One of the degradation processes of zirconium-based nuclear fuel assemblies is irradiation-induced growth, an anisotropic, stress-independent, macroscopic deformation mechanism that elongates fuel cladding tubes axially. Irradiation-induced growth is driven by the irradiation-induced formation of dislocation loops, where the evolution of the loop structure can be complex, with the initial formation of loop generating transient growth, while the later formation of component dislocation loops, or loops, leads to accelerated growth. A full mechanistic understanding of loop nucleation is as yet unforthcoming. This thesis utilizes the diffraction peak broadening analysis software, named extended Convolutional Multiple Whole Profile, to study the dislocation structure evolution of neutron- and proton-irradiated zirconium alloys in order to validate proton-irradiation as a effective tool for the study of irradiation damage in relation to irradiation-induced growth. The diffraction profiles obtained exhibit unexpected features present in the tails of the Bragg peaks, tentatively attributed here to either strained regions of matrix, or diffuse scattering from severely distorted regions around nucleating precipitates, both originating from an increased solute concentration. The diffraction results indicate that the proton-irradiated samples exhibit qualitatively similar behaviours as seen from neutron-irradiation, such as a threshold irradiation dose before the formation of loops, however, a continued increase of loop dislocation density determined from peak broadening analysis is not observed by transmission electron microscopy. It is also shown that the Nb-containing Low-Sn ZIRLO® alloy has a lower dislocation density than the Nb-free Zircaloy-2 after the formation of loops correlating well with the relative irradiation-induced growth behaviours observed in- reactor. A correlation between a reduction in the loop dislocation density and the formation of loops is observed in Low-Sn ZIRLO® and Zr-1.60Sn-0.033Fe, providing support for the hypothesis that vacancy loops transform into loops. Zr- 0.61Sn-0.024Fe and Zr-1.60Sn-0.033Fe alloys show a rapid increase in the loop dislocation density in the initial stages of proton-irradiation, likely due to the low irradiation-resistance of the precipitates present in these alloys.

Este trabalho consta de uma introdução teórica tratando, do conceito de cristal, da interação entre o raio-X e o meio cristalino e dos fundamentos dos métodos de determinação de estruturas moleculares de pequeno porte aplicados na solução das estruturas cristalinas dos complexos: Praseodímio, Neodímio e Európio com Perrenato e Trans-l, 4-ditiano-l, 4-dióxido,(TDTD), tendo fórmula geral [Ln(H2O)4(&#951 TDTD) (&#951 &#8217 ReO4) (&#956-&#9512-TDTD)]n (ReO4)2n &#8226 nTDTD onde, Ln= Eu, Pr, Nd e Metil-2,6-anhidro-3-azido-4-0-benzoil-3-deoxi-&#945-D-iodopiranosideo, um novo derivado de 2,5-dioxabiciclo [2,2,2] octano. Determinou-se que os complexos envolvendo íons latanídeos, tem estruturas isomorfas, que refinaram para os valores finais: R(eu)=0.067, R(Pr)= 0.074, R(Nd)= 0.061. As características principais das estruturas são as seguintes: a) sistema cristalino ortorrômbico; b) o íon Ln3+ é coordenado por nove átomos de oxigênio dos grupos TDTD, perrenato e H2O. Os átomos de oxigênio que coordenam o cátion formam formam uma configuração antiprisma quadrado de Arquimedes com chapéu; c) o íon de terra rara se encontra em posição especial de simetria C2; d) a estrutura possui uma desordem ocupacional com relação a três átomos de oxigênio descoordenados do perrenato que coordena o íon Ln3+ através de um oxigênio situado também em posição de simetria C2. Explica-se os resultados do espectro de emissão do Eu3+ à luz dos resultados estruturais obtidos, comparando estes resultados com outros descritos na literatura. A estrutura do complexo orgânico, com fórmula química C14H15N3O5, foi determinada utilizando métodos diretos. A conformação do anel de seis membros foi determinada como sendo aproximadamente um barco torcido. / This work consists of a theoretical introduction to the concept of a crystal, the interaction between X-ray and the crystalline medium and some aspects concerning the methods of structure determination, applied to the crystal structure of the complexes: Praseodymium, Neodymium and Europium Perrhenate with Trans-l,4-dithiane-l,4-dioxide (TDTD) of general formula: [Ln(H2O)4(&#951 TDTD) (&#951 &#8217 ReO4) (&#956-&#9512-TDTD)]n (ReO4)2n &#8226 nTDTD, where Ln= Eu, Pr, Nd and Methyl-2,6-anhydro-3-azido-4-0-benzoyl-3-deoxy-&#945-D-iodopyranoside, a new 2,5-Dioxabicycle [2,2,2] octane derivative. It was determined that the complexes involving lanthanide ions are structurally isomorphous, the structures refined to the final values of: R(Nd)=0.061, R(Pr)=0.074, R(Eu)=0.067. The principal characteristics of these structures are: a) the crystal system is orthorhombic; b) the ion Ln3+ is coordinated by nine oxygen atoms of TDTD, perrhenate and water molecules. The coordinated oxygen have an approximate Antiprismatic Arquimedian Capped Square conformation; c) the rare earth atom is located on a crystallographic C2 position; d) the structure has an occupational disorder, with relation to three uncoordinated oxygen atoms of the perrhenate group that coordinates the cation by the oxygen located on the special position with exact point symmetry C2. The emission spectra of the Eu3+ ion is explained based on the structure information obtained from x-ray analysis. Also a comparison is traced with other coordination compounds, with the lanthanide ion Ln3+, revealing some important aspects of these structures. The structure of the compound with chemical formula C14H15N3O5 was determined using direct methods. The six member ring C(1)-O(5)-C(4)-C(3)-C(2) is in an approximate twist-boat conformation.

