Polymer-derived ceramics are a new class of materials synthesized by thermal decomposition of polymer precursors. Previous studies have shown that the materials exhibit excellent thermo-mechanical properties and can be stable at temperatures up to 2000oC. Furthermore, the novel polymer-to-ceramics process enables the manipulation of the ceramic structures at the atomic/nano level by designing the chemistry of polymer precursors and controlling the pyrolysis conditions, thereby, the properties of ceramics. In this dissertation, oxidation/hot-corrosion behavior and the structural evolution of Si-Al-C-N ceramics have been studied. The structural evolution and crystallization behavior of the SiCN and SiAlCN ceramics are investigated using FT-IR, XRD, and NMR. The results revealed that aluminum could greatly affect the structural evolution and crystallization behavior of polymer-derived ceramics, resulting to better stability. The oxidation kinetics of the SiCN and SiAlCN ceramics in air is determined by directly measuring the thickness of the oxide scale with SEM as a function of oxidation time. The results revealed that while the oxidation of the SiCN ceramics follows parabolic kinetics in all of the ranges of testing temperatures, oxidation of the SiAlCN ceramics is complicated: their oxidation rates are similar to that of SiCN ceramics at the earlier stage, but they decrease to very low levels after a certain time. The oxidation rate of the SiAlCN ceramics is more than an order of magnitude lower than any other silicon based ceramics previously reported. The transportation behavior of oxygen through the oxide scales is studied by 18O diffusion. The results indicate that oxidation is controlled by molecular oxygen diffusing through the oxides for both SiCN and SiAlCN ceramics; however, the oxygen diffusion rate in the oxides on SiAlCN ceramics is remarkably retarded. The structures of the oxides are characterized by XRD and NMR. A structural model is advanced to account for the aluminum effect on the oxygen diffusion in the oxide. The oxidation and hot-corrosion kinetics of the SiCN and SiAlCN ceramics in water vapor are determined by measuring their weight changes as a function of annealing time. The kinetic constants, kp and kl, are obtained by fitting the weight-change data with a paralinear model. The results reveal that the SiAlCN ceramics have a much better corrosion resistance than the SiCN and CVD SiC/Si3N4. After annealing at 1400oC for 300 hours, the SiAlCN-20 still retains more than 70% of its original strength, while the SiCN only retains about 20% of its original strength. The improvement in oxidation/hot-corrosion resistance of the SiAlCN ceramics is attributed to the low activity of the SiO2 in the Al2O3-containing silica. In summary, I have developed a new class of high-temperature materials, Si-Al-C-N ceramics. It is demonstrated that these new materials have excellent oxidation and corrosion resistance and thermal stability. Together with their easy processability, the materials will find many high temperature applications such as environmental barrier coatings, ceramic matrix composites, and MEMS for harsh environments.

