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At least 1,243 records · Page 69

Ammonia-fed reversible protonic ceramic fuel cells with Ru-based catalyst

Abstract The intermediate operating temperatures (~400–600 °C) of reversible protonic ceramic fuel cells (RePCFC) permit the potential use of ammonia as a carbon-neutral high energy density fuel and energy storage medium. Here we show fabrication of anode-supported RePCFC with an ultra-dense (~100%) and thin (4 μm) protonic ceramic electrolyte layer. When coupled to a novel Ru-(BaO) 2 (CaO)(Al 2 O 3 ) (Ru-B2CA) reversible ammonia catalyst, maximum fuel-cell power generation reaches 877 mW cm −2 at 650 °C under ammonia fuel. We report relatively stable operation at 600 °C for up to 1250 h under ammonia fuel. In fuel production mode, ammonia rates exceed 1.2 × 10 −8 NH 3 mol cm −2 s −1 at ambient pressure with H 2 from electrolysis only, and 2.1 × 10 −6 mol NH 3 cm −2 s −1 at 12.5 bar with H 2 from both electrolysis and simulated recycling gas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical interaction and enhanced interfacial ion transport in a ceramic nanofiber–polymer composite electrolyte for all-solid-state lithium metal batteries

This article reports the synergy between ceramic nanofibers and a polymer, and the enhanced interfacial Li-ion transport along the nanofiber/polymer interface in a solid-state ceramic/polymer composite electrolyte, in which a three-dimensional (3D) electrospun aluminum-doped Li 0.33 La 0.557 TiO 3 (LLTO) nanofiber network is embedded in a polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) matrix. Strong chemical interaction occurs between the nanofibers and the polymer matrix. Addition of the ceramic nanofibers into the polymer matrix results in the dehydrofluorination of the PVDF chains, deprotonation of the –CH 2 moiety and amorphization of the polymer matrix. Solid-state nuclear magnetic resonance (NMR) spectra reveal that lithium ions transport via three pathways: (i) intra-polymer transport, (ii) intra-nanofiber transport, and (iii) interfacial polymer/nanofiber transport. In addition, lithium phosphate is coated on the LLTO nanofiber surface before the nanofibers are embedded into the polymer matrix. The presence of lithium phosphate at the LLTO/polymer interface further enhances the chemical interaction between the nanofibers and the polymer, which promotes the lithium ion transport along the polymer/nanofiber interface. This in turn improves the ionic conductivity and electrochemical cycling stability of the nanofiber/polymer composite. As a result, the flexible LLTO/Li 3 PO 4 /polymer composite electrolyte membrane exhibits an ionic conductivity of 5.1 × 10 -4 S cm -1 at room temperature and an electrochemical stability window of 5.0 V vs. Li/Li + . A symmetric Li|electrolyte|Li half-cell shows a low overpotential of 50 mV at a constant current density of 0.5 mA cm -2 for more than 800 h. In addition, a full cell is constructed by sandwiching the composite electrolyte between a lithium metal anode and a LiFePO 4 -based cathode. Such an all-solid-state lithium metal battery exhibits excellent cycling performance and rate capability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Gel composite electrolyte – an effective way to utilize ceramic fillers in lithium batteries

Achieving synergy between ion-conducting polymers and ceramics in a composite electrolyte has been proven to be difficult as the complicated ceramic/polymer interface presents challenges to understand and control. In this work, we report a strategy to utilize discrete ceramic fillers to form a gel composite electrolyte with enhanced transport properties for lithium metal batteries. The matrix of the composite membrane is crosslinked poly(ethylene oxide) with bis(trifluoromethane)sulfonimide lithium salt (LiTFSI). The membrane is plasticized with tetraethylene glycol dimethyl ether (TEGDME). The incorporation of doped-lithium aluminum titanium phosphate particles (LICGC™) into the membrane greatly improves the membrane's cycling characteristics against the lithium electrode, exhibiting lower interfacial impedance, lower overpotential and higher rate capability. The underpinnings of the superior performance of the gel composite electrolyte are discussed in depth. LICGC™ can immobilize the TFSI - anions in the polymer matrix and simultaneously promote Li+ transport by increasing the plasticizer to Li + ratio. Further, the transport enhancement is achieved without sacrificing mechanical properties. The composite membrane shows significantly improved handleability and processability. This work sheds light on the design strategy for a safe electrolyte towards stable Li metal batteries.