The ability to diagnose the structure of a material at extreme conditions of high-pressure and high-temperature is fundamental to understanding its behaviour, especially since it was found that materials will adopt complex crystal structures at pressures in the Terapascal regime (1TPa). Static compression, using the diamond anvil cell coupled with synchrotron radiation has to date been the primary method for structural studies of materials at high pressure. However, dynamic compression is the only method capable of reaching pressures comparable to the conditions found in the interior of newly discovered exo-planets and gas giants where such exotic high-pressure behaviour is predicted to be commonplace among materials. While generating extreme conditions using shock compression has become a mature science, it has proved a considerable experimental challenge to directly observe and study such phase transformations that have been observed using static studies due to the lack of sufficiently bright X-ray sources. However, the commissioning of new 4th generation light sources known as free electron lasers now provide stable, ultrafast pulses of X-rays of unprecedented brightness allowing in situ structural studies of shock compressed materials and their phase transformation kinetics in unprecedented detail. Bismuth, with its highly complex phase diagram at modest pressures and temperatures, has been one of the most studied systems using both static and dynamic compression. Despite this, there has been no structural characterisation of the phases observed on shock compression and it is therefore the ideal candidate for the first structural studies using X-ray radiation from a free electron laser. Here, bismuth was shock compressed with an optical laser and probed in situ with X-ray radiation from a free electron laser. The evolution of the crystal structure (or lack there of) during compression and shock release are documented by taking snapshots of successive experiments, delayed in time. The melting of Bi on release from Bi-V was studied, with precise time scans showing the pressure releasing from high-pressure Bi-V phase until the melt curve is reached off-Hugoniot. Remarkable agreement with the equilibrium melt curve is found and the promise of this technique has for future off-Hugoniot melt curve studies at extreme conditions is discussed. In addition, shock melting studies of Bi were performed. The high-pressure Bi - V phase is observed to melt along the Hugoniot where melting is unambiguously identified with the emergence of a broad liquid-scattering signature. These measurements definitively pin down where the Hugoniot intersects the melt curve - a source of some disagreement in recent years. Evidence is also presented for a change in the local structure of the liquid on shock release. The impact of these results are discussed. Finally, a sequence of solid-solid phase transformations is observed on shock compression as well as shock release and is detected by distinct changes in the obtained diffraction patterns. The well established sequence of solid-solid phase transformations observed in previous static studies is not observed in our experiments. Rather, Bi is found to exist in some metastable structures instead of forming equilibrium phases. The implications these results have for observing reconstructive phase transformations in other materials on shock timescales are discussed.

