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At least 883 records · Page 49

In situ growth of ceramic quantum dots in polyaniline host via water vapor flow diffusion as potential electrode materials for energy applications

In situ preparation of polyaniline-ceramic nanocomposites has recently demonstrated that the electrical properties are highly improved with respect to the typical ex situ preparations. In this report, we present for the first time, to the best of our knowledge, the in situ growth of titanium oxide quantum dots in polyaniline host via water vapor flow diffusion as an easily adaptable route to prepare other ceramic-polymer nanocomposites. The main relevance of this method is the possibility to prepare ceramic quantum dots from alkoxide precursors using water vapor flow into any hydrophobic polymer host and to achieve good homogeneity and size-control. In addition, we perform full characterization by means of high-resolution transmission electron microscopy, X-ray powder diffraction, small angle X-ray scattering, thermogravimetric and calorimetric analyses, confocal Raman microscopy and impedance spectroscopy analyses. The presence of the polymer host and interparticle Coulomb repulsive interactions was evaluated as an influence for the formation of ~3–8 nm equally-sized quantum dots independently of the concentration. The polyaniline polaron population showed an increase for the quantum dots diluted regime and the suppression at the concentrated regime, ascribed to the formation of chemical bonds at the interface, which was confirmed by theoretical simulations. In agreement with the previous observation, the in situ growth of ceramic quantum dots in polyaniline host via water vapor flow diffusion could be very useful as a novel approach to prepare electrode materials for energy conversion and storage applications. - Highlights: • In situ growth of titanium oxide quantum dots in polyaniline host via water vapor flow diffusion. • Polyaniline charge carriers at the interface and charge interactions between quantum dots. • Easy extrapolation to sol-gel derived quantum dots into polymer host as potential electrode materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electronic transport in highly conducting Si-doped ZnO thin films prepared by pulsed laser deposition

Highly conducting (ρ = 3.9 × 10{sup −4} Ωcm) and transparent (83%) polycrystalline Si-doped ZnO (SiZO) thin films have been deposited onto borosilicate glass substrates by pulsed laser deposition from (ZnO){sub 1−x}(SiO{sub 2}){sub x} (0 ≤ x ≤ 0.05) ceramic targets prepared using a sol-gel technique. Along with their structural, chemical, and optical properties, the electronic transport within these SiZO samples has been investigated as a function of silicon doping level and temperature. Measurements made between 80 and 350 K reveal an almost temperature-independent carrier concentration consistent with degenerate metallic conduction in all of these samples. The temperature-dependent Hall mobility has been modeled by considering the varying contribution of grain boundary and electron-phonon scattering in samples with different nominal silicon concentrations.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Modifications produced on a large magnetized plasma column by a floating end-plate that is partially emissive: Experiment and theory

An experiment is performed on a large plasma device operated by the Basic Plasma Science Facility at the University of California, Los Angeles, in which an electrically floating structure is placed near the end of the 18-m magnetized plasma column. The structure consists of a flat carbon plate that acts as a mask for a smaller, ring-shaped LaB6 emissive surface whose temperature can be externally controlled. This configuration has been previously used to study electron heat transport and pressure-driven avalanches [B. Van Compernolle and G. J. Morales, Phys. Plasmas 24, 112302 (2017)] by biasing the LaB6 ring-cathode with respect to a distant anode in a cold afterglow plasma. In contrast, the present study is performed during the active portion of the steady-state discharge in which the nominal plasma parameters are determined by the injection of an electron beam from a BaO cathode at the opposite end. It is found that, even without an applied bias on the LaB6 cathode, the self-consistent potential and current profiles are modified near the end plate as the LaB6 temperature is increased, resulting in density increases on the field lines in contact with the ring-cathode. In the absence of enhanced ionization, at the largest cathode temperatures, the ambient density can be doubled. A theoretical model is presented that provides a quantitative explanation for the experimental observations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Spark plasma sintering of structure-tailored ultrahigh-temperature components: First step to complex net shaping

The net-shaping capability in spark plasma sintering (SPS) of ultrahigh-temperature ceramics has been explored in this study. The annular or ring-like shape is considered here as the first step to a more complex geometry compared to a solid cylinder or disk. ZrC powders have been SPS processed in specially designed graphite tooling to achieve the annular shape geometry. Experimental runs have been carried out to determine the optimal processing parameters for producing highly dense ZrC specimens in this geometry. Finite-element modeling framework has been constructed to determine the internal stress evolution, as well as densification, during the SPS of the annular-shaped ZrC. The formulated processing schemes for ZrC have been adapted to process SiC/ZrB2 composite powder with the purpose of making tooling components for SPS applications. The applicability of the obtained composite SPS tooling has been evaluated at high temperature and high pressure associated with SPS regimes.