25 ENERGY STORAGE↗

Room temperature dielectric and magnetic properties of Gd and Ti co-doped BiFeO{sub 3} ceramics

Room temperature dielectric and magnetic properties of BiFeO{sub 3} samples, co-doped with magnetic Gd and non-magnetic Ti in place of Bi and Fe, respectively, were reported. The nominal compositions of Bi{sub 0.9}Gd{sub 0.1}Fe{sub 1–x}Ti{sub x}O{sub 3} (x = 0.00-0.25) ceramics were synthesized by conventional solid state reaction technique. X-ray diffraction patterns revealed that the substitution of Fe by Ti induces a phase transition from rhombohedral to orthorhombic at x > 0.20. Morphological studies demonstrated that the average grain size was reduced from ∼1.5 μm to ∼200 nm with the increase in Ti content. Due to Ti substitution, the dielectric constant was stable over a wide range of high frequencies (30 kHz to 20 MHz) by suppressing the dispersion at low frequencies. The dielectric properties of the compounds are associated with their improved morphologies and reduced leakage current densities probably due to the lower concentration of oxygen vacancies in the compositions. Magnetic properties of Bi{sub 0.9}Gd{sub 0.1}Fe{sub 1–x}Ti{sub x}O{sub 3} (x = 0.00-0.25) ceramics measured at room temperature were enhanced with Ti substitution up to 20% compared to that of pure BiFeO{sub 3} and Ti undoped Bi{sub 0.9}Gd{sub 0.1}FeO{sub 3} samples. The enhanced magnetic properties might be attributed to the substitution induced suppression of spiral spin structure of BiFeO{sub 3}. An asymmetric shifts both in the field and magnetization axes of magnetization versus magnetic field curves was observed. This indicates the presence of exchange bias effect in these compounds notably at room temperature.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Nd:AlN polycrystalline ceramics: A candidate media for tunable, high energy, near IR lasers

We present processing and characterization of Nd-doped aluminum nitride (Nd:AlN) polycrystalline ceramics. We compare ceramics with significant segregation of Nd to those exhibiting minimal segregation. Spatially resolved photoluminescence maps reveal a strong correlation between homogeneous Nd doping and spatially homogeneous light emission. The spectroscopically resolved light emission lines show excellent agreement with the expected Nd electronic transitions. Notably, the lines are significantly broadened, producing near IR emission (~1077 nm) with a remarkable ~100 nm bandwidth at room temperature. We attribute the broadened lines to a combination of effects: multiple Nd-sites, anisotropy of AlN and phonon broadening. These broadened, overlapping lines in a media with excellent thermal conductivity have potential for Nd-based, tunable lasers with high average power.

36 MATERIALS SCIENCE↗

In-situ transmission electron microscopy study of oxygen vacancy ordering and dislocation annihilation in undoped and Sm-doped CeO 2 ceramics during redox processes