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<p>  </p> <p>Fossil fuel has dominated the global energy market for centuries, and the world is undergoing a great energy revolution from fossil fuel energy to renewable energies, given the concerns on global warming and extreme weather caused by the emission of carbon dioxide. Lithium ion batteries (LIBs) play an irreplaceable role in this incredible energy transition from fossil energy to renewable energy, given their importance in energy storage for electricity grids and promoting the mass adoption of battery electric vehicles (BEVs). Extreme fast charging (XFC) of LIBs, aiming to shorten the charging time to 15 minutes, will significantly improve their adoption in both the EV market and grid energy storage. However, XFC has been significantly hindered by the relatively sluggish Li+ transport within LIBs.</p> <p>Herein, effects caused by increasing charging rates (from 1C, 4C to 6C) on LiNi0.6Mn0.2Co0.2O2 (NMC622) || graphite cell were systematically probed via various characterization methods. From electrochemical test on their rate/long term cycling performance, the significant decrease in available capacity under high charging rates was verified. Structural evolutions of cycled NMC622 cathode and graphite anode were further probed via ex-situ powder diffraction, and it was found that lattice parameters <em>a</em> and <em>c</em> of NMC622 experience irreversible evolution due to loss of active Li+ within NMC622; no structural evolution was found for the graphite anode, even after 200 cycles under 6C (10 minutes) high charging rates. The aging behavior of liquid electrolyte was further analyzed via inductively coupled plasma-optical emission spectrometry (ICP-OES) and gas chromatography-mass spectrometry (GC-MS), increased Li+ concentration under higher charging rates and show-up of diethyl carbonate (DEC) and dimethyl carbonate (DMC) caused by transesterification both suggest faster aging/degradation of liquid electrolyte under higher charging rates.  </p> <p>Given the structural evolution of NMC622 caused by irreversible Li+ loss after long term cycling, the structural evolution of both NMC622 cathode and lithiated graphite anode were further studied via operando neutron diffraction on customized LiNi0.6Mn0.2Co0.2O2 (NMC622) || graphite cell. Via a quantitative analysis of collected Bragg peaks for NMC622 and lithiated graphite anode, we found the rate independent structural evolution of NMC622: its lattice parameters <em>a</em> and <em>c</em> are mainly determined by Li+ contents within it (<em>x</em> within Li<em>x</em>Ni0.6Mn0.2Co0.2O2) and follow the same evolution during the deintercalation process, from slowest 0.27 C charging to the fastest 4.4 C charging. For graphite intercalated compounds (GICs) formed during Li+ intercalating into graphite, the sequential phase transition from pure graphite → stage III (LiC30) → stage II (LiC12) → stage I (LiC6) phase under 0.27 C charging is consistent with previous studies. This sequential phase transition is generally maintained under increasing charging rates, and the co-existence of LiC12 phase and LiC6 was found for lithiated graphite under 4.4 C charging, mainly due to the large inhomogeneity under these high charging rates. Meanwhile, for the stage II (LiC12) → stage I (LiC6) transition, which contributes half the specific capacity for the graphite anode, quantitative analysis via Johnson-Mehl-Avrami-Kolmogorov (JMAK) model suggests it to be a diffusion-controlled, one-dimensional transition, with decreasing nucleation kinetics under increasing charging rates. </p> <p>Based on the LiC12 → LiC6 transition process, strategies to improve the Li+ transport properties were further utilized. Various cosolvents with smaller viscosity, from dimethyl carbonate (DMC), ethyl acetate (EA), methyl acetate (MA) to ethyl formate (EF), were further tested by replacing 20% (weight percent) ethyl methyl carbonate (EMC) of typical 1.2 M LiPF6 salt solvated in ethylene carbonate (EC)/EMC solvents (with a weight ratio of 30:70). From the measurement of their ion conductivity, the introduction of these cosolvents indeed enhanced the Li+ transport properties. This was further verified by improved rate performance from 2C, 3C to 4C charging for liquid electrolytes using these cosolvents. Both X-ray absorption spectroscopy (XAS) and X-ray powder diffraction (XRD) indicated the increase of Ni valence state and structural evolution of NMC622, all resulting from the irreversible loss of active Li+ within the NMC622 cathode. From long term cycling performance and further analysis of interfaces formed between electrode and anode, the best performance of electrolyte using DMC cosolvent was attributed to the most stable solid electrolyte interphase (SEI) and cathode electrolyte interphase (CEI) formed during the cycling. </p>