Pressure and temperature are two environmental variables that are increasingly being exploited by solid-state researchers probing structure-property relationships in the crystalline state. Modern high-pressure apparatus is capable of generating many billions of Pascals in the laboratory, and therefore can produce significantly greater alterations to crystalline materials than changes in temperature, which can typically be varied by only a few thousand Kelvin. Many systems such as single-molecule magnets exhibit interesting properties under low-temperature regimes that can be substantially altered with pressure. The desire by investigators to perform analogous single-crystal X-ray diffraction studies has driven the development of new high-pressure apparatus and techniques designed to accommodate low-temperature environments. [Ni(en)3][NO3]2 undergoes a displacive phase transition from P6322 at ambient pressure to a lower symmetry P6122/P6522 structure between 0.82 and 0.87 GPa, which is characterized by a tripling of the unit cell c axis and the number of molecules per unit cell. The same transition has been previously observed at 108 K. The application of pressure leads to a general shortening of O···H hydrogen bonding interactions in the structure, with the greatest contraction (24%) occurring diagonally between stacks of Ni cation moieties and nitrate anions. A novel Turnbuckle Diamond Anvil Cell designed for high-pressure low-temperature single-crystal X-ray experiments on an open-flow cryostat has been calibrated using the previously reported phase transitions of five compounds: NH4H2PO4 (148 K), ferrocene (164 K), barbituric acid dihydrate (216 K), ammonium bromide (235 K), and potassium nitrite (264 K). From the observed thermal differentials between the reported and observed transition temperatures a linear calibration curve has been constructed that is applicable between ambient-temperature and 148 K. Low-temperature measurements using a thermocouple have been shown to vary significantly depending on the experimental setup for the insertion wire, whilst also adding undesirable thermal energy into the sample chamber which was largely independent of attachment configuration. High-pressure low-temperature single-crystal X-ray diffraction data of [Mn12O12(O2CMe)16(H2O)4] (known as Mn12OAc) reveals a pressure-induced expulsion of the crystallized acetic acid from the crystal structure and resolution of the Jahn-Teller axes disorder between ambient pressure and 0.87 GPa. These structural changes have been correlated with high-pressure magnetic data indicating the elimination of a slow-relaxing isomer over this pressure range. Further application of pressure to 2.02 GPa leads to the expansion of these Jahn-Teller axes, resulting in an enhancement of the slow-relaxing magnetic anisotropy as observed in the literature. Relaxation of pressure leads to a resolvation of the crystal structure and re-disordering of the Jahn-Teller axes, demonstrating that this structural-magnetic phenomenon is fully reversible with respect to pressure. The space group of the Prussian blue analogue Mn3[Cr(CN)6].15H2O has been re-evaluated as R-3m between ambient pressure and 2.07 GPa using high-pressure single-crystal X-ray and high-pressure neutron powder data. Reductions in metal-metal distances and gradual distortions of the Mn octahedral geometry have been correlated with previously reported increases in Tc and declines in ferrimagnetic moment in the same pressure range. Increasing the applied pressure to 2.97 GPa leads to partial amorphization and results in a loss of long-range magnetic order as shown by the literature. The application of pressure (1.8 GPa) to the structure of K2[Pt(CN)4]Br0.24.3.24H2O (KCP(Br)) causes a reduction in the Pt intra-chain and inter-chain distances, and results in an enhancement of the overall conductivity under these conditions as demonstrated in the literature. Almost no changes occur to the high-pressure crystal structure upon cooling to 4 K, except in the Pt-Pt intra-chain distances which converge and suppress the Peierls distortion known to occur at 4 K, resulting in a comparatively greater electrical conductivity under these conditions.

No description available.