Ceria (CeO 2 ) based ceramics have been widely used for many applications due to their unique ionic, electronic, and catalytic properties. We report our findings in investigating into the redox processes of undoped and Sm-doped CeO 2 ceramics stimulated by high-energy electron beam irradiation within a transmission electron microscope (TEM). The reduced structure with oxygen vacancy ordering has been identified as the CeO 1.68 (C-Ce 2 O 3+δ ) phase via high-resolution TEM. The reduction of Ce 4+ to Ce 3+ has been monitored by electron energy-loss spectroscopy. The decreased electronic conductivity of the Sm-doped CeO 2 (Sm 0.2 Ce 0.8 O 1.9 , SDC) is revealed by electron holography, as positive electrostatic charges accumulated at the surfaces of SDC grains under electron beam irradiation, but not at CeO 2 grains. The formation of the reduced CeO 1.68 domains corresponds to lattice expansion compared to the CeO 2 matrix. Therefore, the growth of CeO 1.68 nuclei builds up strain inside the matrix, causing annihilation of dislocations inside the grains. By using in-situ high-resolution TEM and a fast OneView camera recording system, we investigated dislocation motion inside both CeO 2 and SDC grains under electron beam irradiation. The dislocations prefer to dissociate into Shockley partials bounded by stacking faults. Then, the partials can easily glide in the {111} planes to reach the grain surfaces. Even the Lomer-Cottrell lock can be swept away by the phase change induced strain field. Our results revealed the high mobility of dislocations inside CeO 2 and SDC grains during their respective redox processes

36 MATERIALS SCIENCE↗

Thermal conductivity evaluation of ion irradiated Si 3 N 4 and ZrN ceramics using spatial domain thermoreflectance

Nitride ceramics have been investigated for different applications in the nuclear industry, such as space nuclear power, fusion reactor diagnostics and plasma heating, inert matrix fuels, and accident tolerant fuels. Although thermal conductivity remains one of the most important properties to track following irradiation, traditional techniques such as laser flash and xenon flash are limited to bulk sample characterization, which requires lengthy and cost-consuming neutron irradiation. This work used spatial domain thermoreflectance (SDTR) for the micrometer-scale measurement of thermal conductivity in 15 MeV Ni ion-irradiated silicon nitride and zirconium nitride from 1 to 50 dpa and 300 to 700 °C. Here, the SDTR-measured unirradiated thermal conductivity was found to be consistent with the published data on bulk samples. Electrically conductive ZrN exhibits modest reduction after irradiation which is minimal at the highest irradiation temperatures. In electrically insulating Si 3 N 4 , the reduction is more significant and unlike ZrN, the reduction remains significant even at a higher irradiation temperature. The thermal resistance evolution following irradiation was compared with lattice swelling, which was determined using grazing incidence x-ray diffraction, and radiation-induced defects were observed using transmission electron microscopy. A saturation value was observed between 15 and 50 dpa for thermal conductivity degradation in both nitride ceramics and a direct correlation with high-temperature defect recombination was observed, as well as the potential presence of additional carrier scattering mechanisms.

36 MATERIALS SCIENCE↗

Effects of a refractory metal protective barrier on uranium carbonitride ceramic–metallic composites exposed to a high temperature hydrogen environment

Uranium nitride has been under consideration at NASA and the Department of Energy for nuclear thermal propulsion applications intended for deep space exploration vehicles. It is critical to the success of the technology development that the behavior of the fuel system is properly characterized in operational environments. This body of work fabricated ceramic metal composites consisting of uranium ceramic fuel in a molybdenum and molybdenum–tungsten metal matrix, both with and without an exterior molybdenum barrier. Specimens were introduced to a high temperature hydrogen environment and characterized through x-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy to identify characteristic changes. A portion of the specimens was fabricated with a 1.27 mm thick molybdenum barrier in order to isolate the material from the hydrogen environment. Instability of the uranium nitride occurred as low as 2073 K, leading to aggressive instability approaching 2658 K. Carbon reactions with the metal matrix were observed as well as alloying between the uranium and metal matrix constituents. The liquid uranium resulting from the instability of the uranium nitride was observed to attack the grain boundaries of the refractory metal, resulting in the formation of a liquid uranium molybdenum eutectic melt. Specimens encased in a barrier experienced similar results. The authors conclude this is a significant challenge to applications of this cermet at these temperatures. Alternate configurations with resilient hermetic seals or lower temperature applications such as power reactors may have more success.