Viruses are the most abundant biological entity in the biosphere and are known to infect hosts from all domains of life. The aim of my work is to identify conserved and non-conserved features among the capsid structures of related and divergent icosahedral viruses via cryogenic electron microscopy, sequence analysis, molecular modeling, and other techniques. Bird polyomaviruses often cause severe disease in their hosts whereas mammalian polyomaviruses generally do not. Avian polyomavirus is a type of bird polyomavirus with an unusually broad host range compared to the restricted tropism of other polyomaviruses. Although most polyomaviruses have a conserved, rigid capsid protein structure, avian polyomavirus has a flexible capsid shell and a non-conserved C-terminus in its major capsid protein. A β-hairpin motif appears to stabilize other polyomaviruses but is missing in avian polyomavirus. The lack of this structure in avian polyomavirus may account for its capsid flexibility and broad host range. A minor capsid protein unique to bird polyomaviruses may be located on the inner capsid surface. This protein may have a role in the acute disease caused by bird polyomaviruses. The solution-state capsid structure of satellite tobacco mosaic virus was unexpectedly different than the previously solved crystalline structure. The conformational differences were accounted for by a shift of the capsid protein about the icosahedral fivefold axis. Conversely, the RNA core was consistent between solution and crystalline structures. The stable RNA core supports previous observations that the viral genome stabilizes the flexible capsid. Halophage CW02 infects Salinivibrio bacteria in the Great Salt Lake. The three-dimensional structure of CW02 revealed a conserved HK97-like fold that is found in all tailed, double-stranded DNA viruses. The capsid sequence of CW02 shares less than 20% identity with HK97-like viruses, demonstrating that structure is more conserved than sequence. A conserved module of genes places CW02 in the viral T7 supergroup, members of which are found in diverse aquatic environments. No tail structure was observed in reconstructions of CW02, but turret-like densities were found on each icosahedral vertex, which may represent unique adaptations similar to those seen in other extremophilic viruses.

Diagenetic and structural aspects of tight gas sandstones must be addressed concurrently in order to fully understand low-permeability sandstones and to better predict their reservoir quality attributes that arise from a combination of pore-scale and fracture distribution characteristics. This dissertation focuses on aspects of rock evolution that are germane to concurrent structural and diagenetic evolution, such as loading and thermal history, rock mechanical property evolution, and fracture timing. I tested the hypothesis that the cement precipitation step, governed by thermal exposure and grain surface attributes, governs how sandstone attributes evolve using observations from the Late Cretaceous Williams Fork sandstones from the Piceance Basin, Colorado. My research shows that essential information for predicting and understanding fracture patterns in sandstone can be obtained by unraveling cement precipitation (diagenetic) history. Fractures depend on the mechanical properties existing during fracture growth. I show that key rock mechanical properties (subcritical crack index, Young's modulus and Poisson's ratio), petrophysical behavior, and reservoir quality depend in a systematic way on time-temperature history and the intrinsic grain surface attributes of these sandstones. I classified the Williams Fork lithofacies petrographically and correlated those with log responses to create a model that can be used to predict reservoir quality and diagenesis directly from well logs. I determined rock mechanical characteristics by measuring the subcritical crack index (SCI), a mechanical property that influences fracture distribution characteristics, and by examining log-derived bulk mechanical properties. To quantify the influence of quartz cementation on the SCI and to determine the range of SCI values for sandstone of given framework composition at different diagenetic stages, I measured SCI on Williams Fork core samples and their outcrop equivalents. Diagenetic modeling is applied to determine the sandstone characteristics during fracturing. / text