Hydrolysis products of aluminum that exist in aqueous solutions play an important role in controlling the fate and transport of contaminants and are also used for coagulants to purification of wastewater streams. Adsorption of contaminants such as heavy metals and organics are widely recognized, but the molecular level understanding of the mechanism of action has not been clearly defined. In this research we present the crystallization, structural characterization and chemical characterization of three novel Keggin-type aluminum polycations including ((Al(IDA)H2O)2(Al30O8(OH)60(H2O)22)(2,6 NDS)4(SO4)2Cl4(H2O)40) (Al32-IDA),[(Cu(H2O)2(µ2-OH)2)2(Al2(µ4-O)8(Al28(µ2-OH)50(µ3-OH)6(H2O)26(2,6-NDS)9(H2O)52]-(CuAl30) and [(Zn(NTA)H2O)2(Al(NTA)(µ2-OH)2)2(Al30(µ2-OH)54(µ3-OH)6(µ4-O)8(H2O)20(2,6-NDS)5(H2O)64]-(ZnAl32) where IDA = iminodiacetic acid, NTA- Nitrilotriacetic acid, and 2,6 NDS = 2,6 napthalene disulfonate. These compounds are the first ever reported Keggin-type aluminum species that have been functionalized with organics and heavy metal cations. Structural characterization of these compounds was done by means of single crystal X-ray diffraction along with FTIR, TGA, SEM/EDS and PXRD techniques for chemical characterization. This study provides more insight into the coagulation process and can be employed in developing optimized coagulants for enhanced water purification.

<p>In a time of global environmental problems due to overuse of fossil fuels, and a subsequent depletion of the supplies, hydrogen is considered as one of the most important renewable future fuels for use in clean energy systems with zero greenhouse-gas emission. Hydrogen storage is the main issue that needs to be solved before the technology can be implemented into key areas such as transport. The high energy density, good stability and reversibility of metal hydrides make them appealing as hydrogen storage materials. In this thesis research on synthesis and hydrogen absorption properties for intermetallic compounds based on scandium and aluminium is reported. The compounds were synthesized by arc melting or induction melting and exposed to hydrogen in a high pressure furnace. Desorption investigations were performed by thermal desorption spectroscopy. The samples were analyzed by x-ray powder diffraction and electron microscopy. ScAlNi, crystallizing in the MgZn2-type structure (space group: P63/mmc; a = 5.1434(1) Å, c = 8.1820(2) Å), was found to absorb hydrogen by two different mechanisms at different temperature regions. At ~120 °C hydrogen was absorbed by solid solution formation with estimated compositions up to ScAlNiH0.5. At ~500 °C hydrogen was absorbed by disproportionation of ScAlNi into ScH2 and AlNi. The reaction was found to be fully reversible due to destabilization effects which lowered the decomposition temperature of ScH2 by ~460 °C.</p>

Synthesis and structural characterisation of metal hydrides in two important systems are presented. The first system presented is low valent cobalt and nickel complex hydrides with the compositions BaMg5Co2H10, RbMg5CoNiH10, SrMg2CoH7and Sr4Mg4Co3H19 featuring nickel with oxidation state of 0 and cobalt with oxidation state +I and -I. The second system presented is polyanionic gallium complex hydrides with the compositions RbGaH2, RbxK(1−x)GaH2 (0.5≤x≤1), CsxRb(8−x)Ga5H15 (0≤x≤8) and Cs10Ga9H25 featuring novel hydrogenous polyanionic gallium hydride clusters mimicking common hydrocarbons. The syntheses of the compounds were performed at elevated temperatures and at moderate hydrogen pressures (50-100 bar). The structural investigations were mainly done by X-ray powder diffraction (XRPD) and neutron powder diffraction (NPD). The metal-hydrogen bond was investigated by vibrational spectroscopy using Fourier Transform IR-spectroscopy (FTIR) and Inelastic Neutron Scattering (INS).By subtle changes in the compositions of the hydrides it was possible to induce major changes in band gaps, oxidation states and structures. / <p>At the time for the doctoral defence the following papers were unpublished and had a status as follows: Paper 1: Manuscript; Paper 2: Accepted; Paper 5: Manuscript</p>

There are many causes of structural failure. One of the most important factors leading to material failure is residual stress. This stress represents effects left in structures after processing or removal of external loads including changes in shape and crystallite size. In aggregate, residual stress changes the mechanical behaviour of materials. Various measurement techniques encompassing destructive, semi destructive, and non-destructive testing can be used to measure residual stresses. Thin plates are common in engineering applications. This thesis analyzes residual stresses on circular AISI 1020 steel alloy plates after removal of external loads using two-dimensional X-ray diffraction. Two identical thin circular plates are used in this experiment; one of which is statically loaded. The other plate is used as a control specimen. Residual stresses in the plates are measured using two-dimensional X-ray diffraction and the measurements are compared to those obtained using finite element analysis. It was found that experimentally measured residual stress occurred due to manufacture processing. Also, modules A and B showed the external effect of applying not enough to reach the plastic region to deform specimen 2 and obtain residual stress results distribution.

