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238 records · Page 14

Thermally reconfigurable monoclinic nematic colloidal fluids

Fundamental relationships are believed to exist between the symmetries of building blocks and the condensed matter phases that they form. For example, constituent molecular and colloidal rods and disks impart their uniaxial symmetry onto nematic liquid crystals, such as those used in displays. Low-symmetry organizations could form in mixtures of rods and disks, but entropy tends to phase-separate them at the molecular and colloidal scales, whereas strong elasticity-mediated interactions drive the formation of chains and crystals in nematic colloids. To have a structure with few or no symmetry operations apart from trivial ones has so far been demonstrated to be a property of solids alone, but not of their fully fluid condensed matter counterparts, even though such symmetries have been considered theoretically and observed in magnetic colloids. In this work, we show that dispersing highly anisotropic charged colloidal disks in a nematic host composed of molecular rods provides a platform for observing many low-symmetry phases. Depending on the temperature, concentration and surface charge of the disks, we find nematic, smectic and columnar organizations with symmetries ranging from uniaxial to orthorhombic and monoclinic. With increasing temperature, we observe unusual transitions from less- to more-ordered states and re-entrant phases. Most importantly, we demonstrate the presence of reconfigurable monoclinic colloidal nematic order, as well as the possibility of thermal and magnetic control of low-symmetry self-assembly. Our experimental findings are supported by theoretical modelling of the colloidal interactions between disks in the nematic host and may provide a route towards realizing many low-symmetry condensed matter phases in systems with building blocks of dissimilar shapes and sizes, as well as their technological applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

On-Demand Designing of Cathode Internal Surface Architecture for Dramatic Enhancement of SOFC Performance and Durability

This project is aimed to design and modify the internal surfaces of porous composite cathode from currently commercially viable Solid Oxide Fuel Cells (SOFCs), using additive manufacturing process of Atomic Layer Deposition (ALD). The material systems being investigated are commercial composite electrodes complex three-dimensional topographies. In term of the chemistry of the ALD layer applied on the internal surface of the porous cathode, this project has employed commercially relevant electrolyte, electrocatalyst and noble metal materials set. Such materials are fully compatible with the commercial fuel cells, and this project has developed special nanostructure on the surface of the commercial composite cathodes. The formation of the designed nanoarchitecture on the surface of SOFC cathode has been achieved through precise control of ALD parameters and their effect on overall cell performance and resultant electrochemical reaction mechanism of cathodes has been investigated through full cell electrochemical performance testing and nanostructure characterization by transmission electron microscopy (TEM). Under the support of this award, following has been achieved: (1). For cathode materials in solid oxide fuel cells (SOFCs), such as perovskite mixed conductor La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-x (LSCF), cation surface segregation and consequently losing conductivity and active sites for the oxygen reduction reaction (ORR) are problematic. To mitigate the cation segregation and enhance SOFC durability, further decorating the internal backbone surface using the desired electrocatalysts could be a promoting approach. Commonly, the cation segregation such as Sr is very volatile, so the effective surface decoration is ideally conformal. Nevertheless, the conformal surface coating would inevitably alter the ORR pathways that initially take place on the surface of the backbone. To reveal the impact of the conformal coating on both the catalytic activity and the conductivity of the cathode, the unary electrocatalyst of Pt or CoO x , was applied to the LSCF/SDC composite electrode of inherently functional SOFCs, respectively. Both ALD coating layers evolve strong interaction with the LSCF composite cathode. Upon operations, the Pt coating layer remains conformal on LSCF grain surfaces but turns into discrete particles on SDC grain surfaces. Meanwhile, CoO x conformal coating grows to be the discrete nanograins on both the LSCF and SDC grains. ALD coating of the cathode alone reduces the ohmic resistance up to 28 % for the entire cells. The increased conductivity induced by the ALD coating of Pt or CoO x is ascribed to different mechanisms. For the inherent functional SOFCs, the present study presents a novel and feasible approach to apply a conformal, dense coating layer on the surface of a mixed conductor, simultaneously increasing the conductivity and durability of the SOFC cathode. (2). High resistance of the oxygen electrode still significantly hinders the state-of-the-art Solid Oxide Fuel Cells (SOFCs). In particular, for an oxygen electrode consisting of mixed electronic and ionic conductors, such as perovskite lanthanum strontium cobalt ferrite (LSCF), it deteriorates due to its low chemical stability of the grain surface. Such degradation is often associated with the segregation of cations. To prevent the cation surface segregation and its resultant perovskite phase decomposition, we demonstrate a conformal ultra-thin (7-10 nm) surface heterogeneous coating layer consisting of subjacent discrete Pt nanoparticles capped with a superjacent fully dense conformal CoO x layer. The performance studies indicate the ALD coating reduces the cell series resistance by up to 40 %. The conformal CoO x layer consists of randomly orientated but single-layered nanograins, with high-density intergranular and surface grain boundaries serving as the electrochemical reaction sites and facilitating mass transport. The conformal coating layer appears to have successfully suppressed the Sr outward diffusion and confined the Sr enriched layer to a ~ 2 nm interface perovskite phase between the coating layer and the LSCF grain surface. Moreover, this ultra-thin Sr enriched perovskite layer presumably possesses high oxygen vacancy and high ionic conductivity and further imposes tensile strain to the LSCF grain surfaces. With the combination of a conformal CoO x nanoionics, Sr enriched layer, and its strained interface, the ALD coating induced surface layer is estimated to have a conductivity of ~ 1.27x10 4 S/cm, which is over two orders magnitude of that from LSCF at 750 ºC.