Dans un procédé de séchage, l'évacuation de l'eau induit des modifications structurelles et physicochimiques qui engendrent des difficultés d'écoulement dans le séchoir. Cette étude a porté sur la modélisation du séchage continu par contact avec agitation. Nous avons développé un modèle markovien pour décrire les transferts de masse, de chaleur et l'écoulement dans un séchoir continu. Les paramètres d'entrée du modèle ont été déterminés expérimentalement sur un produit pâteux, tandis que d'autres paramètres ont été obtenus à partir de la littérature scientifique. L'étude de sensibilité de la teneur en eau et de la masse sèche retenue dans le séchoir a permis d'analyser et de hiérarchiser les effets des différentes variables opératoires. Enfin, nous avons étudié l'influence des variables opératoires sur le profil de teneur en eau, le temps de passage et les courbes de distribution de temps de séjours simulées. L'évolution structurelle du produit a été mise en évidence dans le modèle. / In a drying process, the evacuation of water induced structural and physico-chemical modifications that generate difficulties of flow in the dryer. This study focused on the modeling of agitated indirect continuous dryer. We developed a Markov model to describe the mass transfer, heat transfer and flow in a continuous dryer. The input parameters of the model were determined experimentally on a pasty product, while other parameters were obtained from the scientific literature. The sensitivity study of the moisture content and dry mass retained in the dryer was used to analyze and treat on a hierarchical basis the effects of different operating variables. Finally, we studied the influence of variables operating on the profile of moisture content, the passage time and the simulated curves of residence time distribution. The structural evolution of the product was considered in the model

Dans cette thèse, nous décrirons les effets structuraux (structure moyenne et à l’ordre local) engendrés par la substitution de l’aluminium par du bore dans la gehlénite (Ca2Al2-xBxSiO7). Les modifications des environnements atomiques à courtes et moyennes distances ont pu être déterminées grâce à une analyse poussée par diffraction sur poudre et à l’utilisation des dernières techniques de RMN haute résolution en phase solide. La première partie du manuscrit donne une description complète de la structure du minéral non substitué Ca2Al2SiO7. L’ensemble des 7 environnements de l’aluminium a été décrit par une simulation combinée de spectres RMN MAS et MQMAS 27Al acquis à différents champs et attribué à l’aide d’expériences d’édition spectrale. L’existence de liaisons Al-O-Al a été démontrée. Par ailleurs, la détermination de la proportion des unités Q3(2Al) nous a permis d’accéder à l’enthalpie de mise en ordre Al/Si dans ce système. Le mécanisme de substitution Al/B et l’évolution structurale de la solution solide Ca2Al2-xBxSiO7 (0 x 2), synthétisée par cristallisation de verres de même composition, ont été caractérisés par affinements Rietveld de données collectées par diffraction des rayons X et des neutrons. Des observations effectuées par RMN MAS sur les trois noyaux du système (27Al, 29Si et 11B) nous ont permis de compléter ces résultats. Un nouveau borosilicate de calcium de formule CaSi1/3B2/3O8/3, appartenant au diagramme de phase Ca2Al2SiO7-Ca2B2SiO7, a pu être identifié et synthétisé. Sa structure a été déterminée in situ et ab initio en combinant des techniques de diffraction, de microscopie électronique en transmission et de résonance magnétique nucléaire. / This work describes the structural modifications (average structure and local order) due to the substitution of boron for aluminum in gehlenite (Ca2Al2-xBxSiO7). The modifications of the short and medium range in the structure order have been determined using neutron and X-ray powder diffraction and recent advanced high resolution solid-state NMR techniques. The first part of this manuscript provides a full description of the structure of the non substituted mineral (Ca2Al2SiO7). All the 7 aluminum sites are identified and quantified by 27Al MAS, MQMAS and spectral editing NMR experiments performed at 9.4 and 17.6T. The existence of Al-O-Al linkage is demonstrated. The quantification of the Q3(2Al) species by 29Si MAS NMR allows the determination of the enthalpy related to the Al/Si ordering in the system. The Al/B substitution mechanism and the structural evolutions of the Ca2Al2-xBxSiO7 (0 x 2) solid solution, synthesised by crystallisation from glass, have been characterised by Rietveld refinements from Xray and neutron powder diffraction data. These results have been completed by solid-state NMR experiments (11B, 27Al and 29Si). A new calcium borosilicate phase (CaSi1/3B2/3O8/3), observed in the Ca2Al2SiO7-Ca2B2SiO7 phase diagram, has been identified and synthesised. The in situ and ab initio structure determination of this phase has been performed using the charge flipping method by combining powder diffraction, transmission electron microscopy and solid-state NMR analyses.