<p><i>Lactococcus lactis,</i> prolidase (<i>Lla</i>prol) hydrolyzes Xaa-Pro dipeptides. Since Xaa-Pro is known as bitter peptides, <i>Lla</i>prol is potentially applicable to reduce bitterness of fermented foods. <i>Lla</i>prol shows allosteric behaviour and substrate inhibition, which are not reported in other prolidases. Computer models of <i>Lla</i>prol based on an X-ray structure of non-allosteric <i>Pyrococcus furiosus</i> prolidase showed that a loop structure (Loop^32-43) is located at the interface of the protomers of this homodimeric metallodipeptidase. This study investigated roles of four charged residues (Asp³⁶, His³⁸, Glu³⁹, and Arg⁴⁰) of Loop^32-43 in <i>Lla</i>prol using a combination of kinetic examinations of ten mutant enzymes and their molecular models. Deletion of the loop structure by Î36-40 mutant resulted in a loss of activity, indicating Loop^32-43 is crucial for the activity of <i>Lla</i>prol. D36S and H38S exhibited 96.2 % and 10.3 % activity of WT, whereas little activities (less than 1.0 % of WT activity) were observed for mutants E39S, D36S/E39S, R40S, R40E, R40K and H38S/R40S. These results implied that Glu³⁹ and/or Arg⁴⁰ play critical role(s) in maintaining the catalytic activity of <i>Lla</i>prol. These observations suggested that the loop structure is flexible and this attribute, relying on charge-charge interactions contributed by Arg⁴⁰, Glu³⁹ and Lys¹⁰⁸, is important in maintaining the activity of <i>Lla</i>prol. When the loop takes a conformation close to the active site (closed state), Asp³⁶ and His³⁸ at the tip of the loop can be involved in the catalytic reaction of <i>Lla</i>prol. The two active mutant prolidases (D36S and H38S) resulted in modifications of the unique characteristics; the allosteric behaviour was not observed for D36S, and H38S <i>Lla</i>prol showed no substrate inhibition. D36E/R293K, maintaining the negative charge of position 36 and positive charge of position 293, still possessed the allosteric behaviour, whereas the loss of the charges at these positions (D36S of this study and R293S of a previous study (Zhang et al., 2009 BBA-Proteins Proteom 1794, 968-975) eliminated the allosteric behaviour. These results indicated the charge-charge attraction between Asp³⁶ and Arg²⁹³ is important for the allostery of <i>Lla</i>prol. In the presence of either zinc or manganese divalent cations as the metal catalytic centre, D36S and H38S enzymes also showed different substrate preferences from WT <i>Lla</i>prol, implying the influence of Asp³⁶ and His³⁸ on the substrate binding. D36S and H38S also showed higher activities at pH 5.0 to 6.0, in which range WT <i>Lla</i>prol steeply decreased its activity, indicating Asp³⁶ and His³⁸ are involved in the active centre and influence the microenvironment of catalytic His²⁹⁶. The above observations are attributed to modifications of their local structure in the active centre since the temperature dependency and thermal denaturing temperature indicated little effects on the overall structure of the <i>Lla</i>prol mutants.</p> <p>From these results, we concluded that the unique behaviours of <i>Lla</i>prol are correlated to Loop^32-43 and Asp³⁶ and His³⁸ on it. When Loop^32-43 takes a closed conformation, Asp³⁶ interacts with Arg²⁹³ via charge-charge attraction to form an allosteric subsite. The saturation of the allosteric site with substrates further allowed the communications of His³⁸ with S₁ site residues to complete the active site. When the substrate concentration becomes higher than it is required to saturated productive S₁' site, His³⁸, Phe¹⁹⁰ and Arg²⁹³ would resemble the residue arrangement of S₁' site residues (His²⁹², Tyr³²⁹, and Arg³³⁷) and bind to the proline residue of substrates. This non-productive binding would prevent the conformational change of Loop^32-43, which further results in the substrate inhibition. For further confirmation of this mechanism, crystallographic studies will be conducted. In this thesis, we have indentified the conditions to produce crystals of <i>Lla</i>prol proteins.</p>