30 DIRECT ENERGY CONVERSION↗

2D Semiconductor Nanosheets Supported on Colloidal Quantum Cubes

Two-dimensional (2D) colloidal nanocrystals bridge the physics of epitaxial quantum wells with the synthetic scalability of solution-processed nanomaterials, making them an attractive platform for future LEDs, lasers, and photodetectors. However, their strongly anisotropic 2D morphology complicates the formation of close-packed films required for electrically interfaced devices. Here, we address this limitation by introducing semiconductor quantum cubes (QCs) in which 2D CdSe nanosheets are conformally grown on six faces of CdS cubic scaffolds. This architecture preserves excitonic physics of quasi-2D nanosheets while leveraging the mechanical rigidity and self-assembly of nanocubes, enabling close-packed films with improved electronic coupling and electrical conductivity. By extending CdS/CdSe QCs into a CdS/CdSe/CdS core/shell/shell structure, we realize 2D quantum wells that exhibit unusual multiexciton behavior. In particular, CdS/CdSe/CdS QCs show repulsive exciton–exciton interactions, which decouple CdSe facets into quasi-independent emitters. This leads to the suppressed Auger recombination, long multiexciton lifetimes, and broadband optical gain. The demonstrated combination of unusual multiexciton photophysics and favorable film self-assembly characteristics in QCs presents opportunities for solution-processed optoelectronic devices.

perovskites↗

Quantifying Properties for a Mechanistic, Predictive Understanding of Aqueous Impact on Aging of Medium and Low Voltage AC and DC Cabling in Nuclear Power Plants