36 MATERIALS SCIENCE↗

Advanced Gasification and Novel Transformational Coal Conversion Technologies Development: Final Technical Report

This report summarizes the work carried out in furtherance of the NETL/DOE award, OTM-Enhanced Coal Syngas for Carbon Capture Power Systems and Fuel Synthesis Applications. The overall objective of the project was to further develop Oxygen Transport Membrane (OTM) technology and assess the potential for integration in coal power generation. OTM technology has the potential to enhance the quality of syngas produced by coal gasifiers, reduce the amount of cryogenic-derived oxygen required in Integrated Gasification Combined Cycle (IGCC) power plants, and allow for coal and natural gas integration. Process simulations and techno-economic analyses were carried out to estimate the cost and performance of OTM enhanced IGCC plants, IG-NGCC plants, and OTM enhanced Fischer Tropsch (FT) Liquids from coal and natural gas plants. The OTM enhanced power plants achieved higher carbon capture rates, higher efficiencies, and lower cost of electricity compared to the base cases. The most significant benefits were achieved for cases which used low rank coal as the feed. Fischer-Tropsch coal to liquids plants with iron-based catalysts and natural gas integration utilizing OTM technology showed improved carbon conversion, improved thermal efficiency and lower cost of production. With respect to OTM core technology development, significant advances have been made in several areas. The development and implementation of a third-generation membrane materials and manufacturing process has resulted in the availability of robust and reliable, high performance membranes, that can be manufactured at high yield. Progress towards the goal of higher pressure operation has been demonstrated with the development of improved metal-ceramic seals and components of the panel array module that integrate membrane-seal assemblies with primary and secondary reforming catalysts have been further developed and demonstrated. Work concluded with the successful start-up and operation of a multi-panel pilot-scale system which is the final step in technology development ahead of demonstration.

20 FOSSIL-FUELED POWER PLANTS↗

Microstructured ion-conducting composites and uses thereof

A composite membrane with nanostructured inorganic and organic phases is applied as an ion-selective layer to prove processability, prevent dendrite shorting, and increase power output of lithium-metal anodes through better Li-ion conductivity. Nanoconfinement, as opposed to macroscale confinement, is known to dramatically alter the properties of bulk materials. Control over a ceramic's size, shape, and properties is achieved with polymer templates. This is a new composition of matter and unique approach to composite membrane design.

Frischmann, Peter David↗

Surface exsolving perovskite ceramics as catalyst for microwave methane pyrolysis to co-generate hydrogen and carbon nanotube

In this study, we have successfully developed a novel surface exsolving perovskite ceramic, which demonstrates the ability to simultaneously generate CO x -free hydrogen and carbon nanotubes (CNTs) through methane pyrolysis under the influence of microwave irradiation. We conducted an extensive survey and optimization of various perovskite materials specifically tailored for microwave applications. Among the materials investigated, nickel-doped strontium titanium oxide (STON) emerged as the most promising candidate, exhibiting both a satisfactory methane conversion rate and excellent responsiveness to microwave irradiation. Refinement of STON was carried out by fine-tuning the Ni content, optimizing the reduction dwell time, and adjusting the reduction temperature. Notably, SrTiNi 0.08 O 3 (STON8), demonstrated an impressive initial methane conversion rate of up to 40%. Transmission Electron Microscopy (TEM) provided visual evidence of the correlation between Ni content and reduction temperature, with respect to the exsolved Ni metal particle size. This finding highlights the immense potential of surface exsolving perovskite ceramics as a highly effective catalyst for the simultaneous production of CNTs and COx-free hydrogen via methane pyrolysis under microwave irradiation. Furthermore, it represents a step forward in the field of catalytic materials and microwave-driven processes.