The Gulf of Mexico Basin Opening project (GUMBO) is a study of the lithological composition and structural evolution of the Gulf of Mexico (GoM) that uses Ocean Bottom Seismometer (OBS) data from four transects in the Northern GoM. I examine 39 OBS shot records in the easternmost transect for shear wave arrivals and pick shear wave travel times from the 11 usable records. I then carry out a tomographic inversion of seismic refraction travel times. I use the resulting shear-wave velocity model in conjunction with a previously constructed P-wave model to examine the relationship between Vp and Vs. I compare velocities in the sediment and basement with empirical velocities from previous studies for the purpose of constraining lithological composition below the transect and make an interpretation of the structural evolution of the eastern GoM. The seismic velocities for crust landward of the Florida Escarpment are consistent with normal continental crust. Seaward of the Escarpment, velocities in the upper oceanic crust are anomalously high (Vp = 6.5 – 7 km/sec; Vs = 4.0 – 4.6 km/sec). A possible explanation for this observation is that GoM basalt formation consisted of basaltic sheet flows, forming oceanic crust that does not contain the vesicularity and lower seismic velocities found in typical pillow basalts. Increased magnesium and iron content could also account for these high velocities. Seismic refraction and reflection data provide a means of investigating the nature of the Moho in the northeastern GoM. I use a finite difference method to generate synthetic record sections for data from eight instruments that are part of the two easternmost GUMBO seismic lines (lines 3 & 4). I then vary the thickness of the Moho in these synthetic models and compare the results with the original receiver gather to examine the effects this variability has on amplitudes. The data from the instruments chosen for these two lines are representative of continental and transitional crust. The finite difference models indicate that the Moho beneath GUMBO 3 is ~1500 m thick based on the onset and amplitudes of PmP arrivals. All five instruments display consistent results. The instruments along GUMBO 4 suggest a Moho almost twice as thick as GUMBO 3 on the landward end of the transect that grades into a Moho of similar thickness (1750 m) in the deep water GoM. The three instruments used to model the Moho in this area show that the Moho ranges from ~1750 to 3500 m in thickness. The sharper boundary beneath continental crust in GUMBO Line 3 supports other evidence that suggests magmatic underplating and volcanism in the northern GoM during the mid-Jurassic. The thicker Moho seen on the landward end of GUMBO Line 4 that is overlain by continental crust was likely unaffected by GoM rifting. Therefore, the Moho beneath the Florida Platform might be as old as the Suwannee Terrane, and complex Moho structure is not uncommon for ancient continental crust. / text

A detailed structural study of Rock Canyon (near Provo, Utah) provides insight into Wasatch Range tectonics and fold-thrust belt kinematics. Excellent exposures along the E-W trending canyon allow the use of digital photography in conjunction with traditional field methods for a thorough analysis of Rock Canyon's structural features. Detailed photomontages and geometric and kinematic analyses of some structural features help to pinpoint deformation mechanisms active during the canyon's tectonic history. Large-scale images and these structural data are synthesized in a balanced cross section, which is used to reconstruct the structural evolution of this portion of the range. Projection of surficial features into the subsurface produces geometrical relationships that correlate well with a fault-bend fold model involving one or more subsurface imbrications. Kinematic data (e.g. slickenlines, fractures, fold axes) indicate that the maximum stress direction during formation of the fault-bend fold trended at approximately 120°. Following initial thrusting, uplift and development of a thrust splay produced by duplexing may have caused a shift in local stresses in the forelimb of the Rock Canyon anticline leading to late-stage normal faulting during Sevier compression. These normal faults may have activated deformed zones previously caused by Sevier folding, and reactivated early-stage decollements found in the folded weak shale units and shaly limestones. Movement on most of these normal faults roughly parallels stress directions found during initial thrusting indicating that these extensional features may be coeval with thrusting. Other zones of extension and brittle failure produced by lower ramp geometry appear to have been activated during Tertiary Basin and Range extension along the Wasatch Fault Zone. Slickenline data on these later normal faults suggest a transport direction of nearly E-W distinguishing it from earlier events.