To address the gap in knowledge in understanding degradation in relevant service conditions, this project aimed to develop a mechanistic, predictive model of medium and low voltage cable failure based on the primary environmental degradation parameters of aqueous immersion time, temperature, and the oxidation extent. To do so, we took a two-fold approach toward evaluating degradation as related to the aqueous condition. First, we evaluated the chemical, mechanical, and electrical properties of polymers that comprise the cabling insulation under varied aqueous conditions at different temperatures. Secondly, we evaluated the performance of insulation materials under similar accelerated aging conditions in addition to the dielectric breakdown of the cabling under submersion conditions. Thermal oxidation and immersion of LDPE thin films were done using a Parr vessel and the extent of oxidation was monitored using the carbonyl index from ATR-FTIR spectrum, a ratio quantifying the carbonyl functionality produced on the LDPE film surface. Increasing the temperature, oxidation time, and oxygen pressure increased the water-vapor permeability and the carbonyl content. Thermogravimetric analysis of the films confirmed that there is indeed an initial weight loss of the smaller molecular weight molecules and volatiles. At higher temperatures, there is a secondary mass loss. Up to 70°C, the mass loss curves were similar until 80°C, when the aged films decreased at a much greater rate with respect to increasing temperature. This was seen in the 10, 50, 90% weight loss temperatures. The mechanical properties of sheet PP and HDPE as well as injection molded LDPE, HDPE, HDPP dog bones were plotted with respect to the time spent in the Parr vessel during thermal oxidation. For the sheet PP and HDPE, the UTS and the modulus of elasticity decreased while the elongation increased. The injection-molded LDPE, HDPE, and HDPP dog bones experienced a similar trend where the changes in the properties were within experimental uncertainty. This analysis of LDPE in dry and immersive oxygen-rich environments is an important baseline for future experiments looking at other degradation mechanisms. A predictive aging model for low-density polyethylene insulative cable housings was developed. This model revealed a combination of physical and chemical processes which lead to an increase in permeability and a decrease in strength of the insulator. In creating this predictive model, a gap of knowledge in the literature was revealed in two areas: understanding how the crystallinity of a polymer changes with time and visualizing the predicted pores formed through the insulator which leads to failure. Developing and using an adapted ATR-FTIR method, crystallinity was monitored and compared to bulk crystallinity found via DSC. Inhomogeneity in crystallinity changes were observed but the FTIR method but was found to be less reliable. Pore visualization was found utilizing electrical impedance spectroscopy saturated aged polyethylene films with synthesized citrate-capped gold nanoparticles, and chloroauric acid precursor. results indicate a decreasing impedance of the polyethylene films caused by the transport of ions through the film. SEM imaging was then performed for elemental analysis of the films and counter electrodes for the presence of ions. Chloride and gold ions were detected; however, no nanoparticles were found. This gives an estimated pore size of at least 0.3 nm through the aged film. Cyclic submergence of polyethylene and polypropylene in aqueous solutions of copper sulfate and Harrison’s solution were examined. It was discovered that aging in these mixed conditions and at 90°C did cause a small, yet significant increase to tensile strength for both unaged polyethylene and polypropylene. The PE and PP in cycled and submerged conditions did not have tensile strengths significantly different from dry-aged after 16 weeks. For both solutions, it was determined that capacitance increases with both water tree depth and cable temperature and is relatively independent of changing water tree AR. As for resistance, there is no apparent change between depth percentages of 10 and 80 for both solutions. This is because the water tree has not yet entered the conductor and thus there is no shorting current flowing through the tree yet. Between 80 and 100% water tree depth, it is observed that for both solutions there is a rapid decrease in resistance because the tree is now impacting the conductor shield and allowing shorting current to flow through it. The relationship between resistance and temperature was found to be inversed. As temperature increases, resistance decreases for both water tree solutions with distilled water having the most apparent difference across the range of temperatures simulated. With regards to water tree AR, resistance was found to be relatively independent at depth percentages of 10, 50, and 70, but there was some relationship at 100% depth for both solutions. At this depth, as water tree AR increased, resistance was found to also increase. Through the examination of voltage and electric field distribution plots, it was confirmed for EPR cables that increasing water tree depth leads to increasing distortion. The increase in shorting current at 100% depth for aqueous copper sulfate compared to distilled water was also visualized. Lastly, the relationship between shorting current and temperature for narrow water trees was visualized and validated using the distribution plots. This study has led to a better understanding of the effect of cable temperature, water tree solution, and geometry of the tree region on cable degradation. Furthermore, this study has documented simulation results of water tree degradation in EPR MV cables, which had been previously lacking in information. Future work in this area will add frequency into the mix and examine what effect it has on the rate of cable degradation as a result of water treeing. To compliment the work being carried by UMD on different polymer chemistries, harvested medium voltage (MV) cables were selected for accelerated aging study at ORNL. These medium voltage cables are representative of the vintages and materials that are currently in use at existing nuclear power plants (NPPs). These cables were immersed in water at 90°C and energized for a period of two years at elevated voltage. Partial discharge was measured during this period of time to track potential degradation. Unfortunately, due to the absence of failure, the extent of integration between the UMD techniques and the harvested MV insulation was limited. However, based on the findings and from the UMD research in the previous sections on polyethylene and polypropylene, follow-on characterization for harvested MV cable insulation should focus on sample preparation to take advantage of the UMD techniques to better understand mechanistic degradation in MV cable insulations. This would include: 1.) Utilization of solutions and impedance measurement insulation to track permeability in harvested and accelerated aging insulation samples, 2.) Adaptation of gold nanoparticle synthesis for electrical impedance spectroscopy with supporting SEM characterization to study pore formation in harvested and accelerated aged insulation samples, & 3.) ATR-FTIR crystallinity with multiple temperature dependent harvested MV cable insulation under different air and submerged accelerated aging. In addition, low voltage dielectric spectroscopy and high voltage dissipation factor, tan δ, could be implemented as a condition monitoring tool for harvested MV cable insulation in submerged environments.

24 POWER TRANSMISSION AND DISTRIBUTION↗