08 HYDROGEN↗

Electrical and optical properties of NdAlO{sub 3} synthesized by an optimized combustion process

Nanocrystals of neodymium aluminate (NdAlO{sub 3}) are synthesized using an optimized single step auto-ignition citrate complex combustion process. The combustion product was characterized by X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy and Ultraviolet–visible reflection spectroscopy. The combustion product is single phase and composed of aggregates of nanocrystals of sizes in the range 20–40 nm. The NdAlO{sub 3} crystallized in rhombohedral perovskite structure with lattice parameters a = 5.3223 Å and c = 12.9292 Å. The absorption spectrum of the NdAlO{sub 3} nanocrystals shows characteristic absorption bands of the Nd atom. The polycrystalline fluffy combustion product is sintered to high density (∼ 97%) at ∼ 1450 °C for 4 h and the microstructure was characterized by scanning electron microscopy. The electrical properties of the sintered product were studied using dielectric measurements. The sintered NdAlO{sub 3} has a dielectric constant (ε{sub r}) and a dielectric loss (tan δ) of 21.9 and ∼ 10{sup −3} at 5 MHz, respectively. - Highlights: • NdAlO{sub 3} nanocrystals were synthesized through a citrate combustion process. • The nanocrystals were sintered to ∼ 97% of theoretical density. • The materials were characterized using a number of analytical techniques. • Nanostructured NdAlO{sub 3} showed crystal field splitting of Nd ions. • Dielectric properties of the sintered NdAlO{sub 3} ceramics were studied.

36 MATERIALS SCIENCE↗

Review on dielectric properties of rare earth doped barium titanate

Rare earth doped Barium Titanate (BaTiO{sub 3}) were studied due to high permittivity, excellent electrical properties and have wide usage in various applications. This paper reviewed on the electrical properties of RE doped BaTiO{sub 3} (RE: Lanthanum (La), Erbium (Er), Samarium (Sm), Neodymium (Nd), Cerium (Ce)), processing method, phase transition occurred and solid solution range for complete study. Most of the RE doped BaTiO{sub 3} downshifted the Curie temperature (T{sub C}). Transition temperature also known as Curie temperature, T{sub C} where the ceramics had a transition from ferroelectric to a paraelectric phase. In this review, the dielectric constant of La-doped BaTiO{sub 3}, Er-doped BaTiO{sub 3}, Sm-doped BaTiO{sub 3}, Nd-doped BaTiO{sub 3} and Ce-doped BaTiO{sub 3} had been proved to increase and the transition temperature or also known as T{sub C} also lowered down to room temperature as for all the RE doped BaTiO{sub 3} except for Er-doped BaTiO{sub 3}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

HGMS: Glasses and Nanocomposites for Hydrogen Storage

The primary goal of this project is to fabricate and investigate different glass systems and glass-derived nanocrystalline composite materials. These glass-based, two-phased materials will contain nanocrystals that can attract hydrogen and be of potential interest as hydrogen storage media. The glass materials with intrinsic void spaces that are able to precipitate functional nanocrystals capable to attract hydrogen are of particular interest. Proposed previously, but never practically implemented, one of promising concepts for storing hydrogen are micro-containers built of glass and shaped into hollow microspheres. The project expanded this concept to the exploration of glass-derived nanocrystalline composites as potential hydrogen storage media. It is known that the most desirable materials for hydrogen storage do not interact chemically with hydrogen and possess a high surface area to host substantial amounts of hydrogen. Glasses are built of disordered networks with ample void spaces that make them permeable to hydrogen even at room temperature. Glass-derived nanocrystalline composites (two-phased materials), combination of glasses (networks with ample voids) and functional nanocrystals (capable to attract hydrogen), appear to be promising candidates for hydrogen storage media. Key advantages of glass materials include simplicity of preparation, flexibility of composition, chemical durability, non-toxicity and mechanical strength, as well as low production costs and environmental friendliness. This project encompasses a fundamental research into physics and chemistry of glasses and nanocrystalline composite materials, derived from glass. Studies are aimed to answer questions essential for considering glass-based materials and composites as potential hydrogen storage media. Of particular interest are two-phased materials that combine glasses with intrinsic voids spaces for physisorption of hydrogen and nanocrystals capable of chemisorption. This project does not directly address any hydrogen storage technical barriers or targets in terms of numbers. Specifically, hydrogen sorption and desorption tests or kinetics measurements were not part of the project scope. However, the insights gained from these studies could help to answer fundamental questions necessary for considering glass-based materials as hydrogen storage media and could be applied indirectly towards the DOE hydrogen storage technical targets such as system weight and volume, system cost and energy density. Such questions are: Can specific macro-crystals, proven to attract hydrogen when in a macroscopic form (bulk), be nucleated in glass matrices as nanocrystals to create two-phased materials? What are suitable compositions that enable to synthetize glass-based, two-phase materials with nanocrystals that can attract hydrogen via surface or bulk interactions? What are the limits of controlling the microstructure of these materials, especially limits for nanocrystals density and size? Finally, from a technological point of view, the fabrication of glass-derived nanocomposites that we explore is a very simple, fast and inexpensive process that does not require costly or specialized equipment which is an important factor for practical applications.