36 MATERIALS SCIENCE↗

High entropy ceramics for applications in extreme environments

Abstract Compositionally complex materials have demonstrated extraordinary promise for structural robustness in extreme environments. Of these, the most commonly thought of are high entropy alloys, where chemical complexity grants uncommon combinations of hardness, ductility, and thermal resilience. In contrast to these metal–metal bonded systems, the addition of ionic and covalent bonding has led to the discovery of high entropy ceramics (HECs). These materials also possess outstanding structural, thermal, and chemical robustness but with a far greater variety of functional properties which enable access to continuously controllable magnetic, electronic, and optical phenomena. In this experimentally focused perspective, we outline the potential for HECs in functional applications under extreme environments, where intrinsic stability may provide a new path toward inherently hardened device design. Current works on high entropy carbides, actinide bearing ceramics, and high entropy oxides are reviewed in the areas of radiation, high temperature, and corrosion tolerance where the role of local disorder is shown to create pathways toward self-healing and structural robustness. In this context, new strategies for creating future electronic, magnetic, and optical devices to be operated in harsh environments are outlined.

36 MATERIALS SCIENCE↗

How Interface Evolution at the Nanoscale Dictates Protonic Ceramic Cell Behavior

Understanding the effects of heterointerfaces in nanodevices remains a challenge in interface engineering for systems applied in solid oxide fuel cells, catalysis, sensors, and memristors [1]. Previous studies have shown that the presence of interfaces in ceramic oxide nanodevices affects their impedance properties compared to bulk systems [2]. In this work, we analyze a thin-film model system designed to study the interfaces between representative electrode and electrolyte materials employed in protonic ceramic electrochemical cells for the reversible conversion of hydrogen o electricity. The investigated device features a 21-layer architecture that alternates between an electrode material PBSCF (PrBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5+ϵ ) and a proton-conducting electrolyte BZY (BaZr 0.8 Y 0.2 O 3-δ ), with uniform 20 nm thickness for each layer. Here, the device was fabricated using Pulsed Laser Deposition (PLD) and supported on a conductive Nb-doped STO (Nb-SrTiO 3 ) substrate.

dos Santos, Gabriel T. [Northwestern University, E↗

Simulation and measurement of beam-induced heating of ceramic vacuum chambers

In this article, we summarize recent theoretical and experimental studies of the impedance and beam-induced heating of titanium-coated ceramic vacuum chambers used in the NSLS-II injection kickers. The impedance was calculated using the field matching theory assuming planar approximation and compared with the mpedanceake2 code. For the coating thickness of a few microns, we demonstrated that the beam-induced power is dissipated in the titanium coating and that the longitudinally averaged two-dimensional power density is approximated by an analytical expression, thus allowing the use of a simplified model of the power density as input for the code to simulate the temperature distribution with realistic nonuniform thickness of the Ti coating. For a few values of the NSLS-II beam current, we measured the beam-induced heating of two ceramic chambers using thermal sensors installed along the chamber and compared the measurement results with the simulations. Published by the American Physical Society 2024

36 MATERIALS SCIENCE↗

How relative defect migration energies drive contrasting temperature-dependent microstructural evolution in irradiated ceramics

Ceramic materials have become widely used in various fields of material science, and ceramic oxides such as cubic zirconia (c- ZrO 2 ) and magnesia (MgO) are candidate materials for nuclear energy applications. For the corresponding in-service conditions of these materials, there is a crucial need in studies at moderate or high temperatures of the physical phenomena underlying the damage buildup under irradiation. Here in the present work, we show, using x-ray diffraction, that these two materials exhibit a similar damage accumulation process under ion irradiation at fixed temperature. However, they display an unexpected opposite damaging rate to changes in the irradiation temperature. In fact, as the temperature is increased, the final damage state is reached earlier in c- ZrO 2 while it is delayed in MgO. Rate equation cluster dynamics simulations show that defect clustering is favored over defect recombination in c- ZrO 2 , but the situation is reversed for MgO, explaining the observed opposite response to temperature of the two materials. This contrasting behavior can be rationalized in terms of nonequivalent interstitial versus vacancy defect migration energies in MgO. We finally demonstrate that these results allow for a qualitative prediction of the evolution of the experimental irradiation-induced disorder with temperature, henceforth potentially reducing the cost in selecting and developing ad hoc materials.

