), that generates a periodic signal whose frequency is tuned by a voltage, is a key building block in any integrated circuit systems. A sine wave oscillator can be used for a built-in self testing where high linearity is required. A bandpass filter (BPF) based oscillator is a preferred solution, and high quality factor (Q-factor) is needed to improve the linearity. However, a stringent linearity specification may require very high Q-factor, not practical to implement. To address this problem, a frequency harmonic shaping technique is proposed. It utilizes a finite impulse response filter improving the linearity by rejecting certain harmonics. A prototype SC BPF oscillator with an oscillating frequency of 10 MHz is designed and measurement results show that linearity is improved by 20 dB over a conventional oscillator. In radio frequency area, preferred oscillator structures are an LC oscillator and a ring oscillator. An LC oscillator exhibits good phase noise but an expensive cost of an inductor is disadvantageous. A ring oscillator can be built in standard CMOS process, but suffers due to a poor phase noise and is sensitive to supply noise. A RC BPF oscillator is proposed to compromise the above difficulties. A RC BPF oscillator at 2.5 GHz is designed and measured performance is better than ring oscillators when compared using a figure of merit. In particular, the frequency tuning range of the proposed oscillator is superior to the ring oscillator. VCO is normally incorporated with a frequency synthesizer (FS) for an accurate frequency control. In an integer-N FS, reference spur is one of the design concerns in communication systems since it degrades a signal to noise ratio. Reference spurs can be rejected more by either the lower loop bandwidth or the higher loop filter. But the former increases a settling time and the latter decreases phase margin. An adaptive lowpass filtering technique is proposed. The loop filter order is adaptively increased after the loop is locked. A 5.8 GHz integer-N FS is designed and measurement results show that reference spur rejection is improved by 20 dB over a conventional FS without degrading the settling time. A new pulse interleaving technique is proposed and several design modifications are suggested as a future work.