08 HYDROGEN↗

High Temperature CMC Nozzles for 65% Efficiency

GE Gas Power has executed a development project that targeted cooled high-temperature ceramic matrix composite (CMC) nozzles as an innovative turbomachinery component that contributes toward the DOE’s goal for advanced gas turbines that are capable of at least 65% efficiency in combined cycle application. This technology advancement has potential to also benefit gas turbines used in coal-based IGCC applications with pre-combustion carbon capture and hydrogen as the resulting fuel. The development of this technology built upon CMC capability advancements made under earlier DOE programs. The objective for this project was to develop the application of ceramic matrix composite for nozzle application in an industrial gas turbine hot gas path. The CMC component development activity done in this project facilitates high firing temperatures through improved cooling designs and concepts, better sealing, reduced leakage, advanced manufacturing processes to facilitate high performing turbomachinery, and revolutionary component architecture to improve the gas turbine performance in a combined cycle application.

20 FOSSIL-FUELED POWER PLANTS↗

Carbonized Microvascular Composites for Gas Receivers

This project is focused on the development and characterization of a novel carbonized microvascular composite intended for use in advanced, gas-phase Concentrating Solar Power (CSP) collectors, a muVASC receiver. These are polymer-fiber composites with directly integrated microchannels that will be carbonized to form a lightweight, high-absorptivity material that includes an embedded microvascular network of channels. The topology of these microchannels will be engineered to optimize heat transfer to a supercritical carbon dioxide (sCO2) heat transfer fluid. This system is based on the microVasc technology which enables the formation of defined channels within a composite material through selective depolymerization of polymer fibers. The resulting composite can then be carbonized and coated with an oxidation resistant coating, perhaps in situ, to form a thermally efficient, mechanically robust carbon-carbon composite. Carbon- carbon composites are a potential alternative to metallic systems, because these materials have extreme resistance to high temperatures and maintain mechanical properties with little change from room temperature up to almost 1800 °C and have high thermal conductivity. Compared to metallic microchannel receiver systems, we expect that the proposed system will allow for more efficient heat transfer, improved mechanical durability, and enhanced response to off-axis heating. These advantages will be realized through a combination of material performance and improved microchannel architectures as they are not constrained by available machining processes (weaving and 3-D printing for composites vs. machining for metal).

14 SOLAR ENERGY↗

Crystal development during carbonation of lime-based mortars in different environmental conditions

Highlights: • High CO{sub 2} and DiloCarb® treatment favour advanced carbonation and self-healing. • In the lime mortar without ceramics, channel type pores occur in the aggregate border. • In the lime mortars with ceramics, vug type pores are produced in the binder during kneading. • The formation of tabular CaCO{sub 3} polymorphs caused an increase in stress leading to microshrinkage cracks. • The use of a ceramic provoked dissolution and then re-precipitation of more stable polymorphs. - Abstract: This study examines crystal development during the carbonation of lime mortars according to the additives used and curing conditions. Two types of samples were prepared, one with sand and the other one additionally including Roman ceramics. These mortars were cured: 1) by spraying with a carbonation accelerator product under laboratory conditions; 2) in a climate chamber under 20 °C, 60% relative humidity, and 1600 ppm CO{sub 2}; and 3) under laboratory conditions as controls. Polarized light microscopy, SEM-EDS and XRD were used at 28, 90, 120 and 180 days to monitor the carbonation process. Observations indicate the development of different CaCO{sub 3} polymorphs, which appeared as metastable phases. The early nucleation of a well-defined calcite phase as the most stable CaCO{sub 3} polymorph was only identified in the chamber-cured samples. Differences in the pore network were observed depending on the composition and morphology of the mortar components and the environmental curing conditions.