36 MATERIALS SCIENCE↗

Mechanisms of Enhanced Thermal Stability of Polarization in Lead-Free (Bi 1/2 Na 1/2 ) 0.94 Ba 0.06 TiO 3 /ZnO Ceramic Composites

(Bi 1/2 Na 1/2 )TiO 3 -based solid solutions, one of the major systems of lead-free piezoelectric ceramics, exhibit a low thermal depolarization temperature ( T d ~100°C). It was reported that by incorporating 30 mol% ZnO particles to form a ceramic composite of (Bi 1/2 Na 1/2 ) 0.94 Ba 0.06 TiO 3 /ZnO, the depolarization process can be shifted up to ~250 °C. In the present work, a variety of advanced transmission electron microscopy techniques, including in situ heating, annular bright-field, high-angle annular dark-field, geometric phase analysis, energy-dispersive spectrum and electron energy-loss spectroscopy, are employed to investigate the underlying mechanisms for the enhanced thermal stability of polarization in the composite. Furthermore, it is found that the abrupt depolarization in (Bi 1/2 Na 1/2 ) 0.94 Ba 0.06 TiO 3 at T d becomes diffused over a wide temperature window up to the temperature at maximum dielectric constant ( T m ) under the combined actions of the incorporation of Zn into the perovskite lattice, the presence of residual stresses, and the pinning effect on micron-sized domains provided by ZnO particles.

36 MATERIALS SCIENCE↗

Increasing Multilayer Ceramic Capacitor Lifetime With Bipolar Voltage Cycling

Enhancing the lifetime of multilayer ceramic capacitors (MLCCs) is critical in many aerospace, naval, or electrical grid applications, where device failure could lead to catastrophic consequences. The migration of oxygen vacancies from the ceramic to the electrode interface under constant bias is known to reduce the lifetime of oxide-based MLCCs. Bias cycling presents an opportunity to enhance MLCC lifetime by reducing oxygen vacancy migration. The ideal frequency range is expected to lie between frequencies low enough to avoid self-heating but high enough to avoid interfacial defect formation. However, the impact of low-frequency bipolar voltage cycling (BVC) on MLCC degradation mechanisms has not been well studied. This work investigates the impact of periodic BVC on the degradation of MLCCs through highly accelerated lifetime testing (HALT) on X7R capacitors. HALT tests were conducted at 255 °C and 60 V using different switching frequencies: 0 (dc), 0.1, 2.5, and 10 Hz. BVC was found to improve the lifetime of MLCCs compared to dc test conditions. MLCCs tested at 10-Hz BVC showed a 311% increase in average time to failure compared to the dc case. Impedance spectroscopy shows that BVC decreases the rate of resistance degradation within MLCCs, indicating that oxygen vacancy migration to the electrodes is mitigated. The impedance spectra taken on BVC samples highlight how grain boundaries play a vital role in trapping oxygen vacancies. Periodic cycling causes oxygen vacancies to become trapped at grain boundaries, resulting in oxygen vacancies taking longer to reach the electrode interface and thus increasing MLCC lifetime. This work highlights not only how BVC can be used to increase MLCC lifetime but also how periodically cycling MLCCs could increase lifetime in extreme environments, such as at elevated temperatures and electric fields.