36 MATERIALS SCIENCE↗

Continuous Enzymatic Hydrolysis Development for Improved Saccharification Performance

The Continuous Enzymatic Hydrolysis Development (CEHD) project aims to reduce the cost and commercialization risks of Gen2 biorefinery sugar/lignin/ethanol production through development of a deployable continuous enzymatic hydrolysis process. Recent changes in the technical landscape of commercial enzymatic hydrolysis of Gen2 pretreated biomass dictate that the existing hybrid SSF approach be reconsidered. Most importantly, the current practice of "finishing hydrolysis" in SSF must be abandoned due to the fact that new cellulase/hemicellulose formulations from Novozymes, now the sole supplier of commercial Gen2 enzymes in North America, are now not rated for SSF (see NZ CTec3HS product bulletin). We have recently developed bench scale CEH tools to optimize saccharification of DMR pretreated biomass where, unlike SSF with yeast or Zymomonas, the pH, temperature, oxygen tension, LPMO mediator concentration, and/or removal of end-product inhibitors can be precisely controlled. In scale up, the goal is to use existing commercial cross flow ceramic membrane filtration external loops coupled to enzymatic hydrolysis (EH) reactors. Pretreated biomass solids and enzymes are retained for reaction while solubilized product sugars are removed in situ, with high extents of conversion and longer enzyme lifetimes achieved through a series of reactor-membrane unit stages. The CEHD project is focused on advancing CEH as a transformational, process-intensified, lower-cost method for producing soluble clarified biomass sugars and insoluble lignin-rich streams.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗

Interfacial Characteristics Investigation for One-Step EDM Drilling of Cooling Holes in TBCs

In this study, the one-step electrical discharge machining of inclined cooling holes is performed in thermal-barrier-coated nickel-based superalloys via the assisting electrode method. The effects of the process parameters, including the inclination angle, peak current, pulse duration, and duty cycle, on interfacial characteristics of cooling holes were investigated. The research results are as follows: After machining, the hardness of TBCs increases slightly and the adhesion strength of ceramic coating has a slight reduction. Delamination prevailingly appears at the ceramic coating/bonding coating interface, and its length at the trailing edge is greater than that at the leading edge. Increasing either the discharge energy or the duty cycle also aggravates the severity of the delamination. Under an excessive peak current of 22.5 A, the complete spalling of the ceramic coating occurs in the vicinity of the holes. Additionally, a reduction in the inclination angle results in a significant increase in delamination cracking and poorer interface integrity. The interfacial microstructure features of the holes vary with the inclination angle. The large-scale spalling of ceramic coating is prone to occur at the trailing edge when using an inclination angle of 30°. The spattering is susceptible to appear at the entrance of the holes under inclination angles of 60° and 75°, and its composition is primarily Ni, C, Zr, Cr, Nb, Fe, and Cu.

36 MATERIALS SCIENCE↗

Oxygen redox and instability in energy ceramics

Energy ceramics, including solid electrolytes and catalysts for high-temperature fuel/electrolysis cells and oxide cathodes for batteries, often experience harsh chemical and electrochemical conditions. Practical and new applications require that these devices are operated under ever more extreme redox conditions for higher energy density and power density. This challenges the stability of the energy ceramic materials and calls for a better understanding of the degradation mechanisms and innovative strategies for degradation mitigation. Here we present our analysis and perspectives on degradation phenomena in three categories of electrochemical devices of practical interest, including solid oxide fuel/electrolysis cells, protonic ceramic fuel/electrolysis cells, and lithium-ion batteries. We also discuss the stability/degradation of the key ceramic components from the view of oxygen redox and instability arising from anodic bias, transport limitation, and coupled electro-chemo-mechanics at the virtual and physical interfaces. We hope these perspectives provide design principles for electroceramic chemistry, microstructure, and processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