Chuong, Kayla Y.↗

Torsional Shear Strength Tests for Glass-Ceramic Joined Silicon Carbide

A torsion test on hour-glass-shaped samples with a full joined or a ring-shaped joined area was chosen in this study to measure shear strength of glass-ceramic joined silicon carbide. Shear strength of about 100 MPa was measured for full joined SiC with fracture completely inside their joined area. Attempts to obtain this shear strength with a ring-shaped joined area failed due to mixed mode fractures. However, full joined and ring-shaped steel hour-glasses joined by a glass-ceramic gave the same shear strength, thus suggesting that this test measures shear strength of joined components only when their fracture is completely inside their joined area.

36 MATERIALS SCIENCE↗

The Uniaxial Tensile Response of Porous and Microcracked Ceramic Materials

The uniaxial tensile stress-strain behavior of three porous ceramic materials was determined at ambient conditions. Test specimens in the form of thin beams were obtained from the walls of diesel particulate filter honeycombs and tested using a microtesting system. A digital image correlation technique was used to obtain full-field 2D in-plane surface displacement maps during tensile loading, and in turn, the 2D strains obtained from displacement fields were used to determine the Secant modulus, Young s modulus and initial Poisson s ratio of the three porous ceramic materials. Successive unloading-reloading experiments were performed at different levels of stress to decouple the linear elastic, anelastic and inelastic response in these materials. It was found that the stress-strain response of these materials was non-linear and that the degree of nonlinearity is related to the initial microcrack density and evolution of damage in the material.

anelasticity↗

Scalable measurements of tow architecture variability in braided ceramic composite tubes

Abstract The performance of braided ceramic matrix composites has been shown to depend on the spatial arrangement of tows; therefore, a new class of tools is required to measure irregularities in the composite architecture for components with intricate geometries. We report a scalable and robust reconstruction technique built upon stereoscopic digital image correlation that is able to efficiently measure the position of tows in arbitrarily shaped composites. This method was applied to triaxially braided ceramic matrix composite tubes intended for use as nuclear fuel cladding, which revealed both long‐range “systematic” tow packing defects associated with the manufacturing process and short‐range “intrinsic” defects due to the braid architecture. These findings suggested that the character of tow spacing variation in braided composite tubes was substantially more complex than in planar woven composites. These measurements are expected to lead to improved processing of braided composites and to facilitate the design of statistically representative virtual specimens for finite element modeling.

Heim, Frederick M.↗

Solid-State Sintering of Core-Shell Ceramic Powders Fabricated by Particle Atomic Layer Deposition

The properties of technical ceramics are highly dependent on their microstructure, which evolves during sintering. Sintering is the process by which ceramic parts are subjected to high temperatures to activate chemical diffusion and the consumption of porosity. During the initial stage of sintering, interparticle necks between neighboring particles form and subsequently increase in size, consuming porosity as the particle centers move closer together. To experimentally determine how this process depends on particle surface composition, particle atomic layer deposition (ALD) was used to deposit a thin film of amorphous aluminum oxide (Al2O3) onto yttria-stabilized tetragonal zirconia (3YSZ) particles, producing core-shell structured powders. The uniformity of the Al2O3 film was confirmed with transmission electron microscopy and energy dispersive spectroscopy. Scanning electron microscopy was used to observe microstructural evolution during sintering, and the dihedral angles of Al2O3 and 3YSZ grains were measured to determine the ratio of interfacial energies between the 3YSZ|3YSZ, 3YSZ|Al2O3, and Al2O3|Al2O3 interfaces. Analysis of the densification kinetics revealed that the initial stage of densification is dependent on the material at the surface of the particles (ie, the Al2O3 film) and is controlled by the diffusion of Al3+ cations through Al2O3. Once the Al2O3 film has coalesced, the sintering behavior is controlled by the densification of the core material (3YSZ). Thus, core-shell powders fabricated by particle ALD sinter by a two-step process where the kinetics are dependent on the material present at interparticle contacts.

alumina↗